Contents

Gold is characterized chemically by an

extreme indifference to the action of all
bodies usually met with in nature.
- T.K. Rose and W.A.C. Newman, 1937

Chapter I I. Chemistry, mineralogy and geochemistry of gold

General chemistry and Pt (Group VIII) and the corresponding elements of

Gold, Au: atomic no. 79; atomic wt. 196.967; specific Group IB, namely Cu, Ag and Au. Thus, platinum has only
gravity 19.32 (20°C); melting point 1063.0°C; va- one electron less than gold, and since the energy differences
lence 1,3. are small in the klectronic constitution of the two elements,
Comprehensive reviews of the chemistry and physical metal- the differences in the chemical behaviour of the two elements
lurgy of gold are contained in the works by Mellor (1923), in a few respects are slight. In natural environments, however,
Rose and Newman (1937), Gmelin (1950), Sidgwick (1950), there is no close relationship between gold and platinum
Pascal (1957), Emery and Leddicotte (1961), Badone and except that they tend to occur in the native state, and some
Spence (1961), Pourbaix et al. (1963), Johnson and Davis platinum may be present in certain varieties of native gold
(1973) and Myerscough (1973). The summary that follows and vice versa. There are no particular similarities between
deals principally with the chemical features of gold as they gold and mercury, the corresponding element in Group IIB of
affect the geochemistry of the element. the periodic system. As is well known, however, gold and
Gold is a member of Group IB of the periodic system, mercury form an amalgam, and well-defined compounds
which includes copper (Cu), silver (Ag), and gold (Au). Except occur in the system Au-Hg; natural amalgam is known, but
that the so-called 'coinage metals' exhibit monovalency (ox- formal Au-Hg compounds do not appear to occur in nature,
+
idation state l), there is little resemblance to the alkali or if they do they have not been adequately characterized.
metals of Group IA. In fact, the differences between the two There are marked differences in the chemistry of silver and
subgroups are marked, as shown for instance by the general gold, a consequence that is attributable to the diminishing
decrease in reactivity of the Group IB elements with increase effect of the lanthanide contraction between atomic numbers
in atomic number as contrasted with the reverse behaviour of 57 (La) and 79 (Au).
the Group IA elements. As might be expected from electron Gold is considered by some to be a transition element of
orbital considerations, there is some similarity between Ni, Pd the third series, although it does not fulfil the necessary

Table 1. Energetic properties of copper, silver and gold

Property copper Silver Gold
Outer electron configuration 3&04s1 W05s1 5&06s1
Oxidation states (valence)
(Those in brackets are uncommon) 1,2, (3)
Electronegativity 1.9
Ionization potential, eV Cu(1) 7.724
Cu(II)20.29
Lattice energy coefficient Cu(1) 215
cum630
Atomic radius, A 1.40 (8)
(co-ordinationin brackets) 1.44 (12)
Ionic radius, A Au(1) 1.37
(co-ordination in brackets) Au(1) 1.37
Au(II1) 0.78 (4) sq.
Au(II1) 0.91 (6)
Miscellaneous radii, A Cu(1) (in fluorides) 1.00 Ag(1) (in fluoride) 1.33 Au(1) (hydrated) 1.4
Cu(1) (in oxides) 1.05 Ag(1) (in oxides) 1.35
Cu(I1) (in fluorides) 0.87 Ag (tetrahedral covalent) 1.53
Cu(I1) (in oxides) 0.97 Ag(1) (hydrated) 1.7
Cu (tetrahedral covalent) 1.35
Cu(1) (hydrated) 1.7
Cu(I1) (hydrated) 3.5
1onic cu(I) 1.00 &(I) 0.88 Au(1) 0.73
Cu(I1) 2.44 Au(II1) 3.30
Sources: Szideaky-Kardoss (1958); Green (1959); Sarnsonov (1968); Whittaker and Muntus (1970).
Note: The values given for the various radii are approximations at best. Those chosen appear to be the most satisfactory from the viewpoint of the geochemistry of
gold, but as is well known all radii should be used with caution, since the radius of an element varies widely depending on the structure of the substance
containing the element, the co-ordination configurationof the element and other factors.
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

electronic wnditions16 that characterize transition dements. Table 2. Thermodynamic d a t a o n gold

Gold is a soft, yellow metal with a moderately high melting Formula State AH0 AFO So
point (1063.0°C) and a high electrical and thermal conductivi- Au (metal) c 0.0 0.0 11.32
ty exceeded only among the elements by silver and copper. It Au(I) a'l 39.0
is the most malleable and ductile of metals; 1 oz of gold can Au (111) a‘l 103.6
be beaten into foil some 300 ft2 in area. Of all the elements, A"203 C 39.0
H,AuO; 45.8
gold in its pure state is undoubtedly the most beautiful, HAuOi- a‘l -27.6
especially when it occurs in crystalline groupings or in AuOi- a‘l -5.8
dendritic and arborescent arrangements. Au(OH), c -100.0 -69.3 29.0
The energetic properties of gold, together with those of Au(OH), aq -61.8
AuCl c -8.4 4.2 (24.)*
copper and silver, the two elements with which it is so often AuC1, c -28.3 -1 1.6 (35.)
associated in natwe, are given in Table 1. The thermodynamic AuC1;2H2O c -167.7 -123.3 (54.)
properties of the element, its ions and compounds are given in AuCl, a'l -77.8 -56.2 61.
Table 2. The Pourbaix (Eh-pH) diagrams for some of the AuBr c 4.4 -3.7 (27.)
AuBr; a'l -27.1
common gold species are shown in Figure 1, and the cycle of AuBr, c -13.0 -5.9 (24.)
gold interconversions under natural conditions is displayed in AuBr, aq -9.2
Figure 2. Additional data can be found in the publications by AuBr; a‘l 45.5 -38.1 75.
Kelley (1960), Wicks and Block (1963), Sillkn and Martell AuI c 0.2 -0.76 (28.5)
(1964), Samsonov (1968), Gedansky and Hepler (1969), Han- A"zP3 C -24.1
Au(CN); a'l 58.4 64.4 29.5
cock and Finkelstein (1971), Finkelstein and Hancock (1974), Au(CNS); a‘l 57.7
and Kubaschewski and von Goldbeck (1975). The vapour Au(CNS); a'l 130.1
pressure of gold has been recently discussed in detail by Paule Sources: Latimer (1952); Handbook of chemistry and physics, 53rd ed.; Chemi-
and Mandel(1972). The vapour presswe of the gold standard cal Rubber Co., Cleveland, Ohio, 1972.
Notes: AHo- the standard heat of formation in kilocalories of the substance or
is 9.92 X atm at 1300°K increasing to 1.87 X lo-, atm ion from its elements at 25'C
- - -~

at 2100°K. The heat of sublimation of gold is given as 87 720 AFo - the standard free energy of formation in kilocalories of the
k 210 cal/mole at 298OK; the corresponding value for silver substance from its elements at 25OC
So- the entropy of the substance or ion in cal/degree in its thermody-
namic reference state at the reference temperature of 25'C
c - crystalline
16Strictly speaking, the transition elements are characterized by a n aq - in aqueous solutions
inner d or f level, which is not filled to capacity, e.g., nickel. In gold
*Values in parentheses are estimated
the 5d orbital is completely filled.

GSC
Figure 1 Pourbaix (Eh-pH) diagrams for gold. (a) System Au-H,O at 25OC and 1 atm total pressure; concentrations of all gold species
10-'M. (b) System Au-H,O-CI at 25OC and 1 atm total pressure; concentration of Au(lll) = 10-,M, C1- = 2M. (c) System Au-S at 25OC and
1 atm total pressure; concentration of all sulphur species = 10-'M. [Solid species are shown in bold type, dissolved species in lighter type.
For details of the thermodynamics of the solution chemistry of gold see the works by Latimer (1 952). Pourba~xet a/. (1963). Tyurin
(1 9656). Garrels and Christ (1 965). Goleva e t a / . (1 9706). Hancock and Finkelstein (1 9 7 1) and Finkelstein and Hancock (1 974).]
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

ZEROVALENT Au
occurs in nature as
native gold and in
certain metallic alloys
such as electrum (Au, Ag);
also probably present
Immobile forms: in various tellurides and Immobile forms:
Natural aurous compounds aurostibite,AuSb2.All Natural auric compounds
are unknown. Aurous these may be mobile in are unknown. Auric
complexes may exist as the colloidal (sol) and complexes may exist as
adsorbates on hydrous finely dispersed forms; adsorbates on hydrous
iron and manganese oxide- more generally, however, iron and manganese oxide-
rich gels and on various Au(0) is immobile. rich gels and on various
types of organic matter types of organic matter
such as peat, gyttja, such as peat, gyttja,
humus, etc. humus, etc.

TRIVALENT Au
MONOVALENT Au only anionic forms
only anionic forms prevail as in the
prevail as in the auric complexes
aurous complexes

Mobile forms:
Mobile forms: essentially as soluble
essentially as soluble and/or adsorbed auric
and/or adsorbed aurous complexes of both
complexes of both inorganic and organic
inorganic and organic (humic) derivation; also
(humic) derivation; also as adsorbed forms on
as adsorbed forms on natural inorganic and
natural inorganic and organic (humic) colloids;
organic (humic) colloids; in petroleum
in petroleum

Figure 2. Cycle of gold interconversionsin nature.

is 68 010 2 300 cal/mole. These figures are of interest in telluric and sulphuric or phosphoric acid, readily in sulphuric
natural systems in that they indicate that silver is the more and hydrochloric acid solutions containing an oxidizing agent
mobile of the two elements at high temperatures. such as MnO,, and sparingly in alkali thiosulphate solutions.
Gold is usually found in one of three oxidation states: 0 The element is probably sparingly soluble in solutions con-
+
(native), 1 (aurous) and + 3 (auric) designated further as taining HCl and CuCl, in the presence of an oxidizing agent;
Au, Au(1) and Au(II1) in this volume. Au(I1) and Au(V) states also sparingly soluble in femc chloride and femc sulphate
are also known to occur in certain complex arrangments solutions containing an oxidizer. Finely divided gold is said by
(Bergendahl, 1975). These appear to be relatively unstable some investigations to be slightly soluble in alkali hydroxides.
states and probably do not occur in nature, except possibly in These and other reactions are discussed in the sections on
some organic-rich or chloride-rich natural waters. Gold in the natural waters, soils and oxidation processes in gold-bearing
native state is the most noble of metals. It is chemically deposits. Mercury dissolves or amalgamates about 0.7 per cent
unreactive and is not affected by water or most acids, nor by weight of gold at 25OC, and molten tellurium forms an
attacked by oxygen or sulphur. The halogens react readily intermetallic compound with the element.
with gold as do also solutions that generate them such as aqua Crystallographically gold belongs to a group that includes
regia. Gold dissolves readily in alkali cyanide solutions in the gold, silver, copper and lead. All of these metals are isometric,
presence of air, sparingly in alkali sulphide solutions, readily hexoctahedral - 4/m 5 2/m - and have the copper-type
in selenic acid at about 225OC, readily in solutions containing structure with the atoms lying at the points of a face-centred
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

cubic lattice. This structure conforms to the space group Fm transitory (catalytic) existence of Au(I1) in redox reactions
3m, and the unit cell contains 4 atoms. The cell edges for the involving Fe2+is discussed by Rich and Taube (1954).
four pure metals are as follows: The aqueous chemistry of gold is essentially that of
complex ions since the ions Au" and Au+, are unstable in
water because of their high oxidation potentials (Fig. 1). Both
The atomic radius of gold is identical to that of silver Au(I), rPO,and Au(III), 8,are B-type metal ions, which means
(1.44,&),a feature that permits a continuous alloy series with a that the stability of their complexes tend to decrease with
minimum cell edge at about 20 per cent silver. In nature, increasing electronegativity of the ligand donor atom. Thus,
however, the series appears to be discontinuous. There is the stability order for the halogen complexes is
much less si@larity in the atomic radii of gold (1.44A) and I- >Br->C1- >F- where the order of electronegativities is
copper (1.28& and as a consequence most samples of native F- >C1- >Br- >I-. Similarly the stability of the various
gold contain relatively small amounts of copper (up to 20% complexes with the donor atoms in Groups VA and VIA fall
Cu). Native copper, likewise, usually contains only traces of in the order Bi>Sb>As>P and Te>Se>S>O. This ex-
gold. In the laboratory gold forms alloys with a large number plains why gold tellurides, gold bismuthide and the antimo-
of metals, among which the most important are Ag, Cu, Al, nide (aurostibite) are stable enough to occur as minerals
Cd, Hg, Co, Pb, Fe, Ni, Pd, Pt, Sn, Ga, Ca, In and Zn. Some whereas we do not find natural gold selenides (sensu strictu),
of these elements, such as Ag, Cu, Ni, Pd and Pt, are miscible sulphides, oxides and arsenides. Nevertheless there is a bond
with gold in all proportions. Details of these alloys are given between gold and selenium and arsenic since the precious
by Badone and Spence (1961), Wise (1964), and Raynor metal is often enriched in deposits containing abundant
(1976). Natural gold invariably contains some of the elements selenides, arsenides and their oxidized derivatives. Smirnov
noted above, particularly Ag, Cu, Al, Fe, Bi, Sn, Pb, Zn, Pd and Entin (1975) have also noted a bond between gold and
and Pt. The colour of natural gold alloys is largely dominated phosphorus in genetically diverse phosphatic deposits.
by silver. With increasing content of silver the golden colour is Au(1) generally exhibits linear twofold co-ordination,
attenuated until at about 65 per cent silver the colour of the although tetrahedral fourfold co-ordination is also observed in
alloy is barely distinguishable from pure silver. some aurous substances. Most aurous compounds that are not
The effect of mercury on gold has been known for complexes are insoluble with the exception of AuCN. Aurous
centuries. It is usually said that mercury 'dissolves' gold, but oxide, Au20, and aurous hydroxide, AuOH, are mentioned in
this is an error that has crept into the literature and has been the literature, but recent research throws some doubt on their
repeated for many years (Brown, 1960). In actual fact the existence. Aurous chloride, AuC1, aurous bromide, AuBr, and
solubility of gold in mercury is slight, only 0.13 atomic per aurous iodide, AuI, can be prepared. The chloride slowly
cent at 20°C. The amalgamating effect of mercury is essential- disproportionates in water to yield metallic gold and auric
ly the result of mechanical mixing, wetting and surface chloride. The bromide and iodide behave in a similar manner,
reactions between gold and mercury, about which we know although not as rapidly. Aurous fluoride has not been pre-
little. On the other hand gold forms an alloy with mercury, the pared, probably because it is unstable in the presence of
maximum solid solubility of Hg in Au being approximately 35 water. Aurous chloride dissolves in alkali chloride solutions to
atomic per cent. At least three artificial gold-mercury com- form the chloroaurite (I) complex ion [AuCl,]-. Aurous
pounds are known in the system Au-Hg - Au3Hg, a second bromide and iodide behave in a similar manner in solutions
compound somewhat richer in gold than Au3Hg and an containing an excess of bromide or iodide. Aurous cyanide,
indefinite compound near the composition Au2Hg (Rolfe and AuCN, can be easily prepared. It dissolves in alkali cyanide
Hume-Rothery, 1967; Berndt and Cummins, 1970). Lindahl solutions to form the aurous cyanide complex [Au(CN),]-.
(1970) also synthesized a phase Au,Hg, at 25 and 80°C. Other Aurous sulphide, Au2S, is the most stable of the sulphides of
phases, such as AuHg,, Au2Hg, and Au,Hg,, also seem to be the element. It is insoluble in water (Ksp = < lo-',) but may
stable in the system Au-Hg (Shklyar and Kakovskii, 1972). A form a colloid; it is insoluble in most acids, soluble in strong
compound close to Au,Hg, and called gold amalgam occurs in oxidizing agents such as aqua regia, soluble in alkali cyanide
nature. Its structure and composition require further work. solutions, and soluble in alkali polysulphide solutions to give
In its compounds gold as Au(1) (aurous) and Au(II1) thioaurite(1) compounds of the type Na[AuS]. Aurous polysul-
(auric) has the electronic configuration of dl0-type and phides characterized as Na,[Au,S,], K,[AuS2] and KJAuS,]
@-type respectively and exhibits mainly a covalent character are obtained by the action of polysulphide solutions on aurous
because of the high ionization potentials of the two states of sulphide and other aurous and auric compounds in solution.
oxidation. This is particularly so in its natural compounds These polysulphides are slightly soluble in water. Acidification
such as the tellurides and the antimonide, AuSb, (aurostibite). of a solution containing thioaurite(1) compounds or aurous
There once was some slight evidence for the existence of polysulphides yields aurous sulphide. Treatment of an acidi-
Au(I1) in certain gold-organic complexes, and compounds fied solution of K[Au(CN),] with hydrogen sulphide, like-
with empirical compositions such as AuS and AUCI, might wise, throws down Au,S. Aurous thiosulphates of the type
suggest a (11) oxidation state. It is, however, now generally NaAu(S20,)] can be prepared, but they are not as stable as
agreed that compounds such as AuS wntain equal numbers of the fourfold complex Na,[Au(S,O,),]. Aurous thiosulphate is
Au(1) and Au(II1) species and should be characterized as very soluble in water giving complex ions of the type
mixed compounds written as AU(I)~S.AU(III)~S,. The com- [Au(S,O,)]- and [Au(S,O,),P-. The later complex is apparently
pound Cs,Au,Cl, also appears to wntain gold in both the (I) of the open chain type commonly written as [O,S&Au-
and (111) states rather than in the (11) state. The possible S.S0,I3-. By loss of sulphur, complex sulphites of the form
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

[O,S-Au-SOJ- are derived. Oxy-salts of gold(1) are uncom- al. (1976). Two compounds occur in the system - AuCl and
mon. There is no simple carbonate or nitrate, and the Au,Cl,.
existence of a sulphate is doubtful. The gold(1) thiocyanate, Gold(II1) salts of oxyanions are not particularly stable,
AuSCN, can be prepared. It is highly insoluble in water. but solutions containing complex auric nitrates, sulphates,
summarizing, we observe that gold(1) is characterized by etc., e.g. [Au(NO,),]-, [Au(SO,),]- can be prepared. Gold
numerous wmplexes that are stable in aqueous solution. Most selenate, Au,(SeO,),, and gold selenite, Au,(SeO,),, are rela-
of these are monomeric in character, familiar examples being tively stable.
[AuCl,]-, [Au(CN),]- and [Au(S,O,)]-. Crystalline compounds Gold(II1) cyanides of the type K[Au(CN),]-xH,O are
of the type K[Au(CN),] can be obtained, and the acid known. In solutions containing excess cyanide they are said to
H[Au(CN),] can be isolated. Numerous complexes of Au(1) form the various complex ions [Au(CN),]-, [Au(CN)J- and
with substituted sulphur, arsenic and antimony ligands are [Au(CN),I3-. Gold(II1) thiocyanates are known; the most
also known. Some of these such as [AuSI-, [AuS,I3-, [Au,S3I4-, common of these K[Au(SCN),] is insoluble in water.
[AuSbIZ-and the thioarienito and thioantimonito complexes, Gold(II1) sulphide, Au,S,, can be prepared by the action
of the type [AU(ASS,)]~-and [Au(SbS3)y-, are probably of of H,S on auric salts, but it is readily reduced in water,
great importance in the transport of gold in endogenic yielding Au,S and sulphur. It is soluble in alkali sulphide and
processes in nature. polysulphide solutions to give thioaurate(II1) compounds, but
Gold(1) also forms a number of organometallic com- these are unstable and degrade to the more stable thioaurite(1)
pounds (alkyls, aryls, olefins, etc.) and chelates, but these are species.
much too numerous and complicated to be discussed here. Gold(II1) forms numerous inorganic complexes, some of
The interested reader should cor~sultthe summary by Johnson which have been mentioned above. Most of these are anionic
and Davis (1973) and the specialized reviews by Jack and wmplexes. Relatively little is known about soluble cationic
Powell (1972), Nesmeyanov et al. (1974) and Johnson (1976). and neutral gold complexes but Benel (1967) and Benel and
The organometallic aurous compounds are as a rule not as Riedel (1967) consider that in strongly acid chloride solutions
stable as the corresponding auric compounds. Some of the gold exists prevailingly in the form of undissociated HAuCl,.
aurous organometallic compounds such as the phosphine, With increasing pH, hydrolysis occurs with the formation of
arsine, mercaptide and methylated wmplexes and chelates, positively charged hydrolytic products (pseudocolloids).
may occur in natural settings, especially those rich in humus; Gold(II1) also forms a host of organometallic compounds and
none of these compounds have, however, been characterized. chelates that are too numerous and complicated to be dis-
Gold(II1) commonly exhibits fourfold planar co-ordina- cussed here. They are reviewed by Jack and Powell (1972),
tion, although higher co-ordination numbers, fivefold trigonal Johnson and Davies (1973) and Nesmeyanov et al. (1974).
bipyramidal and sixfold octahedral, are possible. Some of the Some of these compounds and complexes may be of impor-
complexes of Au(II1) are isomorphous with those of Cu(II1) tance in the geochemistry of gold in organic (humic) environ-
and Ag(II1). Most of the auric compounds are powerful ments, but as yet none have been characterized.
oxidizing agents. Gold(II1) hydroxide, Au(OH), is obtained by Gold forms a large number of complex compounds in
the addition of alkali hydroxide to solutions containing which the state of oxidation of the element is multiple or
chloroaurate ion, [AuCl,]-. The hydroxide is probably not a uncertain. Reference to the sulphide AuS has already been
true hydroxide but rather a hydrated acid hydrate of some made; it appears to be a compound of Au,S and Au,S,. The
form. The hydroxide can be dehydrated to give auric acid salt, Na[AuS].H,O, has been isolated. There are a number of
AuO(0H) and ultimately the oxide Aq0,. Both these oxides complex double sulphides, including Ag,AuS,, AgAuS and
have amphoteric properties; in acidic solutions they give Ag,AuS,; a number of tellurides; two selenides AuSe and
complexes of the type [AuCl,]- and [Au(SO,),]-, and in basic Au,Se,; seleno-tellurides of the type Au,SeTe; and mixed
solutions wmplexes characterized as [Au(OH)d]- or [AuOlI-, selenides and tellurides of the types Ag3AuSe, and Ag,AuTe,;
are stable. The last two are commonly referred to as aurate various telluride halides of the type AuXle, (where X = C1,
complexes, the corresponding salts such as, KAu0,-3H,O, Br, I) are also known (Rabenau et a/., 1970). Of all these
being designated aurates. Gold(II1) hydroxide when treated artificial compounds only the tellurides and the silver-gold
with-strong alkalies yields another series of aurates character- selenide are known in nature; some of the double sulphides
ized by the ion Au0,3-; salts such as Na,HAuO, and would seem to be stable enough to persist in nature and may
Na,AuO, have been prepared. occur as minerals. One of these, the double sulphide, Ag,AuS,,
Gold(II1) forms compounds with all of the halides. Auric uytenbogaardtite has recently been described. The antimo-
fluoride is not stable in water and is rapidly decomposed. The nide, AuSb,, occurs in nature as aurostibite and the silver-gold
chemistry of the chloride, bromide and iodide is similar. Auric selenide, Ag,AuSe,, as fischesserite. The arsenide is unknown
chloride and bromide are soluble in water, in which they are as a natural mineral, and as far as the writer can ascertain it
partly hydrolyzed to give species such as [AuCl,OH]-; excess has not been synthesized.
chloride or bromide ion yields the complex chloraurate or Gold has a marked affinity for the elements tellurium and
bromoaurate ions, [AuCl,]-, [AuBr,]-. Chloroauric acid, bismuth and less so for antimony. The reason for this is
HAuCl4.4H,O and the corresponding bromine compound can obviously that the various combinations Au-Te, etc. give a
be isolated, and well defined salts such as KAuCl, and particularly stable electronic configuration. The atoms of Te,
Ca(AuCl,), are known. The stability of the auric halide Bi and Sb have large radii, and this was noted by Goldschmidt
complexes increases in the order I >Br >Cl> F. The phase (1954) who sought to explain the affinity of gold with these
diagram of the gold-chlorine system is discussed by Janssen et elements as due to their ability to form packings such that
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THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

gold could be collected (captured) in their interstices. The distribution curve are determined by the amount of gold, the
phenomena are, however, mainly connected with the elec- nucleation process and the law of growth.
tronegativity of the donor atoms of the complexes as discussed The possible role of gold colloids in the migration of gold
above. There are a number of gold tellurides in nature, a in nature is discussed in a subsequent section.
poorly differentiated bismuthide and an antimonide. Numer- Table 3 lists the solubility constants of some of the
ous artificial Au-Sb compounds are known (Muller, 1974). common salts and other compounds of gold likely to be
Gold does not form a selenide (sensu strictu) in nature, but as encountered in nature.
noted above there is a silver-gold selenide (fischesserite) that
occurs in places (vide infra). The various phases in the system
gold-bismuth-tellurium have been investigated by Gather and Isotopes
Blacknik (1974).
Gold in solution is readily reduced to the metal by nearly Natural gold consists of only one isotope, lg7Au7,,whose half
all of the metals and metallic ions and by numerous com- life is estimated to be greater than 3 X 1016years (Strominger
pound substances. Of interest in this respect in natural et al. 1958). Some 20 artificial radiosotopes are known; all
environments are the ions Fe2+and Mn2+and a great variety have short half-lives, none exceeding 185 days. Mauer and
of organic compounds including citric and acetic acid and Pose (1943) found no evidence of natural fission in gold and
their salts. This feature of the chemistry of gold is discussed in concluded that the half-life for the process is longer than 2 X
more detail in the sections on soils and natural waters and in 1015years.
the chapter on the oxidation of gold-bearing deposits.
Gold forms a colloid readily when a dilute gold solution
is reduced. The particle size is apparently determined by the Abundance and geochemical character: gold in
concentration, temperature and pH. A low pH favours large meteorites. tektites and lunar materials
particles whereas a high pH yields small particles. old The cosmic abundance of gold as given by Green (1959) from
colloids are hydrophobic and generally carry a negative the data of Suess and Urey (1956) is 0.000534 ppm or 0.145
charge. In a recent study Turkevich et al. (1951) have shown atom of Au per lo6 Si atoms. More recent estimated cosmic
that in the formation of gold colloids nucleating agents can be abundances of gold as given by Cameron (1959), Clayton and
identified with reducing agents which form a mixed polymer Fowler (1961), Baedecker and Ehmann (1965) and Cameron
with chlorauric ion before the reduction to the gold nucleus
(1968) are respectively 0.145, 0.13, 0.18 and 0.20 atom of Au
takes place. They also showed that the law of growth of the
per lo6 Si atoms. These values can be compared with the
gold colloids is exponential. The average size, the deviation corresponding value for silver - 0.5 - as given by Cameron
from the average size and the character of the particle size (1968). Ehmann and Gillum (1972) give the cosmic atomic
Table 3. Solubility of some gold compounds abundance of gold as 0.19 (Si = lo6 atoms); that for platinum
Compound Solubility in water, Solubility in other on the same basis is 1.37 giving an Au/Pt atom ratio for the
g/ 100cc (25°C) reagents primitive solar nebula equal to 0.14.
Insoluble Soluble in aqua regia, Gold is a trace constituent of meteorites, its abundance in
KCN, hot H2S0,; the various types of these objects having a considerable range
insoluble in acids and as shown in Table 4. The iron metwrites (siderites) and the
alkalies metal phase of chondrites have the highest gold contents
AuBr Insoluble Dissociates in acids;
soluble in NaCN indicating the marked siderophilic character of gold. The gold
AuBr, Slightly soluble content of the silicate phases of meteorites is low whereas the
AuCl Very slightly soluble Soluble in HCl, HBr sulphide (troilite) phase is relatively high, indicating respec-
AuCl, 68 tively a general poor lithophile tendency and a relatively high
AuCN Very slightly soluble Soluble in KCN,
NH,OH; insoluble in chalcophile habit for gold.
alkalies In the chondrites the Au/Ag ratio is consistently around
HAu(CN,).3H20 Very soluble 1, whereas in the siderites the average ratio is extremely high,
AuI Very slightly soluble Soluble in KI at 40 or more. The ratio in the sulphide (troilite) phase is of
AuI. Insoluble Soluble in iodides the order of 0.05 if the available analyses for silver are
Soluble, dissociates Soluble in HNO,
Insoluble Soluble HCl, reasonably correct. All these data indicate a weak siderophile
concentrated HNO,, character and a marked chalcophile nature for silver com-
NaCN pared with gold, features that are well known to all chemists.
5.7 x 10-l1 Soluble HCl, NaCN, Some of the correlations of gold with other elements in
concentrated HNO, meteorites are of interest. There is a reasonable correlation
Insoluble Insoluble in HCl,
dilute HNO, between nickel, cobalt and gold in some chondrites and
Insoluble siderites according to the data presented by Goldberg et al.
Insoluble Soluble aqua regia, (1951) and Vinogradov et al. (1973). Linn and Moore (1968),
KCN; insoluble in on the other hand, found that the positive correlation of gold
acids
Insoluble Soluble in Na2S concentrations in relation to nickel and to cobalt was not
Insoluble pronounced in their data on iron meteorites. The correlation
Source: Handbook of chemistry and physics, 53rd ed.; Chemical Rubber Co., between gold and iron is not marked in the data on meteor-
Cleveland, Ohio. 1972. ites, although some investigators have observed a positive

14
 Contents

Table 4. Gold and silver contents of meteorites, tektites and the moon*
Type of meteorite, etc. Element N:r,"ifzf Range @ Ss G,
-
XgS SgS

Chondrites (world)

Chondrites,
Abeet
Bentont
Holman Island?
Chondrites, metal
phase (world)
Chondrites, nonmetal
(silicate) phase (world)
Achondrites (world)
Siderolites (50% iron,
50% silicate) (world)
Siderites (irons) (world)

Siderites
Annaheimt

Troilite (sulphide phase)

(world)

Tektites (world)

Lunar rocks and soils

Lunar rocks

Lunar soils and fines

Lunar metal grains

AU/A~ 21.003 10.599
* Sources of information: see the Selected bibliography. Doubtfully high values for gold and silver have been excluded from some of the published data. For details
of individual meteorites and bibliographies on meteoritessee Mason (1962). Middlehurst and Kuiper (1963), Hey (1966), Mason (1971) and Ramdohr (1973). For
information on most of the lunar samples see the volumes containing the papers delivered at the Ist, 2nd. 3rd, 4th and 5th Lunar Science conferences held at
Houston Texas.
t Analyses done in the Geological Survey of Canada laboratories by precise chemical methods (analyst, J.G. Sen Gupta). (For descriptions of the meteorites see
Geol. Sum. Can., Pap. 70-66.)
$ Estimated value.
§ In this and subsequent tables %, is the arithmetic mean; S, the standard deviation; G, the geometric mean; and R g and Sg are respectively the mean and standard
deviation of the data expressed in log,, units.

correlation in some varieties of meteorites; for instance per cent confidence level. Hintenberger et al. (1973) observed
Ehmann et a/. (1970) found such a correlation with the total an antipathetic correlation between gold and mercury in some
iron content in enstatite chondrites. The relationship of gold Antarctic meteorites. Foucht and Smales (1966) noted a
with the various platinoids appears to be rather erratic judging strong correlation between gold and arsenic in iron meteorites
from the overall available data, although Ehmann and Gillum and a weak correlation between gold and antimony. Both
(1972) found a positive correlation for platinum and gold these correlations extend to terrestrial materials as we shall see
within each major chondrite group they investigated. The later. Similar correlation features were noted for gold, arsenic
correlation coefficient was 0.70 which is significant at the 99.9 and antimony in chondritic meteorites by Foucht and Smales
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

(1967). Other correlations and relationships of gold in meteor- sedimentary rocks the range was 0.00179 to 0.00457 ppm. The
ites are briefly commented on by Ehmann (1971). writer estimates the terrestrial abundance of gold and silver to
A number of investigators have suggested that an approx- be respectively 0.005 and 0.05 pprn from analyses quoted in
imation of the average composition of the earth's mantle and this work and a previous report on silver (Boyle, 19686). This
even of the entire earth is provided by the composition of the gives an Au/Ag ratio of 0.1.
chondrites. Others have suggested that the earth derived from Table 5. Abundance of gold, silver and platinum in domains of
an agglomeration of chondrites. If these theories are valid the earth's crust*
there is a strange difference, which requires an explanation, in Source Au Ag Pt
the Au/Ag ratios between chondrites and ultrabasic and basic
rocks supposedly derived from the mantle (Table 13). Perhaps Deep oceanic regions
primitive differentiation processes in the earth are the reason, Suboceanic regions
Continental shield regions
the gold settling into the metallic phase (Ni-Fe core) and the Folded belt regions
silver remaining largely in the mantle. Such a differentiation is Oceanic crust
perhaps supported by the fact that the Au/Ag ratios in Continental crust
siderites are extremely high. All of this discussion is of course Earth's crust
highly speculative to say the least, especially the supposition Crvstalline rocks
~dimentaryrocks 0.0051 0.065 -
that the core of the earth is composed of nickel-iron; it may be
*From Li and Yio ( 1 966).
that chondrites and the other meteorites bear no relationship
whatever to the earth in any of its aspects. In the upper lithosphere gold occurs in the native state
The gold and silver data for tektites (Table 4) is similar to and as a constituent of a few natural alloys. It is also a trace
that for terrestrial igneous rocks (Table 13). The Au/Ag ratio element in various native metals and semi-metals such as iron,
is, likewise, similar. The significance of these facts is obscure. copper and arsenic. These features indicate the strong sidero-
The gold and silver data for the lunar rocks and fines vhile character of the element. The metal also combines
(soils) (Table 4) are extensive and are discussed at length by a readily with tellurium, bismuth and antimony, forming a
number of mineral species, but its chalcophile character is
number of investigators (see the list of references in the
weak since no natural gold sulphides are known as minerals.
Selected bibliography). To generalize one notes that the
The element appears to have no oxyphile character, and there
overall gold and silver contents of the lunar materials are not
are no known natural gold oxides, salts or basic salts.
much different from those recorded for igneous rocks on the
earth (Table 13). A number of investigators have remarked Maclaren (1908) refers to silicate of gold, but there are no
modern investigations to confirm the presence of such a
that the lunar soils are enriched in gold and silver relative to
the rocks, the reason being that the soils have a micrometeor- compound. No silicates of gold are known in nature.
ite component. The enrichment is, however, not great as can Gold combines with a large number of artificial organic
be seen from the statistics recorded in Table 4. compounds, but the occurrence of these in natural environ-
There are no data on the nature of gold in any of the ments is largely uninvestigated. The element is a trace con-
extra-terrestrial materials just described. Presumably in mete- stituent of various terrestrial and marine organisms, but its
orites much of the gold is present in the metallic (mainly biological role, if any, is unknown. Gold is also a trace
Fe-Ni) phases and possibly in part in the sulphide (troilite) constituent of some coals and is found as traces in some
phase; also possibly in some of the iron oxides (magnetite, petroleum residues and in oil shales.
ilmenite) and chromite. In all of these minerals gold may be
present as a submicroscopic dispersed phase or in lattice sites
in the metal alloys, sulphides and oxides. Ramdohr (1973) Of all metals gold is most
mentions the presence of native gold (observed by A.B. frequently found native.
Edwards) in the Wedderburn iron meteorite. He also thinks -Richard Kirwan, 1799
that some osbornite observed in meteorites could be mistaken
for gold and vice versa. This possibility should be checked by Mineralogy of Gold
electron probe.
There is reasonable agreement with respect to the value Gold minerals
of the terrestrial abundance of gold. Goldschmidt (1954) gives The minerals of gold are given in Table 6. Of those listed the
0.005 pprn for the lithosphere; Rankama and Saharna (1950) most common are native gold and the tellurides. For the
give 0.005 pprn as the average for igneous rocks; Green (1959)
-
gives 0.001 pprn as the average for igneous rocks; Vino-
gradov's (1962) estimate is 0.0043 pprn for the crust; and
details of the gold minerals the reader should consult Palache,
et al. (1944, 1951), Ramdohr (1960), Hey (1962, 1963), Hey
and Embrey (1974), Chukhrov (1960-1965) and Berry and
Taylor (1964) has given 0.004 pprn as the continental crustal Thompson (1962). Occurrences of Canadian gold minerals are
abundance of the element, a mean of the basalt (0.004 ppm) noticed by Trail1 (1970).
and granite (0.004 ppm) averages. More recently Li and Yio Native gold crystallizes in a great variety of forms, the
(1966) have given the figures for the abundance of Au, Ag and most common being parallel groups and twinned aggregates
Pt in the various parts of the earth's crust noted in Table 5. branching at 60 degrees parallel to the edges or the diagonals
From their estimates the Au:Ag:Pt ratios are 1:20.4:13.2 and of the faces of (1 11); also commonly reticulated, dendritic,
the Au/Ag ratio is 0.048. Horn and Adams (1966) computed arborescent, filiform, wiry, mossy and spongy. Massive forms
the abundance of gold in igneous rocks to be 0.00357 ppm; in include rounded fragments (nuggets), flattened grains, scales,
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

Table 6. Gold minerals oxidized zones and in associated placers generally contains
Native elements, alloys and metallic compounds lesser amounts of silver and a number of other elements
Gold Au compared with the native gold in the corresponding primary
Argentian gold (electrum) (Au,Ag) ores. Within some specific deposits single crystals and parti-
Cuprian gold (cuproauride) (AWW cles of native gold are frequently relatively homogeneous with
Palladian gold (porpezite) (Au,Pd)
Rhodian gold (rhodite) (Au,Rh) respect to the distribution of trace and minor elements; in
Iridic gold (Au,Ir) other deposits the native gold is heterogeneous, a silver and/or
Platinum gold (Au,Pt) other elemental zoning being present. In some deposits there
Bismuthian gold (Au,Bi) is an increase in the silver and other elemental content from
Gold amalgam Au,Hg3 (?) the centres of the crystals or particles outward; in other
Maldonite Au,Bi
Auricupride AuCu, deposits the reverse is the case. In some gold lodes the crystals
Palladium cuproauride (Cu,Pd)3Au2 and particles of native gold contain numerous inclusions,
Suiphide generally associated gangue minerals such as pyrite, magne-
Uytenbogaardtite Ag3AuS2 tite, chalcopyrite, tellurides, etc.; in other lodes the native gold
Tellurides has a scarce assortment of inclusions; and in still others
Calaverite AuTe, inclusions are virtually absent. Within some single deposits
Krennerite (Au,Ag)Te,
Montbrayite (Au, Sb)2Te3 the intergrain variations and differences in trace and minor
Petzite (antarnokite) Ag,AuTe, element contents are often marked; in other deposits the
Muthmannite (Ag,Au)Te grains and crystals of gold throughout the deposits are
Sylvanite (Au,Ag)Te, relatively homogeneous within narrow limits. An example of
Kostovite AuCuTe, the latter is the gold in some of the Witwatersrand ore shoots.
Nagyagite Pb,Au(Te,Sb),Ss-8
Antimonide Placer gold commonly has thin rims of relatively high purity
Aurostibite AuSb, gold from which, according to some investigators, the silver
Selenide and other trace elements have been leached. This feature of
Fischesserite Ag3AuSe, placer gold is discussed at some length in Chapter 111. The
Tellurate gold in the oxidized zones of certain lodes may also exhibit
Gold tellurate (?) the rim effect; it is uncommon in primary gold ores in most
goldfields. Some investigators claim that the types and other
spangles, sprigs and finely divided particles (flour gold, features of gold deposits such as temperatures of deposition,
mustard gold and paint gold). All of these and other forms are nature of the depositing solutions, etc. can be divined from the
figured by Weinig (1960). analyses of native gold samples. Short resumes of some of the
The purity of native gold, gold bullion, gold coin, etc. is papers of the investigations will illustrate their contentions.
expressed in terms of fineness, which is commonly defined as Warren and Thompson (1944) considered that by thor-
the proportion of pure gold in the sample in parts per ough and detailed work it may be possible, by means of
thousand.17 Thus, native gold which is 900 fine contains 90 spectrographic analysis; to determine the metallogenetic prov-
per cent of the element gold. In some deposits native gold is ince or zone, and in some cases even the deposit, from which a
relatively pure, but more generally it contains some silver, particular sample of gold originates.
copper, and iron and traces to minor amounts of one or More recently Antweiler and Sutton (1970) report results
several of the following elements: Li, Na, K, Be, Mg, Ca, Sr, for 174 quantitative spectrochemical analyses for silver and
Ba, Zn, Cd, Hg, B, Al, Ga, In, Sc, Si, Ge, Sn, Pb, Ti, Zr, As, semiquantitative spectrochemical analyses for 32 other ele-
Sb, Bi, V, Se, Te, Cr, Mo, W, Mn, Co, Ni, Rh, Pd, Ir, Pt, U, ments in samples of lode and placer gold obtained from 67
Th and rare-earths. localities in eight western states of the continental United
There is a vast literature on the composition of native States, including Alaska, and from one locality in Brazil. Of
gold in practically all types of deposits in which the mineral the 24 elements detected (besides gold) in the samples, Ag,
occurs. Some of the papers noticed during the compilation of Cu, Fe and Ti were the most frequently detected. Pb, Pd, Bi,
this chapter include those by Warren and Thompson (1944), V, Ni and Co were identified more often in lode samples than
Ferguson (1950), Perelyaev (1953), Gay (1963, 1964), Denisov in placer samples, but Ti, Zr, La, Y and Cr occurred more
et al. (1966), Jones and Fleischer (1969), Antweiler and Sutton frequently in placer samples. They concluded that their data
(1970), Lantsev et al. (1971), Desborough et al. (1971), could possibly be used in prospecting for deposits of gold and
Badalova et al. (1971), Petrovskaya et al. (1971), Berman et al. other metals and in determining ore depositional conditions or
(1973), Semenenko and Latysh (1973), Kuznetsov et al. genetic associations.
(1973b), Petrovskaya (1973), Davidenko (1973a,b), Igurnnova Lantsev et al. (1971) determined the contents of the
(1974) and Petrovskaya et al. (1976). Some highl~ghtsfrom following trace elements - As, Sb, Te, Pb, Cu, Fe, Bi, Sn, Ni,
some of these papers may be mentioned. Co, Mn,Cr, Ti, Zn, Cd and Ga - in 120 gold samples from 40
There is a great variation in the trace and minor element endogenic deposits formed under various conditions and at
content of primary and secondary native gold, although within various depths. They concluded that the concentration of
some specific deposits the contents of the various elements trace elements in gold deposits increases as one ascends
appear to range within relatively narrow limits. Native gold in through ores formed at greater depths to those of near-surface
"Fisher (1945) defines the true gold fineness as the ratio Au/(Au + genesis. This tendency was found for all elements, with the
Ag) X 1000. This definition eliminates the base metal factor. exception of Cu, during the passage from great depths to
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

medium depths and for Sb, Sn, Zn and Mn during the passage to contain 5 to 10 per cent Pd in solid solution, but samples of
from medium to surface depths. This regularity was thought to this type of gold require restudy to ensure their homogeneity.
be caused mainly by diffusion upwards of isomorphous and It has been reported from Porpez, Taguaril and other localities
mechanical admixtures from gold during the process of in Minas Geraes and Goyaz, Brazil. Recently, palladium gold
recrystallization at high temperature. (Au,Pd) has been described from the Stillwater Complex in
Research based on polished sections and spectrographic, Montana by Cabri and Laflamme (1974). The mineral is
chemical and electron-probe analyses of native gold from face-centered cubic (a =4.047(l)A) and is cream-coloured with
primary deposits and placers carried out by the writer indi- a metallic pinkish cast under reflected light in air. It is
cates that most of the metallic and semimetallic elements may associated with a number of other rhodium and platinum
be lattice constituents of native gold. However, many of the alloys and minerals including platinian rhodium, rhodian
metals and other elements are often contaminants, being platinum, platinum-iron, and braggite/vysotskite.
present in minute inclusions of the minerals commonly Rhodian gold, also referred to as rhodite, is said to contain
associated with native gold, particularly quartz, carbonates, 34 to 43 per cent Rh. It requires restudy to determine its
sericite, sulphides, arsenides, tellurides, selenides, etc. In my homogeneity. Rhodian gold is reported from Colombia and
experience the following elements exhibit a frequency which Mexico.
suggests that they are predominantly lattice constituents when Zridic gold is reported in the old literature to contain up
they are present in pure samples of native gold: Ag, Cu, Fe, to 30 per cent Ir. This type of gold requires restudy to
Ni, Hg, As, Sb, Bi, Te, Pd and Pt. establish its homogeneity. Some of the reported occurrences
Several varieties of native gold are known which contain may be intergrowths of gold and osmium-iridium and plati-
significant amounts of other metals. These have been given num as described by Syrovatskii et al. (1969).
specific mineral names in some cases, but more generally they Platinum gold is reported in the old literature to contain
are referred to by a prefix indicating the contained element, up to 10 per cent Pt. It requires reexamination. Some of the
e.g. argentian gold, palladian gold, etc. reported occurrences may be intergrowths of gold and osmi-
Argentian gold. Normally all native gold contains some um-iridium and platinum as described by Syrovatskii et al.
silver generally in the range 5-15 per cent Ag. Most of this (1969).
silver is a lattice constituent, and there is a complete(?) Gold amalgam is reported by Palache et al. (1944) to
substitutional series from gold through argentian gold to occur in grains and lumps of white to yellowish colour with
aurian silver (kustelite) to native silver. Electrum has been metallic lustre in the Mariposa region, California, with plati-
applied to gold containing 20 per cent or more silver. The num in Colombia and in the vicinity of Pleiari, Borneo. The
name is an ancient one and has been used for centuries, composition of some of the samples analyzed corresponds well
apparently being first applied to the gold won from the with the composition Au,Hg,, suggesting a compound homo-
famous placers of the Pactolus a small river of ancient Lydia logous with the silver mineral, moschellandsbergite, AgHg,.
which joined the Hermus (modern Gediz) after flowing Maldonite or bismuthic gold. Some samples of native gold
through Sardis. Pliny, in his Historia naturalis, said "when the contain traces to minor amounts of bismuth (up to 3% Bi)
proportion of silver in gold is one-fifth, it is called electrum possibly in solid solution. The mineral maldonite was early
and possesses a pale yellow colour." reported to be an intermetallic compound with the formula
The range and sigdicance of the Au/Ag ratio in native Au,Bi. However, microscopic examination of the maldonite
gold and in gold deposits is discussed in Chapter 111. from Maldon, Victoria, the type locality, shows a fine myrme-
Cuprian gold. Most samples of native gold contain only kitic intergrowth of gold and bismuth, derived apparently
traces to minor amounts of copper probably substituting in from the breakdown of Au,Bi, which is said to be stable only
the lattice in most cases. Cases are known, however, where the at high temperatures (Ramdohr, 1953a, 1960).
copper is apparently plated on the gold (Ferguson, 1950). The maldonite from Salsigne (Aude) in France described
Some samples of gold mentioned in the literature contain by Boyer and Picot (1963) averages 64.58 per cent Au and
from 0.10 to 20 per cent Cu. One of the copper varieties has 35.72 per cent Bi, approximating the formula Au,Bi. The
been named cuproauride and given the formula AuCu. Accord- sample in this case appears to have been homogenous. Boyer
ing to Ramdohr (1960) it is rare and requires further investiga- and Picot confirm Ramdohr's opinion that the mineral is
tion. The compound, AuCu,, containing some 40 per cent formed within a relatively narrow temperature interval and
gold, named auricupride is reported by Ramdohr to occur think the mineral is a reliable geothermometer. From the
frequently. It has a high metallic lustre and a yellow colour Au-Bi phase diagram they suggest a temperature of deposition
with a reddish tint. Oen and Kieft (1974) describe a new below or equal to 373OC.
copper-gold alloy with a formula approximating CuAu,,,. The According to Razin et al. (1971) there is some doubt
alloy occurs in the chromite-niccolite ore from Beni-Bousera, about the existence of auricupride, AuCu,. These same authors
Morocco, as irregular grains mostly along grain boundaries of describe a new mineral, palladium cuproauride, in the ores of
niccolite and loellingite. In the auriferous ores of the Kara- the Talnakh copper-nickel deposit, U.S.S.R. The mineral is an
bashsk deposit Novgorodova and Tsepin (1976) observed the intermetallic compound with formula (Cu,Pd),Au,. It contains
following phases among the auricuprides, Cu,Au, CuAu and traces and minor amounts of Rh, Ag, Bi and Ni.
CuAu,. The artificial isomorphous series Cu-Au is complete, The physical properties of native gold, the morphology of
but in nature the copper end members with high contents of gold crystals and particles in deposits and the relationship of
gold (>3% Au) have not been recognized. these parameters to the depositional conditions in gold
Palladian gold termed porpezite in the old literature is said deposits have been extensively studied by many investigators
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

prior to 1970. Papers reviewed during the compilation of this deposition which in turn are predicated on the original or
chapter since that date include those by Korobeinikov (1971), induced porosity of rocks and on structural events such as
Koroleva et al. (1971), Petrovskaya et al. (1971a-d), Ya- fracturing, formation of open spaces along faults, shearing etc.
blokova (1972), Berman et al. (1973) and Dzhantuganov In addition there are also various chemical factors which seem
(1974). Some of the features brought out by all of these to be involved, but about which we have only a superficial
studies, both pre- and post-1970, are summarized briefly knowledge. These include replacement phenomena, exsolution
below. Only the properties of epigenetic gold and that in the reactions, coprecipitation phenomena and so on.
oxidized zones of auriferous deposits are reviewed here; placer Native gold contains gaseous inclusions that have recent-
gold is discussed in detail in Chapter 111. ly been studied in some detail by Petrovskaya et al. (1971~).
The morphology of native gold in epigenetic deposits is They found that some 90 per cent of the gas was CO, and the
exceedingly variable, the most common shapes of the particles remainder mainly nitrogen. The pressure in the inclusions
being nodular and lamellar, lumpy masses, amoeba-shaped studied was estimated at 5 to 20 atm. The authors concluded
masses, simple platy forms, ramifying platy and veinlike that the presence of CO, and N, (also found in gaseous
masses, dendritic masses, wires, sprigs, spear- and splinterlike inclusions in quartz in the same deposits) is due to the
forms, crystals, droplike inclusions in sulphides and other adherence of bubbles of CO, at the surface of hydrophobic
minerals, smears on shear planes, pulverulent aggregates gold grains during their growth. Their further conclusion was
(mustard gold), and spongy masses. There appear to be no that carbon dioxide plays a significant role in the crystalliza-
clear-cut relationships between the shapes of the native gold tion of gold from hydrothermal solutions.
particles and the types or age of the deposits. In general The optical properties of gold have been extensively
crystals are rare in the deposits formed at great depth (mainly investigated by Hodgson (1968), and the determination of the
deposits of Precambrian and Paleozoic age), whereas crystals silver content of natural gold alloys by reflected-light micros-
are relatively common in younger deposits formed near the copy is described by Eales (1968) and Eales and Viljoen
surface especially in those of Tertiary age. Crystals, wires, (1973). A criticism of the first paper has been published by
dendrites, pulverulent aggregates and spongy masses are Stumpfl(1969).
especially characteristic of secondary gold found in the Gold is unique among the precious metals in the variety
oxidized zones of auriferous deposits. Deep-seated deposits, and weight of its placer nuggets. Some have been found that
which include most lodes of Precambrian and Paleozoic age, are beautifully metallic and crystallized, whereas others are
have much more uniformity in the morphology of their native inconspicuous, being rounded, pitted and covered with black
gold particles than near-surface deposits of Mesozoic and manganese oxides, brown limonite, humic compounds, silica,
Tertiary age. The morphology of the gold particles and clay or other nondescript compounds. In weight there are
crystals in the old (deep-seated) deposits is also generally records of nuggets ranging from less than 1 oz up to masses
much simpler than is that of the gold in the younger (near- weighing nearly 2400 oz (200 lb troy). Australia has produced
surface) deposits. many of the largest nuggets, the goldfields of Victoria exceed-
The size of gold particles and crystals in epigenetic ing all others. Of the nuggets officially recorded from Victoria
gold-bearing deposits varies widely, the usual range being 12 exceeded 1000 oz, and 33 were between 1000 and 500 oz.
from less than one thousandth of an ounce up to masses The Dunolly district, which is deeply weathered and oxidized,
weighmg a thousand ounces or more. Deposits formed under has surpassed all others in the number of nuggets found. The
deep-seated conditions (most Precambrian and Paleozoic Welcome Stranger weighed slightly more than 2284 oz and
deposits) generally are marked by fair uniformity in the size of was found in detrital material just below the surface at Black
the gold particles, whereas deposits formed under near- Lead, Mt. Moliagul, near Donolly, Victoria. Another nugget,
surface conditions (many Tertiary deposits) are often charac- the Welcome, weighed 2217 oz and was found in alluvial
terized by great variability in the size of the native gold material at a depth of 180 ft at Bakery Hill, Ballarat, Victoria.
particles and crystals. This variability is said by some inves- Two others, also found in alluvial gravels in Victoria, the
tigators to indicate fluctuating conditions during the deposi- Viscount Canterbury and Viscountess Canterbury, weighed
tion of the gold. In numerous deposits gold is present in an 1114 and 912 oz respectively. In the United States some very
extremely finely divided form in sulphides, sulphosalts or large nuggets have been discovered, the one from Carson Hill,
gauge minerals such as quartz. The division is so fine in some Calaveras County, California weighmg some 2340 oz (Gaard-
deposits that the gold cannot be seen under the highest en, 1940). Another water-worn nugget, the Willard, Dogtown
magnification in minerals such as arsenopyrite and pyrite. The or Magalia nugget, weighmg 54 lb troy, was found at Magalia
nature and significance of this submicroscopic gold is dis- in California in 1859. The discovery of this nugget was the
cussed subsequently. There are no clear-cut relationships signal for a celebration which has been held annually ever
between the size of gold particles and crystals and depth in since (Clark, 1970).
epigenetic deposits as far as this writer can ascertain from the Despite the large amount of gold taken from the Klon-
literature or from his experience. It is of interest to note that dike, Cariboo and other placer areas of Canada few large
the gold of the Witwatersrand is remarkably uniform in its nuggets have been discovered. Robinson (1935) mentions an
size of particles (av. diameter - 80p; 0.08 mm), a feature that 85 oz nugget from the Klondike, and in eastern Canada a
is discussed in more detail in Chapter 111. nugget weighing 52 oz, 11 dwt, 6 grains, called the 'Kilgour
Most investigators agree that the morphology and size of Nugget' was taken from the Gilbert River (Chaudiere),
gold particles and crystals in most epigenetic deposits are Beauce, County, Quebec. In the same area a nugget weighing
essentially dependent upon the size and shape of the sites of 45 oz, 12 dwt called the 'McDonald Nugget' was found on Lot
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

16, De Lury Concession, Gilbert River, Quebec. Numerous +

gruent melting point of 382 S°C, and hence its presence in
other smaller nuggets weiglung a few tens of ounces have been deposits is not necessarily indicative of a low temperature of
taken from the Klondike, Cariboo and other placers in formation. The incongruent melting temperature of sylvanite
Canada (Frontispiece). (354 + 5°C) indicates a maximum temperature for its forma-
Gold nuggets have been found in every conceivable tion. Cabri also found that hessite and petzite are each
geological environment, from birds' nests and crops to pot- characterized by three polymorphs. Continuous solid solution
holes in placers. The origin of gold nuggets is discussed in exists between the highest polymorphs and extends to a
Chapter 111. composition about 7 weight per cent more gold-rich than
Certain of the gold tellurides probably occur in minute stoichiometric petzite. A new phase, termed the 'x' phase, was
amounts in most primary gold deposits judging by the found to be stable along the petite-hessite join from about 2.5
frequency with which traces of tellurium are found in gold to 14.5 weight per cent gold within temperature limits of 50 to
ores and the nearly universal presence of isolated pockets and 415°C. The observations of Forsythe (1968) with respect to
veinlets of tellurides in most gold veins and other types of the occurrence of tellurides at Vatukoula lend support to some
auriferous deposits. In some deposits the tellurides are impor- of Cabri's conclusions.
tant ore minerals of both gold and silver. Localities where Howie and Veale (1966) have discussed the low tempera-
gold (and silver) tellurides are particularly abundant include ture synthesis of gold telluride. They could not make gold
Nagyig and Brad, Romania; Kalgoorlie and Mulgabbie, sesquitelluride by low temperature coreduction and precipita-
Western Australia; Cripple Creek, Colorado; Kirkland Lake, tion techniques; sometimes a metastable telluride of composi-
Ontario; and a number of localities in Japan (Watanabe, tion close to AuTe,,,, was obtained. They state that the
1952); Vatukoula, Fiji; Philippines (Callow and Worley, mineral montbrayite, Au,Te3, may represent an intermediate
1965); and a number of localities in U.S.S.R. (Chukhrov, step in the ordering of this structure.
1960; Amiryan, 1960; and Pankov and Chukhrov, 1962). The relation between the composition and X-ray diffrac-
Krennerite, calaverite, sylvanite, nagyagite, mmuthmannite tion data of gold-silver tellurides is discussed by Cabri and
and petzite appear to be the most common of the gold Rucklidge (1968). Stumpfl (1970) has noted considerable
tellurides, having been recorded in a large number of places. compositional variations in the gold content of specimens of
Montbrayite has been recognized only in the Robb-Montbray gold tellurides from different deposits.
Mine, Montbray Township, Quebec where it is associated with Our semiquantitative and qualitative analyses of the
other tellurides and gold (Thompson, 1949). Kostovite is a new various gold-silver tellurides indicate that most are relatively
mineral and occurs in the copper ore deposit of Chelopech, pure. Traces to minor amounts (tens to thousands of ppm) of
Bulgaria where it is associated with tennantite, chalcopyrite, S, Se, Sb and As are commonly present in most samples
pyrite, native tellurium, native gold, tellurides and other probably replacing Te. In addition to these elements the
minerals (Terziev, 1966). Tunell (1954) has reviewed the main following are commonly found in traces to minor amounts:
features of the crystal structures of the various gold- Cu, Fe, Ni, Co, Pb, Sn, Hg, W, Mo and Bi. Some of these
silver tellurides. elements evidently replace Au and Ag, although some of them
Thompson (1949) has described most of the known gold may be largely in impurities. The platinum metals were not
and silver telluride occurrences in Canada. found in any of the samples.
Markham (1960) has discussed the synthetic and natural The isotope 130Te is radioactive and decays by double
phases in the system Au-Ag-Te and also his findings with beta emission to yield 130Xe.This feature of tellurium minerals
respect to the occurrence of tellurides at Kalgoorlie, Western permits age determinations of gold and silver deposits con-
Australia and Vatukoula, Fiji. He finds that the experimental taining tellurium to be made. Srinivasan et al. (1972) have
data are insufficient to indicate a meaningful range of deposi- determined the half-life for double beta decay of 130Te to be
tional temperatures for any given telluride, but thinks that 2.83 f 0.30 X 10,' years from an analysis of xenon and
when the calaverite-krennerite transition is experimentally tellurium in the tellurides of Kalgoorlie, Australia. Three
determined, it should provide a useful geological thermometer. telluride samples from different locations (Vakukoula, Fiji;
Cloke (1 963) and Petersen (1964) have commented on some of Facebaja, Transylvania, Romania; and Moctezuma, Sonora,
the physico-chemical features of Markham's paper. Mexico) gave ages consistent with geologic age estimates. The
Shcherbina and Zar'yan (1964) have discussed the pa- authors conclude that the method is particularly useful in
rageneses of gold and silver tellurides from Armenian sulphide yielding the age of gold and silver mineralization directly.
deposits in terms of the experimentally determined parts of Some of the facts concerning the occurrence of silver (and
the system Ag-Au-Te. They concluded that the assemblages gold) tellurides may be noted here. The tellurides seldom if
hessite-petite-gold and hessite-petzite-krenneritewere formed ever are associated with the selenides; for some reason they
by deposition from hydrothermal solutions during the galena- seem to be mutually exclusive. It may be that observers have
sphalerite stage of mineralization, and by later replacements. failed to recognize the presence of the two types of minerals
Native silver and tellurium, formed by the decomposition of together, but this seems unlikely considering the amount of
gold-silver tellurides, occur in some assemblages. mineralogical work that has been done on gold ores. Even in
Cabri (1965a) recently camed out a systematic investiga- the highly seleniferous gold ores of Salida, Indonesia there are
tion of the phase relations in the Au-Ag-Te system and found apparently no selenides (or doubtful selenides, naumannite?)
that krennerite, rather than being a polymorph of AuTe,, associated with the various tellurides (sylvanite, petzite, hes-
should be interpreted as a single mineral entity with the site, altaite). There, the tellurides are invariably associated
approximate formula Au,AgTelo. It is stable up to its incon- with galena and the selenium is bound mainly in acanthite,
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

galena and arsenpolybasite (Kieft and Oen, 1973). An alterna- these environments frequently rims some of the gold particles
tive reason for the antipathy of selenides and tellurides in and appears to be younger than gold, but good relationships
deposits may be that the solutions that deposit gold and silver for establishing the paragenesis of the mineral are uncommon.
tellurides are inhibited from carrying selenium and vice versa. In the Czechoslovakian occurrences aurostibite is said to be
This, likewise, seems improbable from a chemical viewpoint. younger than the native gold. In the Victoria occurrences the
There are a number of silver selenides, but no natural gold mineral occurs in the quartz-gold-stibnite veins. According to
selenide sensu strictu is known. The silver-gold selenide, Stillwell (1952) the mineral is best preserved in quartz and,
fischesserite, Ag,AuSe,, is however, stable. Artificially a stable where observed in stibnite, tends to appear as relict areas. Its
phase a-AuSe can be prepared, and while tellurium does not occurrence in a gold grain containing a gold-aurostibite
substitute in the AuSe lattice to a detectable extent, selenium eutectic led Stillwell to conclude that the mineral formed
will substitute up to at least 15 atomic per cent of the above 360°C, a higher temperature than that which the
tellurium atoms in the monoclinic AuTe, (calaverite) lattice at younger stibnite was deposited. Stillwell states that aurostibite
400°C (Cranton and Heyding, 1968). There is also at least one is a relatively unstable compound and has been largely
ternary phase, Au,SeTe, in the system Au-Se-Te. dissociated in the later stages of vein formation, yielding the
The tellurides generally occur in deposits in volcanic dull, rusty, cellular-textured gold that is a common feature of
assemblages, or in rocks closely associated with andesites, stibnite-bearing veins. The dissociation yields native antimony
basalts, etc. Particularly notable is their occurrence in Precam- and gold. The aurostibite in the Gwanda district of Rhodesia
brian greenstones, examples being the Kirkland Lake- contains of the order of 1 per cent nickel and nondetectable
Noranda-Malartic areas of Ontario and Quebec; Porcupine amounts of silver. Much of the aurostibite in these deposits
area, Ontario; Red Lake area, Ontario; Flin Flon, Manitoba; rims gold and is probably late, but some of the purer gold in
and the famous telluride-gold lodes of Kalgoorlie, Western the ore of the Jessie Mine is younger than aurostibite. In the
Australia. In younger (generally Tertiary) volcanic rocks, Indarama Mine in Rhodesia the aurostibite was deposited
notable occurrences of gold and silver tellurides are known at simultaneously with native gold, both minerals being late in
Cripple Creek, Colorado; Brad and Nagyag, Romania (Tran- the general mineral paragenesis.
sylvania); Vatukoula, Fiji and elsewhere. The aurostibite in the Bestyube goldfield in northern
In detail, the gold tellurides occur mainly in quartz and Kazakhstan, U.S.S.R., forms reaction rims around native gold
quartz-carbonate veins and in pyritized, silicified and car- and is thus a late mineral formed by the reaction of the gold
bonated zones in volcanic rocks. Wall-rock alteration effects with antimony-bearing solutions in a reducing environment
characterized by carbonatization, hydration, pyritization and (Naz'mova et al., 1975). Electron microprobe analyses showed
silicification are generally marked in these deposits. Some the aurostibite to contain Au - 44.52; Ag - 0.12; Cu - 0.08;
massive sulphide deposits in volcanic assemblages, particular- Sb - 52.73; and As - 1.73 weight per cent. In the Yakutian
ly those rich in copper, carry gold and silver tellurides but deposits aurostibite occurs in quartz-stibnite veins where it is
with less frequency than the veins and carbonatized-silicified intimately intergrown with or rims native gold (Indolev and
zones. Skarn deposits do not seem to contain gold and silver Zhadanov, 1975). The paragenesis in some samples is native
tellurides in any abundance according to my investigations, gold followed by aurostibite; in a few others stibnite followed
although other tellurides, mainly those of bismuth, may occur successively by aurostibite and a late generation of native
in some quantity in such an environment. The minerals most gold. The aurostibite is considered to have formed in the
commonly associated with gold and silver tellurides include deposits mainly by reactions between early precipitated gold
pyrite, arsenopyrite, pyrrhotite, tetrahedrite-tennantite, native and late stage solutions containing antimony.
gold, native tellurium (rare in Precambrian but common in Barton (1971) has concluded that aurostibite is stable
Tertiary deposits), other tellurides (particularly coloradoite, only under conditions of relatively low sulphur activity, and
HgTe), tellurbismuth, various Cu, Pb, Zn, Ag and Bi sulphides that the assemblage pyrite + aurostibite is stable only at low
and sulphosalts, tourmaline and fluorite. The paragenesis of temperatures (below about 125"C, but the uncertainties are
deposits containing gold tellurides is often quartz and pyrite too large for this to be a useful point on the geothermometric
followed in turn by base metal sulphides, tellurides and native scale). This temperature agrees with the finding of the writer
gold. This sequence is, however, not invariable, gold and (Boyle, 1954) that late quartz, probably of the same generation
tellurides apparently being deposited simultaneously in some as gold and aurostibite, has a temperature of deposition
deposits, or gold may precede the tellurides. (actually decrepitation temperature and liquid inclusion filling
Aurostibite has been recognized in the gold deposits of the temperature) around 150°C.
Yellowknife and Larder Lake areas in Canada (Graham and Fischesserite, the silver-gold selenide, Ag,AuSe,, is isom-
Kaiman, 1952), in the deposits of Krasna Hora and Milesov in etric and isostructural with petzite. It occurs in carbonate-
Czechoslovakia (Sobotka, 1954), in the antimony veins of quartz veins at Predborice, Bohemia, Czechoslovakia associat-
Costerfield, Victoria, Australia (Stillwell, 1952), in the Lone ed with chalcopyrite, naumannite, clausthalite, berzelianite,
Hand and Jessie Gold mines, Gwanda district, Rhodesia gold and other selenides (Johan et al., 1971). It appears to be a
(Eales, 1962), and in the Indarama Gold-Antimony Mine, late mineral in the paragenetic sequence and is commonly
Sebakwe area, Que Que, Rhodesia (Mehliss, 1968). It is situated between the grain boundaries of carbonate minerals.
probably more common than these few occurrences would The mineral has also been recognized in certain unusual ores
suggest. According to my observations (Boyle, 196la) aurosti- in the Texas Gulf massive sulphide body at Timmins, Ontario.
bite is generally closely associated with gold in deposits that Gold tellurate is reported as a supergene mineral at the
contain stibnite and other antimony minerals. Aurostibite in Date Mine, Hokkaido, Japan (Watanabe, 1952). The mineral
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

is evidently derived by the oxidation of gold tellurides. It Table 7. Gold and silver contents of common silicate minerals
requires confirmation. Refer-
A number of synthetic compounds of gold are relatively Mineral and locality Au Ag ence
stable and may occur as minerals, although they have not yet (PP~)
been identified. These compounds include various selenides, Ouurt:
seleno-tellurides, mixed A U ~ A sulphides,
~ the phosphide, the ~S.S.R.
Altai and Transbaikal 0.00060.0042
chloride and various telluride halides of the type AuXTe, (av., 0.0008)
(X=Cl,Br,I). By analogy with AuSb, one might also suspect Altai-Sayan 0.01 1 (av.)
that the compound AuAs, should occur in nature, although a Kazakhstan 0.001 1-0.012
search by electron-microbe by the writer and his colleagues Altai, Transbaikal and Urals 0.0016 (av.)
Urals 0.0017 (av.)
has failed to find such a mineral in auriferous ores carrying U.S.A.
abundant native arsenic, arsenopyrite and other arsenic- Helena, Montana (quartz and
bearing minerals. The reason for the nonappearance of AuAs, feldspar) 0.0060.176
in nature may result from the relatively high instability of the (av., 0.065)
mineral at low temperatures due to the unfavourable electron- Canada
Buckingham, Que.
ic (electronegativity) relationships discussed previously. (See Lansdowne, Ont. (crystals)
further the discussion under gold in pyrite and arsenopyrite.)
Feldspars
Barton et al. (1978) have recently described a double U.S.S.R.
sulphide of silver and gold, uytenbogaardtite, Ag,AuS,, from Altai and Transbaikal 0.0002-0.0005
Tambang Sawah, Benkoelen district, Sumatra, Indonesia; the (av., 0.0003)
Comstock Lode, Nevada, U.S.A.; and Smeinogorski, Altai, Altai-Sayan 0.0040 (av.)
U.S.S.R. At all three localities uytenbogaardtite occurs as Altai-Sayan 0.018
Kazakhstan 0.00 13-0.0052
small (up to 100p) blebs and rims intimately associated with Altai, Transbaikal and Urals 0.0016-0.0017
electrum, acanthite, quartz and other minerals. Urals 0.00160.0017
Canada
Gold in other minerals Eau Claire, Ont. (albite) tO.O1
Villeneuve Tp., Que. (albite) to.01
Gold is a minor and trace constituent of a great variety of Bathurst Tp., Ont. (microcline) tO.O1
minerals, a feature of the geochemistry of the element that has Portland Tp., Que. (microcline) tO.O1
been extensively investigated for many years. A summary of Nain Island, Lab. (Ca feldspar) tO.O1
the status of gold in minerals up to 1969 is contained in the Feldsputhoids
paper by Jones and Fleischer (1969). Canada
The writer's investigations, based on optical and electron Davis Hill, Ont. (nepheline)
microprobe work on polished and thin sections, indicates that Nephton, Ont. (nepheline)
Bancroft, Ont. (sodalite)
the gold in many minerals is present in particulate form,
Micas
generally as native gold but also as gold tellurides and Muscovrre:
aurostibite. In some minerals, however, the traces of gold are U.S.S.R.
probably lattice constituents. Altai-Sayan 0.0038 (av.)
Urals 0.0109 (av.)
Gold in silicates Canada
The older data (prior to 1950) recorded in the literature on the Eau Claire, Ont.
gold content of-silicates are sparse and seemingly unreliable Biotite:
since the values recorded range from 0.5 to >0.5 ppm, U.S.S.R. Altai-Sayan 0.0040 (av.)
amounts that are relatively high considering the abundance of Altai 0.0091 (av.)
gold in nature. Kazakhstan 0.001-0.01 19
Table 7 records some of the more recent (post-1950) Altai, Transbaikal and Urals 0.00 19 (av.)
analyses of silicate minerals, a few from the National Mineral Urals 0.0018 (av.)
Collection of Canada. The latter were specially purified, and U.S.A.
Helena, Montana 0.002-0.924
the gold in these samples was done by a fire assay-atomic (av., 0.076)
absorption method the detection limit being 0.01 ppm. The Canada
silver in the samples was done by spectrographic and atomic Douglas, Ont. t0.01
absorption methods.
As shown by Table 7 the gold content of silicates ranges U.S.S.R.
from about 0.0002 to 0.924 ppm. There is no strikingly Altai-Sayan 0.0059 (av.) - 2
Kuznetsk, Ala-Tau 0.077 (av.) - 2
apparent relationship in the gold content of silicates in the Kazakhstan 0.00260.020 1 4
series quartz-feldspar-mica-amphibole-pyroxene-olivine, al- Altai. Transbaikal and Urals 0.0020 (av.) 5
though there is a positive indication that minerals like biotite Urals 0.0016 (av.1 6
and amphibole contain a little more gold than the others. This U.S.A.
is suggested from recent studies such as those carried out by Helena, Montana (hornblende) 0.003-0.823
(av., 0.100)
Zvereva and Gavrilenko (1971). In the dark silicate minerals Canada
gold may substitute in the iron sites, although we suspect that Wilberforce, Ont.
much if not all of the gold may be present in microscopic Bathurst Tp., Ont.
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

Table 7. (cont'd.) to about 1/700 of the overall amount determined by assay. It

Refer- is concluded, therefore, that the remainder of the gold is
Mineral and locality Au Ag ence present as a lattice constituent of the arsenic. The same
( P P ~ features prevail in the native antimony from West Gore, Nova
Pvroxeues Scotia, except that more of the gold is present in the native
U.S.S.R.
Altai-Sayan 0.0 16 (av.) - 2 form.
Kazakhstan 0.01374.0240 4 Bismuth is notably low in gold content according to my
Canada analyses. The small amounts present are probably lattice
Yates Mines, Sandy Creek, Que. tO.O1 t0.5 7 constituents. Graphite contains a little gold, but most of the
Ball Mines, Haliburton, Ont. tO.O1 t0.5 element is probably present in the small crystals and specks of
Chlorite
U.S.S.R.
pyrite, which are invariably present in graphite from veins.
Altai, Transbaikal and Urals 0.0030 (av.) 5 The values for diamond given by Mirzaev and Khabirov
Urals 0.0025 (av.) 6 (1972) are very low.
Olivine Copper, silver and the various platinoid metals and alloys
U.S.S.R. invariably contain gold, often in relatively large amounts. Pure
Al tai-Sayan 0.014 (av.) - 2
Canada native copper from some deposits, mainly in Ontario and
Bigelow Tp., Que. t 0.0 1 t0.5 7 Michigan, contains only traces of gold according to my
Epidote experience. Other deposits, however, appear to have consider-
U.S.S.R. able amounts of gold in the native copper according to the
Altai, Transbaikal and Urals 0.0026 (av.) 5 published analyses. Probably most of the gold reported in
Urals 0.0025 (av.) 6
Tourmuline native copper is a lattice constituent. Native silver from
U.S.S.R. Cobalt, Ontario is notably low in gold, but that from Kongs-
Altai-Sayan 0.0 12 (av.) 2 berg, Norway in similar deposits, is relatively enriched in the
Canada element according to the published analyses. Aurian silver or
Portland Tp., Que. tO.O1 t0.5 7
Leduc Mine, Wakefield Tp., Que. t0.01 t0.5 7 kustelite is reported from a number of deposits. In this
Villeneuve Mine, Villeneuve Tp., mineral Au substitutes for Ag, and a complete series extends
Que. t 0.0 1 t0.5 7 through argentian gold (electrum) to gold. The various plati-
South March, Ont. t0.005 0.1 7 noids including native platinum, platiniridium, osmiridium,
Sphene
U.S.S.R.
aurosmiridium, iridosmine, etc. generally contain gold, espe-
Altai-Sayan 0.0039 (av.) cially in placers. The quantity of gold varies widely as shown
Altai, Transbaikal and Urals 0.0029 (av.) by the analyses in Table 8. In some deposits most of the gold
Urals 0.0027 (av.) is probably present as a lattice constituent in the native
Gurnn platinoids; in other deposits the platinoids are intergrown
Canada
Labelle Mine, Que. with free gold. In a few deposits such as those in the
Dana Tp., Ont. Kuznetsk, Alatau region of U.S.S.R the gold forms thin
U.S.S.R. blooms and films, and more rarely thin crusts on nuggets of
Urals 0.0052 (av.) osmiridium (sysertskite) and similar platinoids. Small frac-
Zirco!~
Canada
tures may also contain this type of gold which according to
Saramac Mines, Ont. 0.0 1 t0.5 7 Syrovatskii et al. (1969) is definitely secondary and formed
References: I . Anoshin and Potap'yev (1966): neutron activation methods.
within the placers.
2. Shcherbakov and Perahogin (1964); neutron activation methods. Some authors record up to 2.7 per cent Au in native
3. Mantei and Brownlow (1967); neutron activation methods. tellurium, but my research on the mineral indicates that little
4. Zvereva and Gavrilenko (1971); neutron activation methods.
5. Anoshin er 01. (1970); neutron activation methods. gold is partitioned into pure native tellurium. Samples from
6. Bushliakov (1971); neutron activation methods. Cupra mines, Quebec show only traces of gold, whereas
7. Geological Survey of Canada; assay and atomic absorption associated tellurides such as altaite and tellurbismuthite are
methods.
greatly enriched in the element.
inclusions of pyrite and/or magnetite which these minerals The sulphur of gossans on auriferous deposits commonly
often contain. Biotite and other ferromagnesian minerals contains some particulate native gold. A sample of native
devoid of pyrite and/or magnetite contain only very low sulphur from acidic sulphate gossan on cupriferous pyrite
amounts of gold (t0.01 ppm) in our experience. deposits on the island of Cyprus is reported to contain 8200
Gold in native elements ppm Au (H.A. Tourtelot; U.S. Geol. SUN. Circ. 622, p. 5,
Gold is a frequent trace and minor constituent in native 1969). The gold occurs as particles, 10 to 100p across, and the
elements as shown in Table 8. In general the metallic elements smaller ones show poorly formed crystal faces. The larger
contain more gold than the semimetallic and nonmetallic particles are rounded, resembling framboidal pyrite which
varieties such as graphite, sulphur, etc. many geologists believe to be of bacterial origin. The sulphur
Native arsenic occurs in some gold deposits as does also associated with fumaroles, salt domes and other types of
native antimony. Both minerals contain relatively high con- deposits is normally low in gold (t0.01 ppm).
tents of gold. My investigations of native arsenic from Bau, Gold in silver and base metal tellurides and selenides
Sarawak by polished sections and microprobe show that some Gold is a common trace and minor element in practically all
of the gold is present as minute inclusions. This gold amounts of the silver and base metal tellurides and selenides, and in
 Contents

Table 8. Gold and silver contents of native elements

Native element and locality Au Ag Au/Ag ratio Refer-
ence

Arsenic, As
Germany; Andreasberg, Harz 150
Malaysia; Bau, Sarawak 20-40
Germany; Thiiringia 5
Allemontite, (As, Sb)
Canada; Atlin, B.C. 500
Canada; Atlin, B.C. 42 1
Antimony, Sb
U.S.A.; Kern County, California 35.2
Canada; West Gore, N.S. 12.0
Bismuth, Bi
Germany; Altenberg, Saxony 0.03
Canada; O'Brien Mine, Cobalt, Ont. 0.050
Australia; New South Wales 1.8
Graphite, C
Canada; Black Donald Mines, Calabogie, Ont. 0.035
Canada; Buckingham, Que. 0.020
Diamond C
U.S.S.R., various 0.0005&0.003 1
Copper, Cu
Norway; Kviteseid 200
Canada; Indian Mine, Thunder Bay District, Ont. 0.02
U.S.A.; Pewabic bed, Keweenaw Peninsula, Michigan <0.0 1
Various (Chukhrov) 2-3 %
Silver, Ag
Norway; Kongsberg 40
Canada; (Nova Scotia Mine, Cobalt, Ont.) 3.0
Canada; (Castle-Tretheway Mine, Gowganda, Ont.) 4.1
Canada; (Echo Bay Mine, Echo Bay, N.W.T.) 13.5
Aurian silver (kustelite) 0-30%
Iron, Fe
Greenland; Ovifak, Disko 1-5
Germany; Biihl 0.5
Zinc, Zn
Canada; Keno Hill, Y.T. nd
Lead Pb
various tr
Mercury, Hg
various tr-m tr-m
Iridosmine, (Os,Ir)
Australia; New South Wales 800
U.S.S.R.; Urals >1000
Various (Chukhrov) 9000
Osmiridium (Ir, 0s)
Various (Chukhrov) 19.3%
Platinum, Pt
Brazil >1000
U.S.S.R.; Urals 500
Various (Chukhrov) up to 3%
Canada; Similkameen River, B.C. 300
Canada; Horsefly River, B.C. 240
Canada; North Saskatchewan River, Alta. 3600
Platiniridium, (Pt,Ir)
Brazil 200
Sulphur, S
Mexico; San Felipe, Baja California 0.030
Italy: Cianciani <0.01
Canada; Cupra Mines, Quebec < 10
Various (Chukhrov) 0.15-2.788
References: 1 . Analysis by Noddack and Noddack (1931).
2. Analysis by Goldschmidt and Peters (1932).
3. Analysis by Geological Survey of Canada, Mines Branch and Bondar-Clegg and Co., Ltd., Ottawa.
4. Other sources: Hintze (1889-1968), Doelter el al. (1911-1931); Palache et at. (1944); Fischer (195fi-59); Chukhrov (1960-1965); Mirraev and
Khabirov (1972).

Notes: nd - not detected

tr - trace
m - minor element
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

some it occurs in considerable quantities (Table 9). From the on sulphides, arsenides and similar minerals should examine
available data the tellurides amear- to contain more of the
m their specimens for homogeneity by microscopic methods or
element than the selenides, but the two types of minerals better still by means of the electron probe. The data would
rarely coexist in one setting, and the partition of gold between then be of more significance in ascertaining the extent of
the two species is, therefore, relatively unknown. Since natural replacement of one element by another.
gold tellurides are common and natural gold selenides sensu The arsenides and antimonides commonly carry small
strictu have not yet been reported one can assume that the amounts of gold, those containing the platinum metals (sper-
bond of gold to tellurium is much more stable than that to rylite) having the highest concentrations according to our
selenium in nature. In the double selenide, fischesserite, analyses. Other arsenides, particularly the copper-bearing
Ag,AuSe,, the gold content is 27.4 per cent. species, e g , domeykite also appear to contain relatively high
amounts of gold as shown by the analyses of others. In the
Table 9. Gold and silver contents of silver and base metal arsenides and antimonides gold is probably a lattice constitu-
tellurides and selenides ent and substitutes for the platinum metals and copper and
Au/Ag Refer- possibly also for cobalt, nickel and iron.
Mineral and locality Au Ag ratio ence Gold is a common microconstituent in a large number of
(.P.P ~ ) sulphides and sulphide-arsenides, being concentrated mainly
Hessite, AgTe
< -
U.S.S.R.: Krasnvi Klvutsh 2000 62.45% 0.003 1 in the copper, silver and antimony species and in pyrite and
Altaite, ~ b ~ e arsenopyrite. The lead and zinc sulphides and sulphosalts do
Australia; Kalgoorlie 200 4300 0.05 1 not normally contain enrichments of gold, although in some
U.S.S.R.: Altai 400 >1000 t0.40 2 deposits galena and sphalerite are indicators of high gold
~elonite,NiTe,
Australia 3220 770 4.2 values. Where this occurs the gold is mainly in the native form
Clausthalite, PbSe occurring in close associationship with galena and sphalerite
Germany; Tilkerode, Harz 250 > 1000 (0.25 and frequently within these two sulphides as specks and blebs.
~erzelianite,Cu,Se This has been recently confirmed by the researches of
Sweden: Skrikerum 100 >I000 tO.10 2 Mincheva-Stefanova and Stefanov (1972) who analyzed some
~zecho~lovakia; Bukov 0.1 1460 0.00007 3
Umangite, Cu,Se, 65 sphalerites from various lead-zinc and polymetallic depos-
Canada; Beaverlodge dis- its in Bulgaria. Their values range widely (0.0012-4.08 ppm
trict, Sask. 0.3 8450 0.00003 3 Au); most of the gold is present in the sphalerite as very finely
References: 1 . Hintze (1889-1968); Doelter et a/. (191 1-1931); Palache el a/. dispersed inclusions of the native metal. In some sphalerites
(1944); Chukhrov ( 1 960-1965),
2. Noddack and Noddack (1931).
the dark coloured zones were relatively enriched in gold
3. Laboratories, Mines Branch and Geological Survey of Canada. compared with the lighter zones. The greenish shade of a
yellowish green cleiophane (greenish sphalerite with a gold
As shown in Table 9 silver tends to predominate over content of 0.0792 ppm) was thought to be due to the presence
gold in the base metal tellurides and selenides, and the Au/Ag of very finely dispersed gold throughout the mineral. Accord-
ratio is invariably less than 1, often by several orders of ing to my observations, the case for galena may, however, be
magnitude, especially in the selenides. In the tellurides and somewhat different, since some rather pure galenas contain
selenides gold may replace Ag, Pb, Ni, Bi and Cu, although in high contents of gold. In such galenas gold may replace lead,
many of these minerals, especially the tellurides, small the electronic compensation being provided by tellurium in
amounts of gold tellurides may be mixed with the base metal the sulphur positions. Alternatively these galenas may contain
varieties. microscopic specks of gold tellurides. Whatever the mech-
Gold in sulphides, arsenides, antimonides, sulphosalts and similar anism it is common to find tellurium in most auriferous
minerals galenas.
There is a large literature on the gold content of these In a recent paper Parilov and Netaliyeva (1973) camed
minerals. The data in Tables 10 and 11 have been compiled up out a number of leaching experiments on argentiferous sphal-
to the end of 1975 from the most significant works on the erite using NH,OH. Their results indicate that much of the
subject and from the numerous analyses done in the laborato- silver in sphalerite is present in the halide form (AgCl),
ries of the Geological Survey. It is recognized that the data are possibly as epitaxitic inclusions because of the similarities in
incomplete, but the ranges shown give an idea of the gold the crystal structures of ZnS and AgCl. Perhaps some of the
content to be expected in the common sulphides, arsenides, gold in some sphalerites is, likewise, present in the halide
etc. form.
One of the major problems in ascertaining the role of In the various copper, silver and antimony sulphides and
gold in sulphides, arsenides and allied minerals is the matter sulphide-arsenides gold occurs native and apparently as a
of purity of the samples. In a great many occurrences the lattice constituent. Chalcocite, bornite, chalcopyrite and enar-
sulphides, arsenides, etc. are intimately admixed with native gite frequently carry relatively high contents of gold, yet do
gold and gold minerals or contain these minerals as blebs, not exhibit any evidence of the presence of the free metal
specks and small crystals. In many cases the investigators do under the highest magnifications possible with the ore micro-
not state whether the minerals are homogeneous or not, and it scope. In this case it seems probable that gold is a lattice
is impossible to tell if the gold is in the lattices of the minerals constituent substituting in the copper sites. The same situation
or present in one or more admixed gold minerals. Geochem- prevails for a variety of silver minerals, including argentite,
ists doing spectrographic and other types of analytical work freibergite and argyrodite, suggesting that gold in these
 Contents

Table 10. Gold and silver contents of some common sulphides, arsenides, antimonides, bismuthides and sulphosalts
Mineral and Au/Ag
locality Au Ag ratio Reference Remarks
(PP~)
ARSENIDES AND ANTIMONIDES
Niccolite, NiAs
Various Purity unknown
Canada; Cobalt, Ont. Pure
Smalite, [(Co,Ni)Asr,]
Canada; O'Brien Mine, Cobalt, Ont. Contains micro-
inclusions of
silver
Skutterudite, (Co,Ni)As,
Various Purity unknown
Morocco Pure
Canada; Cobalt, Ont. Contains micro-
inclusions of
native silver
Safflorite, (Co,Fe)As,
various Purity unknown
Rammelsbergite, NiAs,
Germany; Schneeberg Purity unknown
Domeykite, Cu,As
Mexico; Paracatas Purity unknown
Sperrylite, PtAs,
Canada; Sudbury, Ont. Purity unknown
Canada; Sudbury, Ont. Pure
Breithauptite, NiSb
Canada; Cobalt, Ont. Contains micro
inclusions of
silver
SULPHIDES AND SULPHIDE-
ARSENIDES
Chalcocite, Cu,S
U.S.A.; Kennecott Mine, Alaska Pure
U.S.A.; Butte, Montana Purity unknown
U.S.A.; Butte, Montana Pure
S.W. Africa; Tsumeb Pure
Canada; Alma, N.B. Pure
Canada; Dorchester, N.B. Pure
Bornite, Cu,FeS,
Germany; Mansfield Purity unknown
Canada; Copper Mountain, B.C. Pure
Canada; Batachewan Bay, Ont Pure
Galena, PbS
U.S.S.R.; Almalyk Purity unknown
U.S.S.R.; Karamazar deposit Purity unknown
Germany; Thuringia Purity unknown
South Africa Purity unknown
Canada; Keno Hill, Yukon Contains minor
amounts of tet-
rahedrite
Canada; Walton, N.S. <0.02 Pure; assay
Canada; Carleton Place, Ont. 0.015 Pure; assay
Canada; Hudson Bay Range, B.C. trace 98%pure
Sphalerite, ZnS
Germany; Silesia Purity unknown
Germany; Biihl Purity unknown
U.S.S.R.; Chukotka Purity unknown
U.S.S.R.; Karamazar deposit Purity unknown
U.S.S.R.; Uzbekistan Purity unknown
Canada; Keno Hill, Y.T. Some specimens
contain tetrahe-
drite
Canada; Yellowknife, N.W.T. Pure; spectro-
graphic analyses
Canada; Hudson Bay Range, B.C. 94-97%pure
Canada; Orchan Mine, Que. Mill concen-
trate
Canada; Normetal Mine, Que. Mill concen-
trate
 Contents

Mineral and Au/Ag

localitv Au Ag ratio Reference Remarks

Chalcopyrite, CuFeS,
Germany; Clausthal Purity unknown
Germany; Zwickau Purity unknown
Germany; Thiiringia Purity unknown
U.S.S.R.; Almalyk Purity unknown
U.S.S.R.; Karamazar deposit Purity unknown
U.S.S.R.; Uzbekistan Purity unknown
Canada; Yellowknife, N.W.T. Pure; spectro-
graphic analyses
Canada; Keno Hill, Y.T Pure; assay
Canada; Walton, N.S. Pure; assay
Canada; Hudson Bay Range, B.C. 97% pure
Canada; Home Mine, Noranda, Que. Mill concen-
trate
Canada; Opemiska Mine, Que. Mill concen-
trate
Canada; Orchan Mine, Que. Mill concen-
trate
Canada; Campbell-Chibougamu Mine,
Que. Mill concen-
trate
Canada; Normetal Mine, Que. Mill concen-
trate
Pyrrhotite, Fel .,S
Norway; FrQysa Purity unknown
Germany; Biihl Purity unknown
U.S.S.R.; Chukotka Purity unknown
East Greenland Analysis by
neutron activa-
tion
Canada; Buckingham, Que. P u r e ; assay
sample from
pegmatite
Canada; Yellowknife, N.W.T. Pure; spectro-
graphic analysis
Canada; Hudson Bay Range, B.C. 98% pure
Pentlandite, (Fe,Ni),S,
Norway; Espedalen Purity uncertain
Germany; St. Blasien Purity uncertain
Stannite; Cu,FeSnS,
England; Cornwall Purity uncertain
Czechoslovakia; Zinnwald Purity uncertain
Argentite (Acanthite), A@
Germany; Freiberg Purity uncertain
Canada; Cobalt, Ont. Pure
Canada; Thunder Bay district, Ont. Pure
Canada; Echo Bay, N.W.T. Pure
Cinnabar, HgS
Spain; Almaden Pure
U.S.S.R.; Khaydarkan deposit Pure
U.S.A.; New Almaden, Calif. Pure
Stibnite, Sb,S?,
Germany; Thuringia Purity unknown
U.S.S.R.; Chukotka Purity unknown
Canada; Yellowknife, N.W.T. Impure; con-
tains native
gold, aurosti-
bite, tetrahe-
drite, etc.
Japan Pure
Bismuthinite, Bi,S3
Canada; Wakefield Tp., Que. Pure
Hungary; B h a t Mines Contains inclu-
sions of native
gold
Molybdenite, MoS,
Various Purity unknown
Germany; Thiiringia Purity unknown
Canada; Yellowknife, N.W.T. Pure
 Contents

Table 10. (cont'd.)

Mineral and Au/Ag
locality Au Ag ratio Reference Remarks
(PP~)
Pyrite, FeS,
South Africa (Rand) Probably con-
tains inclusions
of gold
East Greenland Purity unknown
Germany; Thiiringia Purity unknown
Norway; various Purity unknown
Italy; various Purity unknown
U.S.S.R.; Almalyk Purity unknown
U.S.S.R.; Chukotka Purity unknown
U.S.S.R.; Karamazar deposit Purity unknown
U.S.S.R.; Uzbekistan Purity unknown
Canada; Hudson Bay Range, B.C. 80% pure
Alabandite, MnS
Roumania; Nagyag Purity unknown
Marcmite, FeS,
Germany; Westphalia Purity unknown
Siegenite, (Co,Ni),S,
Germany Purity unknown
Arsenopyrite, FeAsS
Norway; Skutterud Purity unknown
Germany; Saxony Purity unknown
Germany; Thiiringia Purity unknown
U.S.S.R.; Chukotka Purity unknown
U.S.S.R.; Karamazar deposit
U.S.S.R.; Uzbekistan
Canada; Hudson Bay Range, B.C. 99%pure
Cobaltite, CoAsS
Canada; Cobalt, Ont. Purity unknown
Norway; Skutterud Purity unknown
Norway; Skutterud Purity unknown
Sweden; Tunaberg Purity unknown
Germany; various Purity unknown
Germany; T h i i ~ g i a Purity unknown
Canada; Cobalt, Ont. Contains micro-
inclusions of sil-
ver
Gersdorffite, NiAsS
Germany; various
Ullmannite, NiSbS
Germany; various
Germany; Thiiringia
SULPHOSALTS
Tetrahedrite, Cu,,Sb,S,,
England; Cornwall Purity unknown
Austria; Tyrol Purity unknown
Germany; Thiiringia Purity unknown
U.S.S.R.; Karamazar deposit Purity unknown
Canada; Yellowknife, N.W.T. Pure
Canada; Keno Hill, Y.T. (freibergite) Pure
Canada; Clyde Forks, Ont. Pure
Canada; Hudson Bay Range, B.C.
Tennantite, Cu,,As,S,,
Canada: Walton, N.S. Pure
~oulan&te, P~;s~,s,,
Canada; Keno Hill, Y.T. Pure
Jamesonite. Pb. FeSb,S..
Canada; Dublin G U ~ ~ ; Y . T . Pure
Germanite, Cu,(Ge,Ga,Fe,Zn)(As,S),
S.W. Africa; Tsumeb 40 800 0.05 2 Purity unknown
References: 1 . Goldschmidt and Peters (1932). 10. Mine analyses.
2. Ncddack and Noddack (1931). I I . Koch, S. (1948), Acta Mineral. Petrog. vo1.2, p. 4
3. Badalov and Terekhovich (1966). 12. Kirkham (1968).
4. Fischer (1958-1959).
5. Sidorov (1966).
6. Vincent and Crocket (1960).
7. Minguui (1947).
8. Badalov and Badalova (1967).
9. Analyses by laboratories, Geological Survey of Canada, Mines Branch, and Bondar-Clegg and Co. Ltd., Ottawa.
 Contents

Table 11. Gold and silver contents of pyrite, pyrrhotite and arsenopyrite from some Canadian mineral deposits and rocks
Mineral and locality Au Ag Au/Ag ratio As Sb Remarks

Pyrite:
Buckingham, Quebec In pegmatites
(composite sample)
Richardson Mine, In skarn
Eldorado, Ont.
Keno and Galena Hills, 10-265 Not associated with arsenopyrite.
Y.T. (6 samples from No gold seen in polished sections.
Pb-Zn-Ag Deposits) Minor tetrahedrite in some samples
Keno and Galena Hills, 10-1020 Associated with arsenopyrite. No
Y.T. (3 samples from gold seen in polished sections.
gold-quartz deposits) Minor tetrahedrite and other
sulphosalts in some samples
Yellowknife, N.W.T. 5-50 In gold-quartz deposits
Walton, N.S. 40 Associated with chalcopyrite,
(1 composite sample) galena, sphalerite and tennantite in
Pb-Zn-Ag orebody
Blind River, 6 Pure, from uraniferous ore
Elliot Lake, Ont.
Geco Mine, Massive sulphide body
Manitouwadge, Ont.
Flin Flon Mine, Man. Massive sulphide body
Kidd Creek Mine (Texas Massive sulphide body
Gulf Sulphur),
Timmins, Ont.
Nigadoo Mine, Massive sulphide body
Bathurst, N.B.
Heath Steele Mine, N.B. Massive sulphide body
Home Mine, Massive sulphide body
Noranda, Que.
Faro Mine, Y.T. Massive sulphide body
Weedon Pyrite Mine, Massive sulphide body
Que.
Louvem Mine, Massive sulphide body
Val #Or, Que.
New Calumet Mine, Que. Skarn
Cobalt area, Ont. In pyritiferous graphitic schist and
slate interbedded with greenstone.
Minor amounts of chalcopyrite,
pyrrhotite and other sulphides
Keno-Galena Hills, Y.T. 15-34 In quartzite, phyllite and
schist remote from veins
Walton, N.S. 26-124 In shales; well removed from
(10 composite samples) mineralized zones
Walton, N.S. 5-28 In coalified plant zones near minor
(3 composite samples) faults
Ovens, N.S. 6-21 In slates and greywacke
(2 composite samples)
Rawdon area, N.S. 7 In slates
(composite sample)
Wabana, Nfld. Pyritiferous zone in iron beds
(composite sample)
Florence area, Ont. In Devonian shales
Port Hood, N.S. In coal
Stonehaven, N.B. In pyritiferous coal-bearing
sandstone. Minor amount of galena
present
Champlain Lookout, Pyrite cubes in Grenville gneiss
Gatineau Park, Que.
Pyrrhotite:
South of Bancroft, Ont. In quartzites
Buckingham, Que. In pegmatites
Yellowknife, N.W.T. In gold-quartz veins
(spectrographic analyses)
St. Stephen, N.B. In nickel deposit
Argenteuil Co., Que.
Noranda, Que. In Cu-Zn deposit; minor
chalcopyrite
Hastings County, Ont. Pegmatite
MacDonald Mine,
 Contents

Table 11. (cont'd.)

Mineral and locality Au Ag Au/Ag ratio As Sb Remarks

(PP~) (PP~)
Pyrrhotite (cont'd.):
Garson Mine, Sudbury, 0.220 <15 Massive sulphide deposit
Ont.
Alexo Mine, Cochrane, 0.220 <15 Massive sulphide deposit
Ont.
Leroi Mine, Rossland, 2.110 <15 Massive sulphide deposit
B.C.
Arsenopyrite:
Keno-Galena Hills, Y.T. 9.7-17.3 380-1 160 In gold-quartz veins
Dublin Gulch area, Y.T. 2.4 170-190 In gold-quartz veins
Yellowknife, N.W.T. 10 10-100 In gold-quartz veins
West Lake Gold Mine, >500 330 In gold-quartz veins
Mt. Uniacke, N.S.
Marmora Tp., Hastings 3.75 45 Gold-quartz prospect
County, Ont.
Howry Creek Gold Mine, 17.85 50 In gold-quartz veins
Curtin Tp., Sudbury
district, Ont.
Ovens area, N.S. 2.05 0.5 4.1 >40% 12-200 In slates and greywacke
Molega area, N.S. 5.95 0.8 7.4 >40% 180 In slates and greywacke near
gold-quartz veins
*Analyses by Laboratories, Geological Survey of Canada and Bondar-Clegg and Co. Ltd., Ottawa.

minerals occupies some of the silver sites in the lattice. The antimony, as shown in Table 11. With respect to pyrite there
situation with stibnite is complex. Pure stibnite from Japan is no consistent relationship between the arsenic and antimo-
appears to contain relatively little gold and silver. In other ny contents and the gold content; the same is true as regards
deposits, however, the mineral is gold- and silver-bearing as at the antimony and gold contents in arsenopyrite. In pure pyrite
Yellowknife and Red Lake in Canada and in the Chukotka the Au/Ag ratio is generally less than 1 in all types of
deposits, U.S.S.R. In the Canadian deposits examined by the occurrences according to our analyses and those published in
writer the stibnite is intimately intergrown with tetrahedrite the literature. Only rarely have we found exceptions to this
which is gold-bearing and with aurostibite and finely divided generalization, and these are obvious such as in samples where
native gold which cannot effectively be separated from the the pyrite wntains visible gold as blebs or in late fractures. In
antimony sulphide prior to analysis. Hand picked blades of samples of pyrite from the Rand ores we have analyzed we
stibnite from these deposits, however, generally contain only a have noted an Au/Ag ratio generally greater than 1, but some
little gold. These facts suggest that relatively little gold enters samples give ratios less than 1. Those having the high ratios
the stibnite lattice, and that if gold is present in stibnite it generally have specks of native gold which cannot be physical-
occurs predominantly in the native form, as aurostibite, or in ly separated from the pyrite. Many investigators have com-
admixed sulphosalts. It is of interest to note, however, that mented upon the close association of gold and pyrite in the
Dickson et al. (1975) found that synthetic stibnite, orpiment Rand among whom Pelletier (1940), Liebenberg (1955) and
and realgar took up considerable amounts of gold from the Saager (1969) should be mentioned as having made detailed
gold tubes used in their synthetic studies: stibnite from 1000 studies. It is of interest to note that the Au/Ag ratio in the
to 2000 ppm Au; orpiment from 100 to 2000 ppm Au; and pyrite in the relatively nonauriferous Blind River-Elliot Lake
realgar from 50 to 200 ppm Au. The exact nature of the gold quartz-pebble conglomerates have a low ratio (0.05) (Table
in the sulphides was not determined. 11). The Au/Ag ratio in arsenopyrite appears to be erratic
Of the various sulphosalts, the tetrahedrite-tennantite judging from some of my data and those in the literature.
series is the most consistently enriched in gold. Only rarely However, in a number of Nova Scotia deposits where I have
can native gold or other gold minerals be detected in pure carefully examined coexisting pyrite and arsenopyrite, both
auriferous tetrahedrite-tennantite samples suggesting that devoid of secondary gold in fractures, the ratio is generally
most of the gold in these minerals is a lattice constituent greater than 1 in arsenopyrite and less than 1 in pyrite. This
substituting for copper. That gold prefers the copper sul- suggests a tendency for arsenopyrite to concentrate gold
phosalts has been shown by the writer at Keno Hill (Boyle, whereas pyrite tends to take up silver.
1965~).There, tetrahedrite (freibergite) contains from 11 to 45 The problem of the nature of gold (and silver) in pyrite
ppm Au whereas the closely associated lead sulphosalts, and arsenopyrite is an old one that first appeared when
boulangerite and jamesonite, contain of the order of 0.5 ppm metallurgists sought to deal with certain gold ores that are not
Au. In a qualitative way the same is true at Yellowknife, directly amenable to cyanidation processes. Most of these ores
although here great difficulty is encountered in obtaining pure are arsenical and usually contain abundant arsenopyrite,
separates of each mineral. which wntains most of the gold. Some, such as those in the
Gold is commonly found in pyrite and arsenopyrite, Bau area, Sarawak, contain the bulk of the gold in native
especially in auriferous deposits, a feature of the element arsenic and minor arsenopyrite. Others are characterized
which has been known for a long time. Commonly associated mainly by gold-bearing pyrite, and still others contain gold-
elements in the pyrite of both host rocks and deposits are bearing arsenopyrite, sulphosalts and pyrite. Visible and
silver, arsenic and antimony and in arsenopyrite, silver and microscopic native gold is present in most of these deposits
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

but often makes up only a small proportion of the total Some synthetic and detailed analytical studies have been
amount of gold in the ores. The remainder of the gold is in an done on the problem of the state of gold in pyrite and
'invisible' form and can only be won by roasting the ores, arsenopyrite. Burg (1930, 1935), who first investigated the
which liberates the gold in a state amenable to cyanidation. In problem, showed that when natural gold-bearing pyrite from
some gold ores such as those in Fiji and southeastern Ontario Brad is heated to 600°C in a vacuum and the liberated
practically all of the gold is 'invisible' in either arsenopyrite or sulphur vapour is removed, the pyrite is converted to pyrrho-
pyrite. tite, and the gold aggregates into small visible particles. If the
Investigations on the nature of gold (and silver) in pyrite sulphur vapour is retained, the gold reacts with it to form a
and arsenopyrite have been carried out in the past by Biirg gold sulphide with variable stability features. Burg thought
(1930, 1935), Head (1934, 1935a,b), Haycock (1937), Van that his results suggested solid solution of gold in the pyrite.
Aube1(1939), Kurauti (1941), Maslenitsky (1944) and Stillwell Kurauti (1941) and Maslenitsky (1944) synthesized gold-bear-
and Edwards (1946) and more recently by Edwards (1958), ing pyrite in which the gold could not be detected microscopi-
Clark (1960), Boyle (1961a, 1965a), Aubert et al. (1964), cally. Maslenitsky found that his synthetic pryrite, containing
Tyurin (1965a), Schweigart (1965), McPheat et ai. (1969), some 340 ppm gold, when heated in vacuo at 600°C behaved
Korobushkin (1970), Kalitkina (197 l), Badalov (1972), Sak- in a similar manner to the natural pyrite used by Burg. He
harova et al. (1972), Wells and Mullens (1973), Klempert et al. also observed inclusions of gold sulphide in his heated
(1973) and Gavrilov et al. (1974). Two views predominate, one synthetic pyrite, and he was also able to synthesize Au,S, and
that the gold is present in chemical combination in the pyrite determine its optical properties and etching behaviour. Kurau-
and arsenopyrite, and the other that the gold is present in a ti's results are especially significant since he found that up to
finely divided (colloidal?), often submicroscopic state ( t 0 . 1 ~ ) . 2000 ppm gold could be substituted in the pyrite lattice, and
The former view appears the more probable as will be shown further that the lattice constant of pyrite decreased with
in the following. increasing gold content, a feature that proves solid solution of
Examination of most polished sections of gold-bearing gold in pyrite. Tyurin (1965a), on the other hand, found in
pyrite and arsenopyrite at high magnifications generally some experiments that gold concomitantly precipitated with
reveals the presence of minute blebs or stringers of native gold pyrite was present in discrete particles that did not exceed 3~
or other gold minerals that frequently appear to be of a in size. Clark (1960) also found that the solubility of gold in
secondary (exsolved) nature. Calculations of the amount of arsenopyrite at 6W°C was insufficient to measurably affect
gold present in these forms generally agree with the assay the 131 spacing of the mineral. He did not rule out, however,
values within the experimental errors inherent in such work. the possibility of a small gold solubility in arsenopyrite, for
There are, however, a number of deposits where the assay example 0.1 per cent (1000 ppm or approximately 30 oz
values of pyrite and arsenopyrite, particularly the latter, Au/ton of arsenopyrite). In a survey of research for 1969
greatly exceed the amount of gold minerals visible at the (U.S.G.S., Prof. Pap. 650-A, p. A108) it was reported that P.B.
highest magnifications under the microscope. This gold is Barton has found that chalcopyrite can dissolve more than 1.6
generally not amenable to cyanidation and, in my experience, weight per cent Au at 650°C and that much of this gold is
can only be recovered, by complete breakdown of the pyrite exsolved on cooling. In the 600-700°C temperature range,
or arsenopyrite lattice either by roasting or by attack with galena dissolves between 0.1 and 0.5 weight per cent Au.
nitric acid or aqua regia. Under the microprobe, domains or Bismuth increases the solubility of gold, whereas silver de-
points of high gold content in the pyrite and arsenopyrite can creases it. This suggests that the mechanism for the incorpora-
rarely be made out, although in some specimens from Chate- tion of gold in galena involves Au(1) rather than Au(II1). In
let, France, Aubert et al. (1964) were able to distinguish the same range of temperatures, the solubility of gold in
gold-rich areas in arsenopyrite. Microscopic and microprobe pyrite, pyrrhotite and arsenopyrite is less, perhaps much less,
work, therefore, suggest that much of the 'invisible' gold in than 0.1 weight per cent. Korobushkin (1970) determined by
pyrite and arsenopyrite is present in a submicroscopic form, selective chemical methods that gold in gold-bearing pyrite
probably a lattice constituent of these two minerals. This view and arsenopyrite in a deposit in western Kazakhstan was
is confirmed by recent research using a microprobe and other present in two forms - in a cationic form, the gold substitut-
techniques on auriferous pyrite (0.065 oz/ton) by McPheat et ing isomorphously for iron, and in an anionic form, the gold
al. (1969). They found that 0.02 to 0.03 oz/ton gold was in substituting for atoms of arsenic-because of the similarlity of
solid solution and the balance of the metal was finely the atomic radii of the two elements (Au, 1.44A; As, 1.39A).
dispersed as grains throughout the pyrite. Wells and Mullens This view has been reiterated by Badalov (1972). Finally,
(1973), however, opted for the particulate gold theory in the Kirillov et al. (1970) experimented with iron monosulphide
Carlin and Cortez ores of Nevada. Using a microprobe they and dithiosulphatoaurate, Na,[Au(S,O,),] in an attempt to
found that much of the gold in the deposits was present in a synthesize auriferous pyrite at low temperatures. Their results
submicroscopic form ((0.5 p) in tiny grains (t0.005 mm) of indicate that the thiosulphate complex disproportionates in
arsenian pyrite and in the thin rims of larger pyrite grains; aqueous solution in the presence of FeS and that gold passes
also in small grains of arsenopyrite where it is present. They into the precipitate. The precipitate evidently consisted of FeS
concluded that since the gold content varies widely within the grains covered by films of auriferous FeS,. They write equa-
interior of large pyrite grains, within pyrite rims and within tions for the reactions as follows:
the disseminated pyrite and arsenopyrite - some pyrite and
+
arsenopyrite is barren - that the gold possibly occurs as 2Na3[Au(S,0,),] 4H,O+ 2Au + S + 3Na$O, + 3H,S
submicron particles of native gold or of a gold mineral. +
FeS S+ FeS,
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

Extensive chemical and microscopic work on both aurif- preferably along fractures and grain boundaries, in both pyrite
erous pyrite and arsenopyrite by Haycock (1937), Stillwell and and arsenopyrite. During heating tests Klempert et a[. (1973),
Edwards 1946, Edwards (1958) and McPheat et al. (1969) on likewise, observed exsolution of gold from the auriferous
Canadian, Fijian and Australian gold ores strongly suggest ('invisible' gold) pyrite of the Terek deposit in Uzbekistan.
solid solution of gold in the lattice of both pyrite and Narseev and Starova (in Petrovskaya, 1974) noted that some
arsenopyrite. The writer's research on gold-bearing pyrite and 95 per cent of the gold in the Kalba deposits of eastern
arsenopyrite from Yellowknife, N.W.T.; Keno Hill, Yukon; Kazakhstan was dispersed in pyrite and arsenopyrite. After
southeastern Ontario; and Nova Scotia suggests the same heating the pyrite for 20 min. at 250°C enlarged gold particles
phenomenon. and a decrease in the cell parameter of the pyrite took place
There are theoretical reasons for suspecting that gold (from 5.4275 to 5.4095). They suggested that point defects in
(and silver) enter the structure of pyrite and arsenopyrite. In the lattice of pyrite occur at the sites of the dispersed gold.
pyrite (and the closely related arsenopyrite) each iron atom is The decreased microhardness found for the auriferous pyrite
covalently bonded to six sulphur atoms at the comers of a was considered to be due to linear dislocations. For the
nearly regular octahedron. In addition there is also a moderate auriferous arsenopyrite the investigators noted a tendency to
degree of metallic bonding (Fe-Fe) indicated by the metallic fine acicular to finely prismatic habit, increased cell parame-
lustre, especially of arsenopyrite. The octahedral covalent ters a and b and decreased microhardness. Other details of the
radius of ferrous iron in pyrite is 1.23& and for gold in auriferous pyrite and arsenopyrite should be sought in the
aurostibite, AuSb,, a mineral isostructural with pyrite, the original paper.
octahedral radius is 1.40A. There is also a similarity in the Having regard to the above discussion one can postulate,
covalent radius of arsenic (1.39R) and gold (1.40A). GOM will therefore, that early formed high temperature pyrite and
form three rather unstable artificial sulphides, AuS, Au,S and arsenopyrite probably take up gold and silver largely in solid
Au,S, indicating that the bond to sulphur although weak is solution, or as atomic layers on the growing faces of the
nonetheless possible. These considerations suggest that some sulphide minerals, features that appear to be common in some
gold may substitute in the iron sites of pyrite and arsenopyrite of the deposits studied by the writer (e.g., Yellowknife; Boyle,
mainly because of similar octahedral radii, a certain affinity 1961~).These features are also commented on by Haycock
for sulphur, and the isostructural relationship of the two (1937), Stillwell and Edwards (1946), Edwards (1958) and
minerals pyrite and aurostibite.18 There may also be some McPheat et al. (1969). At lower temperatures the presence of
substitution of gold for arsenic in arsenopyrite because of the foreign constituents such as gold and silver distort the pyrite
similar radii and charges of the two elements. In addition the and arsenopyrite lattices, with a consequent rise in the free
metallic binding in the sulphides, especially arsenopyrite, energy of the crystals. In order to reduce the free energy of the
confers certain alloying properties on them, permitting other system to a minimum under the prevailing conditions gold
metals such as gold and silver to reside in the lattices without and silver migrate to nearby low chemical potential sites such
excessive distortion especially at high temperatures. Another as fractures and grain boundaries where they crystallize as
reason why pyrite is commonly auriferous may be due to silver-bearing native gold. This appears to explain the frequent
certain epitaxial relationships which take place when pyrite occurrence of much 'invisible' gold and silver in relatively
and gold are precipitated in veins. Thus, Amosov and Gureev unfractured and unrecrystallized pyrite and arsenopyrite;
(1970) noted that gold forms thin crystalline crusts on pyrite where reworking, recrystallization and fracturing are evident
and concluded that the crystalline data for gold and pyrite the gold is largely present in the native form, although small
suggest epitaxy as a possibility. Further investigations by amounts may remain within the lattice of the two minerals.
Amosov et al. (1975) indicate the cocrystallization of pyrite The exsolution phenomenon described above is probably
and native gold. They suggest that the cocrystallization largely the result of diffusion processes, a conclusion support-
phenomenon is not the trapping of gold particles by pyrite but ed by the experimental work of Clark (1960) who found that
the deposition of gold on the surface of the growing pyrite gold diffused rapidly through arsenopyrite at temperatures of
crystals. Research by Sakharova et al. (1972) on gold-bearing 660°C and higher.
sulphides (pyrite, arsenopyrite, chalcopyrite and pyrrhotite)
from the Darasun deposit in East Transbaikal further con- Gold in halides, carbonates, sulphates, oxides and similar
firms the exsolution hypothesis. They found that during minerals
heating tests of polished sections of the various sulphides that Data on the gold content of some halides, carbonates, sul-
the finely dispersed ('invisible') gold aggregated into larger phates, oxides, etc. are given in Table 12. The nature of gold
particles around 250 to 300°C. A disintegration of some of the in many of these minerals is difficult to determine, particularly
larger 'visible' gold particles was also noted in some cases. in those of supergene derivation because of their finely
They concluded that over a long period of time, gold in the divided, often pulverulent habit, and their common intermix-
sulphides could be redistributed at relatively low temperatures ture with a variety of other supergene minerals.
(150-250°C) during the late stage of hydrothermal processes The common halides contain very little gold, generally
in veins. Kalitkina (1971) also found experimentally that gold less than 0.01 ppm. Seeland (1973a,b) noted the presence of
migrated relatively rapidly by diffusion in the solid state, gold in only one halite sample from Paleozoic rocks in
Michigan. The average gold content in the halite was 0.06
ppm. There appear to be no published analyses of the gold
lsNote that practically all pyrite and arsenopyrite (Table 1I) contains
antimony - sufficient it would seem to bind the gold in the pyrite and content of the various silver halides, nor of the mercury,
arsenopyrite lattice, thus neutralizing any charge differences. copper and lead-copper halides and complex carbonate or
 Contents

Table 12. Gold and silver contents of some halides, carbonates, sulphates, phosphates, arsenates, antimonates, nitrates, tungstates
and oxides.
Mineral and locality Au Ag Au/Ag ratio Reference Remarks
(PP~)
HALIDES
Halite, NaCl
England; Cheshire Purity unknown
Germany; Stassfurt Purity unknown
Canada; Pugwash, N.S. Pure
U.S.A.; Michigan
Sylvite, KC1
Germany; Mecklenburg Purity unknown
Germany; various Potassium salts
Carnallite, KMgCl3.6H,O
Germany; Bernburg Purity unknown
Sylvite, KCl, and Carnallite,
KMgC1,-6H,O
Canada; Ormiston, Sask. Pure
Fluorite, CaF,
Canada; St. Lawrence, Nfld. Pure
Canada; Sandy Creek, Que. Pure
Canada; Madoc, Ont. Pure
Chlorargyrite, AgCl
Chile; Chanarcillo Pure
Australia; Broken Hill, N.S.W. Pure
CARBONA TES
Siderite, FeCO,
Canada; Keno Hill, Y.T. Pure
Dolomite, CaMg (CO,),
Canada; Portage du Fort, Que. Pure
Canada; Bancroft, Ont. Pure
Canada; Actinolite, Ont. Pure
Calcite, CaCO,
Canada; Pinks Lake, Que. Pure
Canada; Brompton Lake, Que. Pure
Mexico; Chihuahua Pure
Calcite (marble)
Canada; Carleton Place, Ont. Pure
Malachite, Cu,(OH),(CO,)
Zaire; Katanga Pure
U.S.A.; Bisbee, Ariz. Pure
Azurite, Cu,(OH),(CO,),
Southwest Africa; Tsumeb Pure
U.S.A.; Bisbee, Ariz. Pure
SULPHA TES
Anhydrite, CaSO,
Germany; Plomnitz Purity unknown
Gypsum, CaS0;2H20
United States; Michigan
United States; Grand Rapids,
Mich. Purity unknown
United States; Salina, N.Y. Purity unknown
Canada; Keno Hill, Y.T. In lead-zinc-silverveins and
lodes
Canada; Walton, N.S. Evaporite beds, minor pyrite
in some samples
Kainite, KMg(S0,)Cl-3H,O
Germany; Plornnitz Purity unknown
Barite, BaSO,
Canada; Keno Hill area, Y.T. In veins (secondary?)
Canada; Madoc, Ont. Pure
Canada; Walton, N.S. Pure
Anglesite, PbSO,
Canada; Keno Hill, Y.T. Oxidation product of galena
Canada; Bathurst, N.B. In oxidized zone of massive
sulphide deposits
Jarosite, KFe,(SO,),(OH),
Various localities Gold probably largely
present in finely divided
native form in most samples
Various sulphates of iron, zinc, etc.
Canada; Keno Hill area, Y.T. Derived from oxidation of
pyrite, siderite, etc.
 Contents

Table 12. (cont'd.)

Mineral and locality Au Ag Au/Ag ratio Reference Remarks

(PP~)
PHOSPHATES, ARSENATES,
ANTIMONATES
Apatite, Ca,(PO,),(F,CI,OH)
Canada; Sandy Creek, Que. Pure
Canada; Sebastopol Tp., Ont. Pure
Canada; Cantley, Que. Pure
U.S.S.R.; various Bone phosphate
Triplite, (Mn,Fe),(PO,)F
South West Africa; Sandamab Purity unknown
Pyromotphite, [Pb,(PO,,AsO,),Cl]
Canada; Keno Hill area, Y.T. Contains some cerussite,
otherwise pure
Germany; Schwarzwald Purity unknown
Scorodite, (Fe,AI)(As0,)2H20
Canada; Keno Hill area, Y.T. Oxidation product of
gold-quartz-arsenopyrite
veins
Beudantite, PbFe,(AsO,)(SO,)(OH),
Canada; Bathurst, N.B. In oxidized zone of massive
sulphide deposits, pure
Bindheimite, Pb2Sb20,(0,0H)
Canada; Keno Hill area, Y.T. Alteration product of galena
and freibergite
NITRA TES
Soda-Niter, NaNO,
Chile Purity unknown
TUNGSTATES
Wolfamite, (Fe,Mn)(WO,)
Canada; Keno Hill area, Y.T. Pure
Scheelite, Ca(W0, )
Canada; Keno Hill area, Y.T. Pure
OXIDES
Magnetite, FeFe20,
United States; Helena, Mont. 0.003-0.329 Range and average of 44
(av., 0.037) analyses
U.S.S.R.; Altai-Sayan 0.048 Average of seven analyses
U.S.S.R.; Kazakhstan t0.0014.0120 In rocks
U.S.S.R.; Urals 0.0036 Average in granitoid rocks
U.S.S.R.: Altai. Transbaikal and
~rais ' Average in granitoid rocks
Canada; Marmora, Crowe Lake,
Ont. In skarn orebody
Canada; Hull, Que. Composite of magnetite
body in skarn
Ilmenite, FeTiO,
U.S.S.R.; Altai, Transbaikal and
Urals Average in granitoid rocks
U.S.S.R.; Urals Average in granitoid rocks
.
Canada: St. Urbain.. Oue. Pure
~ e m a t i t eFezO,
,
Canada; Yellowknife, N.W.T. In giant quartz veins
Canada; Walton, N.S. In oxidized zones of barite
deposits
Canada; Balderson, Ont. Pure
Canada; Plummer Tp., Ont. Pure
Pyrolusite, MnO,
Czechoslovakia; Platten Purity unknown
Psilomelane, BaMnZ+Mn;+O,,(OH),
Germany: Harz Purity unknown
Hausmannite, MnZ+Mn,3+0,
Sweden: Langban Purity unknown
Wad Mn Oxides
Germany; Thuringia 5 tl Purity unknown
United States; various 30-300 - Purity unknown
Various (U.S.A.; Sumatra, etc.) up to 1 Purity unknown
1000 or
more
United States; Arkansas 23 0.03 Purity unknown
Canada; Keno Hill, Y.T. 100-1000 <I In oxidized zones of
Pb-Zn-Ag deposits
 Contents

Table 12. (cont'd.)

Mineral and locality Au Ag Au/Ag ratio Reference Remarks

Wad (cont'd.) (PP~)
Canada; Walton, N.S. tO.O1 0.8-1.4 tl 21 Nodules in limestone
Canada; Walton, N.S. 0.34 0.68 0.5 21 Spring precipitates (average)
Oceans, manganese nodules 0.003 - - 12 Average
Canada; Nova Scotia lakes,
manganese nodules 0.004 - - 12 Average
Limonite, iron oxides
Various 1-35 1-1000 <I General estimate from world
or more literature. All in oxidized
zones of polymetallic
deposits
Canada; Keno Hill area, Y.T. 100-1000 <I In oxidized zones of
Pb-Zn-Ag deposits
Canada; Walton, N.S. 0.5 <l In oxidized zones of barite
deposits
Canada; Bathurst, N.B. 0.5-500 tl In gossans of massive
sulphide deposits
Cassiterite, SnO,
Various localities Purity unknown
Canada; Keno Hill area, Y .T. Pure
Uraninite, UO,
Norway; Brevik Purity unknown
Czechoslovakia; Jachymov Purity unknown
Pitchblende, UO,
Canada; Great Bear Lake, N.W.T. Pure
Thorianite, Tho,
Ceylon Purity unknown
Columbite, (Fe,Mn) (Nb,Ta),O,
Norway; Arendal Purity unknown
Chromite, FeCr,O,
Various localities Purity unknown
Canada; Bird River, Man. Pure
Samarskite. tantalite.
ilmenorutile
Various localities 0.02-0.65 0.2-0.3 - 19 Purity unknown
Note: nd - not determined
References: 1 . Liversidge (1 8 9 7 ~ ) . 12. Harriss et a/. (1 968).
2. Friedrick (1906). 13. Zvereva and Gavrilenko (1 97 I).
3. Lincoln (l9llh). 14. Goubeau and Birckenbach (1938).
4. Goldschmidt and Peters (1932). 15. Yasyrev (1969).
5. Noddack and Noddack (1 93 1). 16. Schmidt (1919).
6. Fischer ( 1958-1959). 17. Bushliakov (1971).
7. Mantei and Brownlow (1967). 18. Anoshin et a/. (1 970).
8. Shcherbakov and Perezhogin (1964). 19. Lunde (1927) and Lunde and Johnson (1928).
9. Hewett, Fleischer and Conklin (1963). 20. Seeland (1973a,b).
10. Clevenger and Caron (1 925). 21. Laboratories, Geological Survey of Canada and
l I . Foley (1 960). Bondar-Clegg and Co., Ltd., Ottawa.

hydroxide halides. Analyses of chlorargyite, AgCl, in laborato- Empire district, Colorado, are reported to contain as much as
ries of the Geological Survey show gold to be generally less 11.7 pprn Au, 10 pprn Te and 0.60 pprn Hg, all well above
than 10 ppm, indicating that there is little enrichment of the background amounts for the area (Lakin, 1969~).Higher-
precious metal in silver halides. than-background amounts of manganese, bismuth, cobalt,
All of the common carbonates have a very low gold nickel and zinc were also detected in the samples. Seeland
content, generally much less than 0.01 ppm. This is probably (1973a,b) noted the presence of gold in one sample of
due to the fact that the bond of gold to the carbonate radical gypsum-anhydrite from Paleozoic rocks in Michigan. The
is very weak or nonexistent. The complex copper carbonates amount recorded was 0.02 pprn Au.
can apparently accommodate small amounts of gold, probably As noted above halite and the common sulphates contain
substituting in the copper sites. only minor traces of gold. Friend and Allchin (1939), however,
Among the simple sulphates investigated the largest report 49 pprn Au in pale blue celestite and 85 pprn Au in
amounts of gold have been noted in anglesite from Keno Hill, deep red celestite from Yate, Gloucestershire, England. Co-
Yukon. Its presence in the mineral from this area, however, lourless crystals contained no detectable gold. In a later paper
appears to be spurious; the element is probably largely the same authors (Friend and Allchin, 1940) found up to 4
present in admixed scorodite, bindheimite and beudantite pprn Au in blue anhydrite from Cropwell Bishop, Notting-
which cannot be physically separated from the anglesite. The hamshire and an average of 23 pprn Au in deep blue Stassfurt
anglesite from the Bathurst area is relatively pure and contains halite. They attributed the various colours of these minerals to
on the average only 0.01 pprn Au. the presence of colloidal gold. The gold values recorded in
Hand-sorted concentrates of supergene sulphates of cop- these halite and sulphate samples are exceptionally high and
per and iron from underground workings of mines in the should be confirmed. The writer has been unable to find more
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

than a trace of gold (C0.01 ppm) in orange gypsum from In rocks and in a few auriferous deposits magnetite
Nova Scotia and in most coloured halite, celestite and anhy- carries gold. Some values are given in Table 12; others are
drite samples from various localities. However, one sample of quoted in subsequent sections on gold in rocks. The amount
blue halite from Heringen, Germany, and a sample of blue of gold in magnetites can range up to 0.05 ppm. The element
celestite from Wogau, Germany contained 0.125 and 0.110 apparently substitutes for iron in the magnetite lattice since
pprn Au respectively. The corresponding silver contents were free gold can rarely if ever be seen in the mineral. Platinum
2.8 and 0.4 ppm. group metals accompany gold in some magnetites from rocks
The basic sulphates of femc iron and other elements, the in the Urals (Fominykh and Znamenskii, 1974).
jarosites, frequently contain relatively high amounts of gold. Of the various supergene oxides, limonite and wad tend
Knopf (1915) recorded up to 7900 pprn Au (234 oz/ton) in to be the most common carriers of gold, especially where they
plumbojarosite from the Boss Mine, southern Nevada, and occur either in or near gold deposits. The presence of gold
Head and Miller (1928) found up to 89 pprn Au (2.6 oz/ton) (and especially silver) in wad (up to 1.3 oz/ton Au and 100
in jarosite from Beatty, Nevada and Marysvale, Utah. In oz/ton Ag or more) is an old problem discussed in great detail
U.S.S.R. Chukhrov et al. (1940) report gold- and silver- in the years past by Clevenger and Caron (1925) and numer-
bearing jarosites from the Maikain deposit, central Kazakh- ous others. The reasons for the extended study were mainly
stan, and Friedrich (1960) found gold in jarosite in the metallurgical since the manganiferous silver-bearing ores and
Rodalquilar deposit, Spain. In all of these deposits most of the some wad ores containing gold are highly refractory and onlv
gold is apparently present in the native state as finely divided yield their silver to cyanide solutions after intensive reduction.
particles. Despite this feature it would seem from my observa- After much study Clevenger and Caron and others concluded
tions that the jarosites, particularly plumojarosite and argen- that much of the silver in wad is held as silver manganite of
tojarosite, can accommodate some gold in their lattices. uncertain composition. More recent work concerning silver in
Argentojarosite may contain up to 18 per cent silver, a feature these ores is discussed by Boyle (19683). With respect to gold
proving considerable substitution of the metal in the alkali in wad-silver ores Clevenger and Caron concluded that the
sites of the jarosite lattice. One can suppose, therefore, that gold in some of these ores is amenable to direct cyanidation.
where mobile gold is present in the solutions from which and hence its extraction is not increased by reduction. In other
jarosite is crystallized that there may be some substitution of ores the gold follows silver, and is more or less refractory; on
Au(1) (1.37A) for Ag(1) (1.13A) because of somewhat similar reduction the recovery of gold is increased from such ores to
radii and similar electronic configurations. an even higher percentage than the silver. More recent papers
There is relatively little gold in any of the apatites on the occurrence of gold in manganese oxides include those
investigated in laboratories of the Geological Survey, but the by Foley (1960) who found up to 0.02 oz/ton Au in the
phosphates, pyromorphite and triplite, can apparently accom- manganese ores of Polk county, Arkansas; Harriss et al.
modate some gold in their lattices probably substituting in the (1968) who recorded the gold contents in manganese nodules
lead or iron sites. Some of the sedimentary bone phosphates in shown in Table 12; and Hrytsyk et al. (1969) who found
U.S.S.R. carry small amounts of gold. Smirnov and Entin native gold in the earthy manganese ores of the Chyvchyn
(1975) have noted a bond between gold and phosphorus in a Mountains, U.S.S.R.
number of genetically diverse phosphatic deposits in U.S.S.R. The occurrence of gold in limonite and other iron oxides,
In certain apatites from these deposits they recorded up to especially in the gossans of precious and base metal deposits.
0.030 pprn Au. is well known and has been repeatedly described in innumera-
~coroditefrom gold-bearing arsenopyrite veins invariably ble publications (see also Chapter IV).
contains gold, frequently in amounts up to 10 pprn or more. In recent years the writer has investigated the nature and
In my experience most of this is present in finely divided distribution of gold (and silver) in wad and limonite from a
native gold, although some pure specimens of scorodite in variety of gold-bearing deposits, mainly in Yukon, Northwest
which gold cannot be seen microscopically nor removed either Territories, New Brunswick and Nova Scotia. The results of
physically or chemically (by cyanide solutions) appear to the research concerning the silver have been published (Boyle,
contain the metal in lattice sites, probably substituting for 19683). The principal results with respect to gold include the
iron. Beudantite and bindheimite. likewise, invariably contain following:
gold, some of which cannot be removed physically nor 1. Some samples of wad and limonite have the gold (and
chemically. Some of this gold (together with silver) probably silver) uniformly distributed throughout the mineral com-
substitutes in the lead sites of the lattices of these minerals. It plexes; in other samples the gold (and silver) is erratically
is interesting to note that gold tends to concentrate in the distributed.
supergene arsenates and antimonates, a feature which suggests 2. Most of the gold- and silver-bearing wads and limo-
a definite coherence between the metal and arsenic and nites carry considerable quantities of silica, alumina, titanium,
antimony. This coherence is of course well known in hypogene phosphorus, arsenic and antimony (see, for instance, Tables
mineral assemblages. 42, 56 and 60 in Boyle, 1965~).
Both of the tungstates, wolframite and scheelite, may 3. In most samples of wad and limonite gold is present in
contain small amounts of gold. The nature of the gold is the native state and can be superpanned from samples of the
unknown. Probably most of it resides in microscopic particles minerals or leached by potassium cyanide. In some samples of
of the native metal. It is worth noting that there is a general wad and limonite the gold follows silver and is tightly bonded
association of tungsten, gold and silver in many types of gold to the manganese and iron complexes and is not readily
deposits. soluble in potassium cyanide or potassium thiosulphate. This
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRYOF GOLD

gold may be present as an adsorbed constituent or as a gold also come into play. During these reactions gold is co-
manganite, or ferrite although lts constitution is apparently precipitated with argentojarosite, plumbojarosite, beudantite,
amorphous (colloidal?) since no distinct X-ray patterns can be bindheimite and other hydrolytic products, all of which may
discerned from those of the wad and limonite minerals. In be intimately associated with the wad and limonite gels. On
certain samples with a relatively high organic content, the gold aging the wad-limonite complex tends to segregate out native
may be bound in organic (humic) complexes of manganese gold and other gold- and silver-bearing minerals.
and iron. In still other samples, particularly in gossans, the
gold (and silver) appear to be an integral part of admixed
minerals such as plumbojarosite or argentojarosite, beudan-
tite, bindheimite, scorodite and anglesite. As for the earth . . . it hath dust of gold.
One of the reasons for the enrichment of gold (and silver)
in wad and limonite, especially in gossans, is the fact that the
simple soluble species of the two elements are readily reduced
Geochemistry of gold in terrestrial materials
to the metals by ferrous and manganous salts. This feature is Summary accounts of the various aspects of the geochemistry
discussed further in Chapter IV. of gold in most terrestrial materials are contained in a large
Another reason for the enrichment of gold (and silver) in number of works including those by Maclaren (1908), Crane
wad and limonite is probably due to the colloidal behaviour of (19O8), Emmons (1917), Mellor (1923), Clarke (1924), Dunn
hydrous manganese dioxide and hydrous femc oxide. Hy- (1929), Goldschmidt and Peters (1932), Lindgren (1933), Van
drous manganese dioxide sols and gels carry a negative charge Aubel (1934), Emmons (1937), Fersman (1939), Zvyagintsev
and strongly adsorb cationic gold (and silver) to their surfaces. (1941), Gmelin (1950-1954), Bateman (1950), Rankama and
With aging, the gold may partake of the structure of the Sahama (1950), Smirnov (1951), Friedensburg (1953),
manganese dioxide complex, giving a gold manganite or some Goldschmidt (1954), Routhier (1963), Shcherbakov and Perez-
other similar compound. Alternatively the gold may simply hogin (1964), Smirnov (1965), Foss (1966u,b), Ziauddin
remain in an adsorbed state either at the grain boundaries of (1970), Uklonskii (1970), Machairas (1970a), Shcherbina
the microcrystals of the complex or perhaps in interstitial (1972), Allmann and Crocket (1972), Petrovskaya (1973),
positions. On recrystallization, after long periods of aging, Simons and Prim (1973) and Smirnov (1974). There is a
some of the gold may also be split out of the complex giving selected annotated bibliography on the geochemistry of gold
nuclei of native gold. Silica sols and gels and humic colloids, by Cooper (1971).
likewise, carry negative charges and tend to adsorb cationic In the following sections there are numerous tables on the
gold to their surfaces. Hence, the presence of these colloids in content of gold in the various earth materials. During the
wad would also tend to increase the amount of gold precipi- compilation of these tables considerable difficulty was en-
tated in the wad-silica-humic complex. Some gold thus pre- countered in deciding which analytical data in the literature
cipitated could conceivably also be bound as gold-manganese- should be used in the calculations because of the different
iron organic complexes. Under other conditions the man- analytical procedures employed, rock nomenclature, possible
ganese dioxide colloids may present a positively charged presence of gold mineralization and so on. These problems are
surface due to adsorption of a variety of cations. This then familiar to all geochemists who attempt to calculate normal or
permits the adsorption and/or coprecipitation of negative background abundance figures. I have been selective in
anionic complexes of gold or negative gold colloids. Another compiling the tables, utilizing only those data which in my
possibility may also account for the adsorption of gold on opinion have been obtained by reliable modern analytical
manganese colloids. The hydrated manganous oxide (hydrox- procedures on earth materials, which seemed to me from the
ide), MnO-H,O, appears to form during the initial stage of descriptions of the samples to be well removed from the
precipitation of manganese under a low oxidation potential, effects of gold mineralization. Admittedly this is a rather
and this gelatinous precipitate is later oxidized to hydrated subjective procedure, and I would stress the fact that the
manganese dioxide, MnO,.H,O. The hydrated manganous abundance figures given in the tables are only estimates at
oxide (hydroxide) adsorbs anions strongly and would, there- best. All of the data sources are given in the Selected
fore, tend to adsorb and/or coprecipitate the available nega- bibliography at the end of the bulletin.
tive anionic complexes of gold or negative gold colloids.
Ferric oxide hydrosols and gels tend to carry a positive Gold in igneous-@pel9rocks
charge and thus adsorb and precipitate various negative ionic The gold content of igneous-type rocks is given in Table 13.
complexes of gold, e.g., [AuCl,] - and the negatively charged The table has been compiled from analyses in the literature
colloids of gold. With aging of the gels the gold is commonly and from analyses done for the Geological Survey of Canada.
split out as the native metal, but in many cases the gold is an Excessively high values have been arbitrarily omitted from
intimate constituent of the limonitic complex. some of the data as have also the gold contents of rocks that
In a milieu where manganese, iron, lead, silica, alumina, are highly altered or have closely associated sulphide and gold
sulphate, phosphate, arsenate, antimonate, etc. are present in deposits.
solution in oxidizing zones, the colloidal reactions must be
very complex indeed. There, normal adsorption phenomena
undoubtedly play a part, but hydrolytic reactions, especially lgThe term igneous-type is used to avoid the controversy on the origin
those involved in the hydrolysis of iron and manganese of granites, ultrabasic rocks and various types of porphyries included
sulphates, soluble arsenates, antimonates and phosphates, etc., in the tables.
 Contents

Table 13. Gold content of igneous-type rocks

Number of - - Ag_* Au/Ag
Rock type samples Range X S G xg Sg X ratio
(PP~) (PP~)
Ultrabasic rocks
Dunite, peridotite, pyroxenite,
kimberlite, anorthosite, etc.
Lamprophyres
Camptonite, minette, etc.
Basic rocks
Intrusives: gabbro, norite, diabase,
etc.
Extrusives: basalt, etc.
Intermediate rocks
Intrusives: granodiorite, syenite,
monzonite, diorite, etc.
Extrusives: andesite, trachyte, dacite,
latite, etc.
Acid rocks
Intrusives: granite, aplite, etc.
Extrusives: rhyolite, obsidian, etc.
Alkali-rich rocks
Ne~helinesvenite. ~honolite.etc.
All ultrabasic rocks
All lamprophyres
All basic rocks
All intermediate rocks
All acid rocks
All alkali-rich rocks 99 0.0001-0.0135 0.0034 0.0032 0.0021 -2.6775 0.4764 0.10 0.0340
All igneous rocks 14439 0.0001-2.9000 0.0119 0.0474 0.0044 -2.3564 0.5414 0.07 0.1700
* The arithmetic mean for silver is taken from a previous compilation by Boyle (19686). It does not refer to the samples quoted in the column-number of samples.

Some of the variations in the data on gold analyses of gold gradually increases in the differentiation series gabbro to
igneous rocks are evidently due to analytical rather than aplite, although the distribution of the element in the various
natural causes, a feature that is difficult to assess. Most of the rock types is frequently irregular. Most of the gold is said to
data from the literature compiled in Table 13 are based on be dispersed in igneous rocks in the native state. They also
neutron activation analyses, which in my experience are not claim an increase in gold with increase in potassium content
always satisfactory for some types of rocks. Most of the during differentiation, and suggest that during the postmag-
Geological Survey analyses have been done by a combined matic stage potassium-rich solutions appear enriched with
fire assay-atomic absorption method, which uses several tens gold, from which gold deposits are formed. In the Kurile-
of grams of rock powder. While not as sensitive as activation Kamchatka volcanic province, however, Anoshin and Kepez-
analyses in some respects the method does give more uniform hinskas (1972) found statistically that the gold content is
reproducible results and tends to smooth out errors due to independent of the basicity of the volcanic rocks; elevated
sample inhomogeneities. gold contents were found, nevertheless, in potassium-rich
There is considerable uncertainty about trends in the volcanics in the basalt-andesite-liparite series. The authors
concentration of gold in the sequence - ultrabasic-basic-inter- concluded that generally there is no significant difference in
mediate-acidic rocks. Some investigators, including Shilin gold content among the groups of volcanic rocks related to a
(1968) and Shcherbakov (1968), maintain that mafic rocks are single differentiation series. In other words gold is inert during
enriched in gold relative to acidic rocks. In central Kamchat- differentiation of basalt magma. In the central Kyzylkum,
ka, Shilin, for example, found the older magmatic rocks of Khamrabaev et al. (1972) noted that there was a general
basic composition to contain more gold than the younger acid tendency for Pb, U and Th to increase in the granitic series
rocks of the same Miocene magmatic epoch. Others, including from older granodiorites to younger granites. Gold showed an
De Grazia and Haskin (1964), Anoshin and Potap'yev (1966) opposite tendency. Ivensen et al. (1974) indicate that gold is
and Voskresenskaya et al. (1970) find a near uniformity of fractionated in magmas during differentiation and crystalliza-
concentration of gold in all igneous rock types. Gottfried et al. tion. They found an inverse correlation between the gold
(1969) report that gold is not concentrated in residual liquids content and the amount of alkali feldspars. The gold content
during magmatic differentiation. In general they found gold was also found to increase with an increase in the basicity of
contents in felsic members of the batholiths sampled to be the rock and the Na content. In a recent paper Kashirin et al.
lower than in the related mafic members and noted that (1975) noted a significant increase in the gold content from
relatively higher gold concentrations are associated with the first to the last differentiates of the granitic intrusions in
earlier crystallizing phases (e.g., magnetite, mafic silicates, the Lena gold-bearing region. Higher gold contents were
etc.). They remarked that this was consistent with the trend of found in the endocontact and apical parts of the intrusions as
progressive depletion of gold from mafic to silicic rocks of well as in parts of the intrusions that were altered (beresitized
calc-alkalic suites. Volarovich and Shilin (1971) report that and sericitized). The granitic bodies were also found to be
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CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

sunrounded by extensive exocontact aureoles, the belt with the tion and metamorphism of basic and ultrabasic rocks gold is
maximum gold contents being located some 500 m from the released, is transferred to melts and hydrothermal solutions,
granitic contact. migrates and is deposited in any available local structures.
Shcherbakov and Perezhogin (1964) find that in the Anoshin et al. (1971) examined the Upper Paleozoic to
Altai-Sayan folded belt of the U.S.S.R. gold is more abundant Lower Mesozoic traprock (tholeiite-basalt) intrusions in the
in extrusive rocks than in their intrusive equivalents. This Tungusian and Putoransk subprovinces of U.S.S.R. and found
trend is also apparent in the data of other investigators. There an average gold content of 0.007 ppm; the minimum and
is also more gold in oceanic basalts than in those of terrestrial maximum contents were 0.002 and 0.074 pprn respectively. In
occurrence according to some investigators (De Grazia and one of the differentiated sills they found an average of 0.008
Haskin, 1964; Anoshin and Emel'yanov, 1969). ppm, which they thought represented the initial content of the
In recent years a number of investigations have been undifferentiated magma. In the gabbro-dolerite horizon of the
conducted on the gold content of layered basic intrusives and sill, containing abundant sulphides and magnetite, and en-
ultrabasic masses to define the differentiation trend of the riched in copper, they found an average of 0.020 pprn Au.
element. Vincent and Crocket (1960) postulated that the Other rocks in the differentiated sequence contained relativelv
initial magma from which the Skaergaard rocks crystallized uniform contents of gold (-0.004 pprn Au). These facts led
contained 0.0046 pprn Au. All the rocks throughout the them to the conclusion that gold is concentrated during the
differentiation series, including the acid granophyres, are sulphide and hydrothermal formation stages of the differentia-
within a factor of 2 of this amount. The ferrogabbro phase tion of traprock magmas. The study of Noril'sk type differen-
with a relatively high copper sulphide content contained ten tiated intrusives (Talnakh and Noril'sk) in U.S.S.R by God-
times the gold content (0.028 ppm) of the average rock; levskii et al. (1970) indicates a similar trend. Gold is wncen-
ferrogabbros with iron sulphides contained relatively little trated in the layered phases of the intrusives impregnated with
gold (0.0029 pprn). Rowe (1969) investigated the differentiated sulphides (up to 0.42 pprn); associated layered differentiates
Great Lake tholeiitic dolerite sheet in Tasmania and found such as gabbros and dolerites have gold contents ranging from
that the gold content of parts of the core is related to the 0.03 to 0.06 ppm, an order of magnitude higher than that for
mafic index [(FeO + Fe,O,) X 100/Fe0 + Fe,O, + MgO]. basic rocks in general.
Certain ultrabasic rocks appear to be greatly enriched in
The variation of gold content with depth and mafic index was
found to be similar to that of copper, indicating in Rowe's gold. Borisenko and Uskov (1971) found the following values
opinion that gold and copper probably crystallized conwmi- in the Gusevogorsk Massif, Urals, U.S.S.R.
tantly from the magma. Crocket and Chyi (1972) noticed Au content
considerable fractionation of gold between dunite, peridotite Rock Range Average
and their serpentinized equivalents in the Mount Albert (PP~)
pluton, GaspC, Quebec. In the peridotites and dunites the gold Diallage and hornblende pyroxenite 0.004-1.3 0.14
content averaged 0.001 1k0.0004 pprn whereas in the serpenti- Olivine pyroxenites 0.002-0.5 0.08
nites the average was 0.0024k0.0007 ppm. Gold is concen- Wehrlites 0.004-0.6 0.08
Hornblendites 0.020-0.3 0.12
trated (0.0034 ppm) in the accessory chrome spinels in
peridotites and dunites. In late deuteric chromitite veinlets the Some of the gold is in the native form and as electrum, both
gold content was only 0.00083 ppm. associated with native platinum. The highest gold contents
Voskresenskaya et al. (1970) found that the distribution were found in layers and zones of the ultrabasic rocks
of gold in the layered Zlatogorsk intrusion of ultrabasic and enriched in sulphides (pyrite, chalcopyrite, bornite) and
basic rocks was relatively uniform around 0.0012 ppm. An characterized by increased contents of hornblende.
exception was the leucocratic norites (0.0049 pprn Au). The In another paper, Borisenko et al. (1972) state that the
Zlatogorsk intrusion is characterized by a substantially lower irregular distribution of the gold content of ultrabasic rocks is
content of gold compared with the Skaergaard and Anakit d u e to the presence in these rocks of discrete inclusions of
intrusions. Shcheka et al. (1971) examined the gold contents of native gold and electrum. The remainder of the gold, which is
various intrusive basic and ultrabasic bodies in U.S.S.R., rather uniformly distributed, occurs in the form of neutral
Korean People's Democratic Republic and the Indian Ocean atoms adsorbed by rock-forming and ore minerals. In the
and found that the rocks of the ultrabasic dunite-harzburgite Noril'sk type of differentiated intrusives (Talnakh and No-
clan were richest in the element (0.021 pprn). Rocks of the ril'sk) in U.S.S.R., Godlevskii et al. (1970) state that the gold
gabbro clan had considerably less gold (0.004 pprn). Their is present in both the native form and as an isomorphic
data led them to the conclusion that gold is fairly uniformly replacement in the rocks and associated ores.
distributed throughout the rocks during differentiation and Dodin et al. (1973) examined the platinoid and gold
auto-metasomatic processes of ultrabasic and basic suites; a contents of a number of basic intrusives in U.S.S.R., some
notable concentration of the element, however takes place nickel-bearing of the Norilsk-Talnakh type. They found that
during the Cu-Ni sulphide stage. Examination of rocks near the content of platinoids in both rock-forming minerals and
contacts indicated that reworking by granitic magmas of basic the rocks and their various ratios were indicative of economic
and ultrabasic rocks leads to considerable loss of gold from nickeliferous intrusives; the gold contents on the other hand
the invaded rocks. Moiseenko and Fat'yanov (1972) developed were independent of the type of intrusion and hence not
this thesis further, pointing out that the primary source of indicative of economic nickel-bearing massifs.
gold in the earth's crust is derived from basic and ultrabasic Ultrabasic inclusions in a kimberlite pipe in northern
magmatic formations arising in the mantle. During granitiza- Yakutia were analyzed by Ukhanov and Pchelintseva (1972).
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THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

Low gold contents were found in garnetiferous peridotite (av. nekansk massif they found no significant differences in the
0.0012 ppm) and garnetiferous pyroxenite (av. 0.0015 pprn). gold contents (-0.002 ppm) of the -different phases. They
Eclogites wntained increased amounts (up to 0.0045 pprn). interpreted this behaviour as due to the inert character of gold
The authors noted an increase in the gold content with the during palingenesis. Shcherbakov and Perezhogin (1963) ex-
ferruginous character of the eclogite but no correlation with amined the gold content of granites and other rocks and their
the various oxides. A direct correlation of gold with vanadium accessory magnetites in the Altai-Sayan gold belt. They noted
was also indicated. They concluded from their preliminary that the average gold content in the granitic masses was higher
data that the gold is largely wntained in clinopyroxene. in the peripheries, in the apical parts and in the region of the
In another study of kimberlite rocks and ultrabasic exocontacts.
inclusions Rozhkov et al. (1973) found the gold content to The data in the literature suggest regional variations in
range from 0.001 to 0.010 ppm. They concluded that none of the gold content of igneous rocks, and there may well be
the kimberlite rocks are gold wncentrators. They further distinct gold geochemical provinces. The variations are, how-
remarked that their values did not confirm the supposition ever, small in most cases, and it is not possible to determine
that the gold in ultrabasic rocks is heterogeneous, nor the whether they are real or due to analytical variance between
hypothesis of an irregular content of the noble metal in the investigators. Nevertheless, the gold contents of some suites of
upper mantle on a regional basis. igneous rocks within certain specific areas exceeds the norm
Serpentinization may reduce the gold content of ultrabas- by factors as high as 10. With respect to gold content there
ic rocks according to the data of Li and Kornev (1972). In the appears to be no universal difference between batholiths and
ultramafic rocks of the Yenisei Range the initial gold content stocks with associated gold deposits and those that are barren.
averages about 0.0041 ppm; in the serpentinites the gold Shcherbakov and Perezhogin (1964) could find no clear-cut
content is 0.0017 ppm, a moderate decrease. difference between the gold content in 'gold bearing' and
The distribution of gold in batholiths and stocks of other intrusives, a feature that agrees with most of our data.
intermediate to granitic cornposition appears to be highly Mantei and Brownlow (1967) and others have, however,
variable although some general trends are apparent. Mantei indicated that some stocks with associated gold deposits have
and Brownlow (1967) showed that the Marysville quartz higher than average gold contents. Shilin (1968) noted that
diorite stock in Montana has an appreciably higher gold certain Miocene magmatic rocks in central Kamchatka have
content in and near the periphery where it averages 0.071 gold contents one order of magnitude greater than others in
ppm; elsewhere it averages about 0.01 ppm. Voskresenskaya the same region. He postulated a Miocene magmatic hearth
and Zvereva (1968) observed small but statistically significant enriched in gold below central Kamchatka. In the Rice
differences in the average contents (0.0011, 0.0016, 0.0021 Lake-Beresford Lake area of southeastern Saskatchewan
ppm) of gold in three granitic complexes in northern Kazakhs- Stephenson and Ehmann (1971) found evidence to indicate
tan. Hybrid rocks of the endocontact zones of the complexes that the mafic intrusions may be the source rocks of the gold
contained from 1.5 to 4.5 times as much gold as the granitic deposits. Some varieties of monchiquite, camptonite, odonite
rocks. Davletov and Dzhakshibayev (1970) used neutron and other lamprophyric rocks appear to be enriched in gold
activation analysis to determine the distribution of gold (and silver) in some areas. Buturlinov and Latysh (1970)
between the minerals in various igneous rocks. Feldspars were found up to 0.08 pprn Au and 3.6 pprn Ag in some of these
found to be the main carriers of gold (50% of the metal in the basic lamprophyric rocks in the Donets Basin, U.S.S.R. Our
rock), whereas biotite was also observed to be a consistent experience with lamprophyric rocks is that they may contain
concentrator mineral. The carriers and wncentrators showed up to 0.05 pprn Au or more where they contain abundant
a progressive increase i n Au content from the centre of an pyrite or where they are albitized and altered.
intrusion to the periphery and from the deep parts to the Gottfried et al. (1969, 1972) and Tilling et al. (1973) have
apical parts. Bushliakov (1971) found that the gold content concluded, following an extensive study of gold in igneous
decreases with increasing rock acidity in the granitoids of the rocks that:
Verkh-Isetsk massif in the Urals. Uvarov et al. (1972) ex- The available data provide little support for the view that gold
amined the gold content (0.0006-0.003 ppm) from three is concentrated in the residual liquids during magmatic differentia-
granitic complexes on the Kalba-Narymsk region of eastern tion in any of the calc-alkalic or alkalic provinces. The variation
trends indicate that gold either remains relatively constant or de-
Kazakhstan. They found a general uniformity of gold contents creases during differentiation processes.
in single complexes but significant differences in the level of The gold content in suites of unaltered igneous rocks spatially
the gold values of the three complexes. Antipin et al. (1969), associated with gold mineralization from selected areas - Boulder
however, found no difference in the content of gold (and batholith region, Montana; Cornwall, Pa.: Jerome district, Arizona:
molybdenum) in granitoids of different ages and geological Bullfrog district, Nevada; Mother Lode, California - is virtually
settings in the East Transbaikal region of U.S.S.R. From this the same as petrographically equivalent rocks from provinces de-
void of mineralization. The relatively high concentration of gold
they reasoned that gold is relatively inert during the processes that exceeds background levels for a given region invariably occurs
of magmatic differentiation of multi-phase intrusions. A only locally in altered rocks and may be ascribed to remobilization
somewhat similar conclusion was reached by Li and Datsenko or secondary introduction. Geochemical abundance data alone
(1973) who investigated the gold content of a variety of neither provide unique criteria in identifying broad segments of the
crust favorable for gold mineralization nor specify processes that
metasomatic and palingenic granitoids of the South Yenisei resulted in the economic concentration of gold. Thus, in any ex-
Range, U.S.S.R. They noticed a slight enrichment (up to 0.150 ploration program, geologic factors, such as petrologic, structural
pprn Au) in the endocontact and central zones of the Taraksk and tectonic setting, must be considered in conjunction with purely
and Posolnensk granitoid massif. In the rocks of the Nizh- geochemical abundance factors.
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

Against this view we have the research by Kushmuradov igneous rocks and the presence or absence of gold deposits is
(1970), who worked in a gold-bearing area in Uzbek, U.S.S.R. unresolved. Part of the problem would seem to be the
and found an average of 0.01 pprn Au in the granitoids of the difficulty in obtaining an adequate sample in that gold is
North Nuratau Mountains, a value some 2 to 3 times higher distributed extremely nonuniformly in unaltered igneous-type
than the average abundance of gold in such rocks. Altered rocks. Even those that are equigranular and massive were
(albitized and silicified) granitoids and sedimentary rocks near found by Rozhkov et al. (1970) to display this habit. The
the Charmitan, Karaulkhon Latta and Koktonly gold deposits sampling problem is even more troublesome in slightly altered
contained 2 to 3 times more gold (0.02 ppm) than the rocks where the gold content can range widely from sample to
unaltered rocks. Dyke rocks, including lamprophyres, granite sample.
porphyries and diorite porphyries, were relatively enriched in To summarize the facts on the general distribution of
gold averaging 0.026 ppm. However, a study of a number of gold in igneous rocks as shown in Table 13 and from the more
intrusive granitoid bodies in U.S.S.R. with diverse associated detailed data in the numerous publications and in my files one
ore mineralization, carried out by Anoshin et al. (1970) found can say that the variation from the mean gold content of
no significant statistical difference in the gold content between igneous rocks is never great. The data suggest that on the
bodies with associated gold ores and those that are barren. average the ultrabasic and basic rocks have slightly more gold
These researchers also found similar gold contents in different than other igneous-type rocks, but the excess amount is not
phases of granitoid bodies with associated gold mineralization. great as shown by the geometric mean. In places there is
They suggested that the increased amounts of gold in some evidence of some trends in the sequence ultrabasic-basic-
intrusions in gold belts was secondary, that is, the metal was acidic rocks with a general depletion in gold toward the acid
introduced or rearranged during the hydrothermal stage. In end of the sequence. This trend is, however, not marked and a
the Chatkal zone of the Tien Shan, Davletov (1974) finds that general uniformity of gold content seems to be present in
relatively high contents of gold occur in igneous intrusives many sequences. Specific observations indicate few definite
spatially associated with the gold mineralization of this zone. trends except in rocks which contain relatively high contents
Wolfe (1975) gives interesting data on barren and aurifer- of sulphides, especially pyrite and chalcopyrite. Such rocks are
ous granitoid bodies from six Early Precambrian felsic intru- generally enriched in gold regardless of type. We have also
sions in Ontario. These range in size from 4 to 88 km2.Four - noted relatively high gold contents in some quartz-feldspar
Dome stock, Red Lake area; Larder Lake stock; Lebel stock, porphyries containing pyrite and other sulphides, but the
Kirkland Lake area; and Cairo stock, Matachewan area - origin of these porphyries and their contained sulphides is
have associated gold deposits and two (Kabenung Lake and somewhat controversial. They may in some cases be of
Coyle Lake) are barren. Wolfe observed that the gold levels in metamorphic rather than igneous origin. There is a suggestion
unmineralized stocks are consistently below the 5 ppb detec- that some of the alkali-rich syenites and similar rocks are
tion limit of the analytical method used. In contrast, analyses higher than normal in gold but only by a small amount. On
of samples from stocks with associated gold mines within their the basis of the available data nepheline syenites and phono-
borders and in nearby metavolcanic-metasedimentary host lites appear to be normal within a range 0.0001 to 0.0135 pprn
rocks show a strongly skewed trace element gold population Au. The nepheline syenites of Ontario are low in gold (t0.005
with a substantial percentage of gold values exceeding 5 ppb ppm), and the alkali basalts investigated by Gottfried et al.
and ranging as high as 320 ppb. Further details on this (1972) appear to have a distinctly lower gold content (-0.0006
research are given in Chapter V. ppm) than most Hawaiian and continental basalts of the
In the granitic rocks and their contact haloes in the tholeiitic magma type with a gold content ranging from 0.002
auriferous Lena region, Kashirin et al. (1975) observed that to 0.0035 ppm. Certain highly alkaline Permian magmatic
the former camed from 0.0016 to 0.0047 pprn Au whereas the rocks investigated by Lisogor and Babakhodzhaev (in Petrov-
latter contained from 0.0007 to 0.0139 pprn Au. They noted skaya, 1974) are, however, enriched in gold compared with
that the concentration of gold increased in the late-stage others in the Karamazar region of U.S.S.R.
differentiates of the granitic magma and in rocks altered by The distribution of gold in some regional suites of
autometasomatic processes. An enrichment of gold was also igneous rocks is lognormal in nature; in others lognormal with
observed in the endocontact and apical facies of the granitic a marked skew; and in still others the distribution is polymo-
bodies. dal. The last type of distribution suggests addition of gold to
In the recent symposium edited by Petrovskaya (1974) the rocks during mineralization processes.
there are a number of papers refemng to the abundance of There is considerable difference of opinion on the dis-
gold in igneous rocks and the presence of auriferous deposits. tribution and nature of gold in igneous rocks. Most investiga-
One by Trunilina and Yakovlev notes that the content of gold tors are agreed that gold is distributed in a nonuniform
in unaltered magmatic rocks of the Charka River Basin manner in igneous rocks; in fact in some rocks its distribution
(northeastern Yakutia) increases with the sulphur content and can be said to be quite erratic according to our investigations.
that these rocks have a high gold content (0.0086-0.0205 ppm) Rozhkov et al. (1970) comment at length on this particular
when auriferous mineralization is present in the area. An feature after applying statistical principles to their data. Three
accumulation of gold in peripheral parts of granitic massifs views seem to be prevalent with respect to the nature of the
and in selvages of dykes is also noted, features that are gold in igneous rocks. One holds that the gold is present in the
ascribed to magmatic differentiation. native form or as electrum; another that the element is
The writer concludes from this diversity of findings and dispersed throughout the rocks and constituent minerals in the
opinion that the relationship between the gold content of form of neutral atoms; and a third that the gold is present as
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSlTS

an atomic and/or ionic substitution in the lattice sites of The gold (and platinum content) of magnetites in rocks
minerals. Probably all three are correct depending on the type can apparently be used to differentiate igneous rocks of
of rock, mineral composition and other factors. Mineral different genesis. In the Urals the granitoids have two origins
separates from igneous rocks show gold to be present in - one as differentiates of basaltic magma and the second
practically all of the minerals although the amounts vary, but derived from sialic material (by granitization). In an interest-
generally only within narrow limits. Data from the literature ing paper on the subject Fominykh and Znamenskii (1974)
and the writer's analyses indicate the following ranges in pprn observed an increased content of gold in the magnetites from
to be expected: quartz, 0.0008-0.002; feldspars, 0.0003-0.002; granitoids of the granite (sialic) formation, with which are
biotite, 0.0024.007; hornblende, 0.0005-0.003; pyroxene, often associated hydrothermal gold-bearing deposits. The gold
0.0005-0.004; olivine, 0.001-0.01; sphene, 0.004-0.009; content of magnetites of this formation ranged from 0.018 to
magnetite, 0.003-0.1; and pyrite and other accessory sul- 0.035 ppm; in addition an increased gold content (0.035 ppm)
phides, up to 0.5 or more. Considerably higher values for was noted in magnetites from more basic varieties of rocks
biotite, hornblende and magnetite are reported in some (quartz diorites and diorites). Magnetites in the granitoids of
igneous rocks by Mantei and Brownlow (1967) and others. In the gabbro (basaltic) formation differ in gold content from
some suites of rocks the sialic minerals, mainly the feldspars, magnetites of the granite formation by an order of magnitude
cany the highest contents of gold. Khairullin et al. (1968) and contain the same amount of gold regardless of the rock
found the highest amounts of gold in the heavy fractions (e.g., composition (av. 0.006 pprn).
biotite and magnetite), and Davletov and ~ z h a k s h i b a ~ e v Platinum group elements are also distributed differential-
(1970) found that biotite is the principal mineral concentrator ly in magnetites from the different groups of granitoids. A
of gold, but the feldspars contain the bulk of the element in high platinum content was noted in magnetites from the
igneous rocks (up to 50% of the total amount of gold present). gabbro group of granitoids, the maximum amounts being
Mantei and Brownlow (1967) and Zvereva and Gavrilenko found in magnetites from diorites, quartz diorites, granosye-
(1971) noticed that the dark minerals including pryoxene, nites and syenodiorites. In the magnetites of the granitoids
hornblende, biotite and magnetite are enriched in gold com- derived from sialic material the platinum content was low and
pared with quartz and feldspar, although the l a t t e r i n ~ e s t i ~ a -did not depend on the rock composition.
tors emphasize the point that the magnetite is not always Finally, experiments camed out by Davletov et al. (1973)
richer in gold than other minerals and that its gold content on the phase leaching of gold from intrusive rocks and mineral
varies within broad limits. Anoshin et al. (1970) for instance carriers of gold in these rocks indicates that gold is not
state that in granitoids the gold content of the rock-forming distributed evenly in the mineral camers as should be the case
minerals is relatively uniform, and that the differences are with isomorphic replacement. Rather, the metal occurs in
statistically insignificant. Their table indicates, however, that microcracks and lattice discontinuities in the minerals and in
quartz and feldspar (0.0016 ppm) have lower average gold microfractures and along intergrain boundaries in the rocks.
contents than biotite, amphibole, magnetite, sphene, etc. These features are of interest in theories of metamorphic
(0.0019, 0.0020, 0.0034, 0.0029 pprn Au respectively). Bush- secretion since gold in microfractures and grain boundaries
liakov (1971) gives the average gold content in rock forming can be easily mobilized (extracted) from these sites. This
minerals in the granitoids of the Urals as determined by circumstance is referred to later in the section on the origin of
activation analyses as follows: quartz, 0.0017 ppm; plagio- epigenetic deposits in Chapter 111.
clase, 0.001 7 ppm; microcline, 0.00 16 ppm; hornblende, The writer's investigations generally confirm the findings
0.0016 ppm; biotite, 0.0018 ppm; muscovite, 0.0019 ppm; of a number of workers that the dark minerals, magnetite,
magnetite, 0.0036 ppm; ilmenite, 0.0022 ppm; sphene, 0.0027 ilmenite and particularly pyrite and chalcopyrite contain the
ppm; apatite, 0.0024 ppm; garnet 0.0052 ppm; epidote, highest amounts of gold in igneous rocks. In our work on
0.0025; ppm; and chlorite, 0.0025 ppm. Sobolev et al. (1974) igneous rocks we have not been able to separate free gold
record the following ranges in parts per million for the various from large quantities of rock nor have we seen free gold in
minerals in basic and ultrabasic formations in the Urals: polished sections of mineral concentrates of magnetite, pyrite,
olivine, 0.0034.010; pyroxene, 0.0006-0.001; plagioclase, chalcopyrite and other sulphides from fresh (unaltered) igne-
0.00054.003; and hornblende, 0.0004-0.0007. Gottfried et al. ous rocks. There are, however, numerous older references in
(1972) found by material balance calculations that in most the literature (e.g., Blake, 1897; Spurr, 1903, 1904; Weed,
igneous rocks, even the very freshest, the gold measured in the 1904a, b; Brock, 1904) of free gold in supposedly fresh
rock tended to be greater than that indicated by the summa- (unaltered) granites, diabase, etc. Some of the descriptions
tion of the gold contribution from the principal rock-forming given are, however, suspicious of alteration or impregnation
minerals. This suggested to them that some of the gold may since many are in or near gold mines or sulphide deposits.
reside elsewhere in the rock, possibly in phases volumetrically Correlations of gold with other elements in igneous rocks
small but comparatively rich in gold (for example, sulfides) or are imperfect and seemingly erratic in many cases. Shcher-
even as intergranular native gold. Keays and Scott (1976) bakov and Perezhogin (1964) claim to have found a correla-
found that the gold contents of the glass rims of oceanic tion of gold with the following metals and metal oxides in
pillow basalts (av. 0.0015 ppm) to be some 5 to 7 times greater decreasing order of correlation as follows: Cu, Fe,O,, MgO, V
than those of the associated crystalline interiors (av. 0.0005 and FeO. They found no correlation with Zn, Pb and other
pprn). They considered that the hosts for the bulk of gold in metals. Rowe (1969), as noted above, found a correlation with
basalts are probably (1) early separated oxide and silicate the mafic index and with copper in the Great Lake tholeiitic
phases such as Cr-spinel and olivine and (2) sulphide phases. dolerite sheet in Tasmania. Zvereva and Gavrilenko (1971)
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

could find no correlation of gold with iron in the minerals from seawater). In the crestal sediments, however, where the
examined in their study. Gottfried et al. (1969, 1972) conclud- gold is significantly higher in content, they considered that a
ed that their data suggest a negative correlation between gold fraction of the gold had a volcanogenic (exhalative) source
content and abundance of some 'residual' trace elements (e.g., (precipitated from seawater).
Th, U and Nb) but a gross positive correlation with chalco- The Red Sea metalliferous sediments (Hendricks et al.,
philic elements such as copper. Shcherbakov et al. (1972) 1969) are enriched in gold (and silver) (Table 14). These
carried out an extensive series of gold analyses (over 2000) on sediments exhibit a wide variation in physical appearance and
a large number of rock types. They found a definite correla- in chemical composition, from oxidized red muds to dark
tion between the iron and gold contents of igneous and sulphide-rich muds and a few light-colowed carbonate-rich
sedimentary rocks, the higher gold contents being present in samples. Hendricks et al. (1969) found extreme variations in
rocks with high iron contents. The main gold concentrator composition between adjacent sample sites, and considerable
mineral in granitoids was found to be magnetite; in skarn, variation was noted even within different splits from the same
hornfels and schists the gold was contained mainly in the core. Extreme vertical variations in the cores were also
femic minerals. Hamrabaev and Urunbaev (1971) noted recorded, sometimes within a few centimetres of depth.
positive correlations of gold with ferrous iron and copper in The data provided by Koeberlin (1934) on the gold
the igneous rocks of Uzbekistan. A possible correlation of content of the volcanic ash in central Chile is interesting, in
gold and sodium was also noticed. Keays and Scott (1976) that there may be areas where such deposits (both uncon-
analyzed a number of oceanic pillow basalts from the mid- solidated and indurated) may be of economic interest. Good-
Atlantic Ridges; in the fresh crystalline interiors of the pillows child (1918) also mentions the fact that certain ash flows
they noted correlations between gold and Cr, Ni and MgO. associated with the volcano La Sufral in Colombia contain
Studies by the writer on the correlation of gold with other from 0.42 to 1.71 ppm Au. Silver, likewise, has been found to
elements in igneous rocks suggest a positive correlation with be enriched in certain falls of volcanic ash in Ecuador, South
Fe and possible positive correlations with Cu, Ag, S, As and America (Mallet, 1887,1890). Taken together these two facts
Sb, but the relationships are often erratic. I think the positive are of prime importance considering the frequent occurrence
correlation with sulphur is genuine, and I have noted a general of gold-silver deposits in or associated with tuffs (sedimented
tendency for gold to be enriched in igneous rocks rich in volcanic ash) or porphyries (crystallized volcanic material) in
pyrite, pyrrhotite or chalcopyrite. The correlation with arsenic, the Canadian Shield, Tertiary terranes, etc. These types of
likewise, seems highly probable most of the arsenic being rocks in the Canadian Shield are enriched in both gold and
present in the sulphides, especially pyrite (Boyle and Jonas- silver and a variety of other associated elements (Boyle,
son, 1973). In the basic-ultrabasic suites of rocks there appears 1968a,b) (Table 15). Such rocks would seem to be an adequate
to be a weak positive correlation between gold and the various source for the derivation of gold-silver veins and other
platinoids, and perhaps with chromium, although at the time deposits by a metamorphic secretion mechanism. (See the
of writing my research on the platinum group is not complete. section on origin of gold deposits in Chapter 111.)
It further appears that certain ultrabasic rocks are enriched in Anoshin et al. (1969) carried out an extensive investiga-
both the platinoids and gold compared with more acidic suites tion of marine sediments in the Atlantic Ocean basin with the
of rocks. results given in Table 14. Their main findings can be summa-
Goldschmidt (1954) estimated the abundance of gold in rized in point form as follows: (Details should be sought in
igneous rocks (lithosphere) to be 0.005 ppm. Others (see the the original paper.)
section above on abundance) have given abundances, based 1. The average gold content in modem sediments is a
mainly on igneous rocks, ranging from 0.001 to 0.0043 ppm. little higher than the average content in felsic, mafic and
Calculations based on the data given in Table 13 yield an ultramafic rocks, but considerably lower than the content in
abundance of 0.0044 ppm (geometric mean) for igneous rocks. oceanic basalts. The most frequent occurring concentrations
Like all abundance calculations this figwe should be taken as of gold (0.003-0.006 ppm) fall within the range of consolidat-
a rough estimate until more accurate figures are available on ed sedimentary rocks or are slightly higher (see also Table 15).
the quantity of each igneous rock type in the earth. 2. The highest gold contents were in coquinoid limestones
from the Black Sea, the lowest in sands and gravels from the
Gold in sedimentary rocks Baltic Sea and Atlantic Ocean and in some pyroclastic
The gold content of a variety of unconsolidated sedimentary sediments from the vicinity of Iceland.
rocks is given in Table 14, and similar data for consolidated 3. In the clastic sediments the gold content increases with
sediments are contained in Table 15. decrease in grain size. The correlation of gold content with the
The data are not extensive for most types of uncon- pelitic (clay) fraction is weak in some types of sediment but
solidated sediments, but those available indicate that certain significant in others.
types of tuffs (volcanic ash) and organic sediments may be 4. The distribution of gold in the unconsolidated sedi-
enriched in gold. Some of the sediments associated with ments coincides closely with the distribution of uranium, an
oceanic ridges and rises appear also to contain slightly higher element often closely associated with organic matter.
than average amounts of gold. Crocket et al. (1973) consider 5. In carbonate sediments very low and very high values
that the gold in the sediments of the East Pacific Rise had a were encountered. The highest contents are apparently con-
submarine volcanic exhalative origin. Piper and Graef (1974) centrated in molluscan shells.
on the other hand think that much of the gold in the flank 6. In general the concentration of gold in biogenic
sediments of this rise had a lithogenic origin (not precipitated carbonate sediments is not dependent on the content of
 Contents

Tablel4. Gold content of some Recent unconsolidated sedimentary rocks

Au/Ag
Rock Type ratio Reference

Volcanic ash, Chile - 1

Deep sea red clay, volcanic ash, etc.,
Atlantic region 0.146 2
Red clay
Brazilian Basin 3
Lutites
Argentinian Basin 3
Recent carbonates
Florida Coast 3
Recent coral
Florida Coast 3
Temgenous sediments (silt, clay, sand,
gravel) (30%CaCO,)
Baltic Sea
Black Sea
Mediterranean Sea
Atlantic Ocean
Biogenic and chemical sediments (coqui-
noids, sand, silt, clay) (>30% CaCO,)
Black Sea
Mediterranean Sea
Atlantic Ocean
Volcanic sediments (silts; 10%pyroclasts)
Atlantic Ocean
(near Iceland)
Mediterranean Sea
(Santorini Lagoon)
Oceanic sediments; Arctic, Antarctic,
Pacific, and Indian Oceans
Oceanic sediments: East Pacific Rise
Red Sea metalliferous sediments
Shelf sediments Carolina Coast, U.S.A.
Alluvial placers (stream, river and marine)
References: I. Koeberlin (1938).
2. Wagoner (1908).
3. De Grazia and Haskin (1964).
4. Anoshin et al. (1969).
5 . Crocket et a/. (1973).
6. Piper and Graef (1974).
7. Hendricks et al. (1969).
8. Pilkey and Bombold (1970).
9. Estimated.

Table 15. Gold content of unconsolidated and consolidated (lithified) sedimentary rocks
Number of - - ~ g *A ~ / A ~ -
Rock type Samples Range X S G xg sg X ratio
(PP~) (PP~)
Unconsolidated sediments, oceans 299 0.0003-2.5000 0.0523 0.2761 0.0035 -2.4615 0.6792 - -
Sandstone, arkose, conglomerate and
sedimentary breccias 3474 0.0002-0.4300 0.0570 0.0499 0.0263
Greywacke and subgreywacke 38 0.0010-0.1000 0.0132 0.0192 0.0076
Witwatersrand and similar auriferous
quartz-pebble conglomerates 0.4-230 8.0
Shale, mudstone, siltstone, argillite 1356 0.0001-0.8000 0.0080 0.0266 0.0039
Sulphidic-schists, pyritic greywacke,
pyritic black shale, pyritic tuff, etc. 19
Tuffs 97
Limestone, dolomite 440
Evaporites:
1) Gypsum, anhydrite 18
2) Halite, sylvite, etc. 15
(See also Table 12)
Chert 3
Phos~horite 1
~ k i & e s enodules 1 0.0002
All sedimentary rocks 5761 0.0001-2.5000 0.0403 0.0831 0.0122 -1.9125 0.7632 0.3 0.1343
* The arithmetic mean for silver is taken from a previous compilation by Boyle (19686). It does not refer to samples quoted in the column-number of samples.
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

CaCO, but probably on the organic content since there is a Certain oil shales and other types of bituminous sedi-
general positive correlation between gold and organic matter ments contain small amounts of gold in excess of the average
(C,,). This suggests that gold is probably absorbed by for normal shales. Varley (1922) has described an investigation
organisms (principally plankton) from seawater which on their involving recovery of gold from such rocks in Wyoming
death are sedimented in the clays and other marine sediments. (Green River Formation) and Utah. He records values ranging
Another process is concerned with the precipitation of gold in from 0.3 to 0.6 pprn (0.01-0.02 oz/ton Au). Cook (1973) in a
organo-metallic compounds absorbed on clays and clastic later paper on the Green River oil shale gives the gold content
material. as t 0 . 1 ppm. The nature of the gold in the shales could not
7. The distribution of gold in some marine sediments be determined by Varley. Korotayeva and Polikarpochkin
appears to depend on the types of rocks in the provenance (1969) also noted enriched contents of gold in the organic-rich
areas and on the mineral composition of the marine rocks of the Nerchinsk Zavod region of eastern Transbaikal,
sediments. U.S.S.R. The enrichment was two- to threefold and in places
ten- to fifteenfold compared with the light (organic free)
shales and siltstones. In other papers by Polikarpochkin et al.
The gold content of modem eluvial and alluvial (placer) (1969) and Gapon (1970) the maximum gold values recorded
deposits may be high enough to provide an economic source in organic (carbonaceous) rocks was 200 pprn with some 50
of the element. The lowest economic unit for exploitation of per cent of the samples containing 5 pprn and more. These
these deposits varies from region to region and from deposit authors ascribe the enrichment of gold in the carbonaceous
to deposit. Roughly it is about 0.1 pprn Au. Most of the gold rocks to physico-chemical processes and calculated that some
in eluvial and alluvial deposits is particulate. Its origin is 50 per cent of the gold in the rock was precipitated from
probably due to both mechanical and chemical processes. solution. In samples of the Athabasca tar sands we found less
These concepts, and descriptions of the deposits, are discussed than 0.005 pprn Au.
in greater detail in the section on placers in Chapter 111. Phosphorites appear to be enriched in gold in places.
In normal types of consolidated sedimentary rocks the Yasyrev (1969) found from tO.O1 to 0.15 pprn in the Meso-
highest amounts of gold unquestionably occur in the conglom- zoic nodular phosphate deposits of the Russian Platform.
erate, sandstone, greywacke suite and in the black shales, Some 10 to 35 per cent of the gold was in the free state; the
carbonaceous argillites, alum shales, oil shales and some remainder was combined in a chemical form. In fossil reptile
phosphorites. Only small amounts of gold occur in normal bones and sawfish teeth the amounts of gold ranged from
shales, limestone, evaporites and other sedimentary rocks. (0.01 to 0.085 ppm. Yasyrev found a correlation of gold
Certain consolidated sandstones and conglomerates are great- content in phosphorites with a number of other trim elements
ly enriched in gold. Most of these constitute fossil placers; including Ti, Zr, etc. This might suggest that detrital processes
they are discussed in some detail under this heading in were the prime factors in the concentration of gold in these
Chapter 111. deposits, but our observations indicate that such elements are
Minnitt et al. (1973) analyzed three suites of essentially also subject to marked hydrolysis phenomena (as is also gold
argillaceous sediment from the Wolkberg Group and the in solution) causing their precipitation. In the United States
Black Reef-Dolomite transition zone (Transvaal Supergroup, and Morocco the marine phosphorites appear to be low in
northeastern Transvaal) for gold, using instrumental neutron gold. Samples of marine phosphate rock from Florida, Mon-
activation analysis. The average gold content of the argilla- tana, North Carolina and Morocco contained only up to 0.003
ceous rocks was found to be 0.0025 ppm, while the more pprn Au as determined by the neutron activation-fire assay
arenaceous sediments carried, on the average, some 0.022 pprn method (Z.S. Altschuler, U.S. Gwl. Surv. Circ. 622, p. 11).
gold. Sediment samples from the old workings on the Crags Evaporites are notably low in gold and silver. ~ o u b e a u
had an average gold content of 0.061 ppm; a value of 0.131 and Birckenbach (1938) found a general average of 0.0014
pprn was determined for one sample from these workings.
- -
pprn total precious metals (Ag, Au, Pt, etc.) in various
Minnitt et al. (1973) concluded from their investigation that potassium salts (sylvanite, carnallite, etc.) in Germany. Our
the background gold concentration in argdlites is, on average, analyses show that all salt deposits including halite, sylvite,
about 10 times lower than in more arenaceous sediments. An etc. generally have less than 0.001 pprn Au. Gypsum and
important exception was found in a carbonaceous silt-shale anhydrite from the Walton area, Nova Scotia, likewise,
r&k from the DolomiteBlack Reef transition zone, which generally has less than 0.001 pprn Au. Pyrite in evaporites
camed nearly 0.090 pprn gold. Such a sediment they thought may, however, be enriched in gold (up to 0.01 pprn). Seeland
could act as proto-ore for gold-quartz reefs of the Pilgrims (1973 a,b) reports higher than average amounts of gold in
Rest-type, which are very often intimately associated with the certain samples of gypsum, anhydrite and halite from Paleo-
carbonaceous shale beds in the Dolomite. zoic rock formations south of the Great Lakes in United
Certain terranes of sedimentary and derived metamorphic States. Twelve per cent of the gypsum and anhydrite samples
rocks appear to be greatly enriched in gold. Thus Li and analyzed contained detectable gold, the mean being 0.020
Shokhina (1974 a,b) noted that the Proterozoic (sedimentary ppm; a similar percentage of halite samples reported gold with
and derived metamorphic) rocks of the Yenisey Range are a mean of 0.06 1 ppm.
characterized by higher than normal contents of gold, in some Popov (1975) investigated the gold content in the Upper
cases by an order of magnitude of the clarke value (0.004 Jurassic Halogenous Formation in the southern part of
pprn). Particularly enriched are certain sandstones and quart- Russian Turkestan. In all some 120 samples were analyzed.
zites and carbonaceous and graphitic phyllites and schists. The average gold values found were: rock salt - 0.0012 ppm;
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

sylvanite - 0.0017 ppm; and sylvanite-carnallite - 0.0031 ppm. ally contain more gold than the Superior (Proterozoic) type.
The content of gold in the associated limestones and anhydrite The Ordovician iron-formation in the Bathurst area of New
was lower. The order of increasing concentration of gold in Brunswick contains only low gold contents, from t0.005 to
the various rocks was found to be anhydrite-anhydrite- 0.01 ppm. Analyses of fossiliferous sedimentary magnetite
limestone-rock salt-potassium salts, indicating that gold was beds (Lower Devonian) in the Nictaux Falls area of Nova
precipitated in increasingly larger amounts from waters of Scotia indicate that the gold contents are less than 0.005 ppm.
increasing salinity. Hematite beds at the base of the Nepean sandstone (Cambri-
There appear to be only limited data on the gold content an) near Delta, Ontario generally contain less than 0.005 ppm
of oxidate sediments. The gold and silver contents of a Au. Seeland (1973 a,b) noted that certain glauconitic sand-
number of iron-formations and associated sedimentary rocks stones (Franconia Sandstone in Wisconsin) were slightly
in Canada are shown in Table 16. It will be noted that the enriched in gold. Some 17 per cent of the samples analyzed
sulphide-bearing members are the most enriched in the two reported gold with a mean content of 0.031 ppm.
elements. The Algoma (Archean) type iron-formations gener- Rozhkov et al. (1971~)have provided some data for the

Table 16. Gold and silver content of Canadian Precambrian* and Paleozoic iron-formations
Locality, type and age Description Au Ag Au/Ag ratio

Temaeami. Ont. Banded pyrite-magnetite chert

~16ma:typeiron-formationt Banded chert with conformable pyrite layer
Precambrian (Archean) Banded chert with minor disseminated pyrite
Jasper and chert with pyrite
Pyritic chert-magnetitebreccia
Balrner Lake, Ont. Magnetic laminated grey chert
- Algoma-type iron-formation
Precambrian (Archean)
Kukatush, Sudbury district, Ont. Magnetite-carbonate-chert iron-formation
Algoma-type iron-formation Thinly banded carbonate iron-formation
Precambrian (Archean) Jasper-magnetite-hematite iron-formation
Geraldton, Ont. Magnetite-carbonate-quartz iron-formation
Algoma-type iron-formation Magnetite-carbonate-quartz-pyrite iron-formation
Precambrian (Archean) Magnetite-carbonate-quartz-pyrite iron-formation
Carbonate-quartz-pyriteiron-formation
Oxide-carbonate facies iron-formation
Schreiber, Ont. Massive pyrite in iron-formation
Algoma-type iron-formation Massive ~vrrhotitein iron-formation
Precambrian (Archean) Massive pyrite, pyrrhotite, minor galena in iron-formation
Michipicoten, Ont. Buff siderite
Algoma-type iron-formation Black siderite, minor disseminated pyrite
Precambrian (Archean) Black siderite with pyrite in quartz-ankerite vein
Siderite-chert iron-formation, minor pyrite
Magnetite-siderite-chert iron-formation
Magnetite-siderite-pyrrhotite-chert iron-formation
Sideritepyrite-chert iron-formation
Hearne Lake, N.W.T. Recrystallized chert-magnetite iron-formation
Algoma-type iron-formation Silicate facies (quartz-chlorite-pyrite and minor chalcopyrite)
Precambrian (Archean)
Kaminak Lake area, N.W.T. Laminated magnetite iron-formation
Algoma-type iron-formation Magnetite iron-formation, some pyrite
Precambrian (Archean) Pyritic cherty iron-formation
Masswe pyrrhotite in iron-formation
Pyritic interflow
Massive carbonate, some pyrite and arsenopyrite
Massive carbonate
Pyritic interflow
Pyritic graphitic-interflow
Cherty carbonate iron-formation
Cherty iron-formation
Magnetite chert bands
Pyritic interflow, some chalcopyrite
Pyritic cherty carbonate interflow
Carbonate-rich tuff
Siderite
Cherty pyritic interflow
Pyritic bands in iron-formation
Cherty pyritic bands
Cherty pyritic bands silicate iron-formation
 Contents

Table 16. (cont'd.)

Locality, type and age Description Au Ag Au/Ag ratio

Kirkland Lake, Ont.

Algoma-type iron-formation Magnetite-chert
Precambrian (Archean) Chert and fine-grained quartz
Scheffe~lle,Labrador-Quebec Nonmagnetic silicate-carbonateiron-formation, Femman sectil
Superior-type iron-formation? Silicate-carbonate member of iron-formation, Wishart section
Precambrian (Proterozoic) Silicate-carbonate member of iron-formation, French section
Oxide facies; Lower Red cherty member of iron-formation,
French section
Oxide facies; Pink Cherty member of iron-formation,
French section
Oxide facies; Grey Cherty member of iron-formation,
French section
Oxide facies; Brown Cherty member of iron-formation,
French section
Oxide facies; Upper Grey member of iron-formation,
French section
Bathurst district, N.B.
Austin Brook area Magnetite-chert-chlorite (composite sample)
Algoma-type iron-formation Magnetite-chert-chlorite-pyrite (composite sample)
Ordovician
Nictaux Falls area, N.S. Magnetite-hematite (composite sample)
Nictaux-Torbrook Formation
Metamorphosed Clinton-type
iron-formation
Upper Devonian
*The samples in these suites of iron-formations were kindly provided by G. A. Gross, R. H. Ridler and J.B. Henderson, Geological Survey of Canada; and H.
Lovell, Division of Mines, Ontario Ministry of Natural resources.
tFor classification of the types of iron-formationssee G.A. Gross (1965), Geology of iron deposits of Canada, vol. 1; Geol. SUN. Can., Econ. Geol. Rep. no. 22,
p. 116.

Krivoi Rog ores of U.S.S.R. as shown in Table 17. It will be into deposits. These and other speculations are considered
noted that the gold contents are an order of magnitude higher further in Chapter 111.
than the contents in most sedimentary rocks. The gold tenor Enrichment of gold in certain red (oxidized) sediments is
in all rocks and ores of the iron-formations was found to be also notable mainly as a result of adsorption and/or co-
O.On ppm. Some of the iron ores are relatively rich in gold; for precipitation by ferric oxide hydrate. Thus, certain red sand-
example martite ore - 0.7 ppm, magnetite concentrate - 0.4 stones and conglomerates may contain higher than normal
to 0.8 ppm. This suggested to the authors that some ore amounts of gold than equivalent grey (reduced) rocks of the
horizons were enriched in gold by sedimentary or metamorph- same type. Polikarpochkin et al. (1969) refer to this situation
ic processes. Data provided by Pletnev (1972) for the Krivoi in the Baleisky, Onokhovsky and Lukinsky grabens where
Rog siliceous ferruginous formations of Lower Proterozoic age they find maximum contents of gold in red conglomerates up
show that in vertical profile the rocks range in gold content to 0.5 ppm. I have found higher than normal gold contents in
from 0.02 to 2 ppm. Two types of gold were recognized - one some Carboniferous, Tertiary and Recent conglomerates con-
related to original sedimentation processes and the other taining abundant iron oxides in various parts of Canada.
representing a superimposed mineralization present in thin These are discussed in the section on placers.
crushed zones. The latter may be a redistribution of the There are apparently no systematic analyses for gold in
former (?). the bedded sedimentary manganese deposits of the world. The
results reported for deep sea manganese nodules generally
Table 17. Gold contents of Krivoi Rog iron ores, U.S.S.R. show the gold content to be tO.OO1 ppm; some wads,
Description Range in gold content however, are richer in gold (Table 12) with values up to 0.7
(PP~) pprn Au or more.
Magnetite-martite ores O-O.00n-0.n Gold is frequently concentrated under unusual conditions
Ferruginous quartzites O-O.On-0.n
Shales O.On-0.n in some types of sediments. Laur (1906) describes remarkable
Mineralized zones in ferruginous concentrations of gold and silver in Triassic sediments in the
quartzites (M.On-0.n-n Meurthe-et-Moselle tegion of France. Up to 29 pprn Au (and
Source: Rozhkov er a/. (1971~). 245 pprn Ag) are recorded for samples of sandy dolomite. The
The various data on iron-formations are interesting in the nature of the gold is not specified. Palmer (1935) has de-
light of the common occurrence of commercial gold deposits scribed an interesting occurrence of gold and silver in petrified
in or near these formations in a number of places in the logs in the Aspen district of Nevada. One log assayed 18.26 oz
Canadian Shield and elsewhere in Precambrian rocks. The of gold and 10.8 oz of silver to the ton, and native gold was
oxidate sediments together with sulphidic slates and schists readily observed under the microscope. Palmer thought that
that commonly accompany iron-formations may be the source the carbonized wood produced the reducing environment that
of the gold that was later concentrated by secretion processes precipitated the gold and silver from circulating solutions that
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

came into contact with the logs. The writer has seen similar Late Cretaceous age contain up to 1.3 pprn Au in Wyoming
occurrences of gold in petrified Sequoia trees in samples from and Colorado according to R.S. Houston (U.S. Geol. Circ.
Alaska (G.B. Robbe collection, Michigan Technological Col- 622, 1969, p. 8). In Wyoming the younger deposits contain the
lege, Houghton, Michigan). higher gold contents.
An interesting occurrence of traces of gold (and silver) is In Canada there are also numerous occurrences of gold-
that in the salt-dome calcitic and gypsiferous cap rocks of bearing conglomerates, sandstones and quartzites. The uranif-
Texas and Louisiana mentioned by Hanna and Wolf (1941). erous conglomerates and quartzites of the Blind River-Elliot
In these rocks the noble metals appear to be associated with Lake area carry small noncommercial amounts of gold in
sulphides, including pyrite, hauerite (MnS,), galena and some beds. The Edmonton Formation in Alberta is gold-
sphalerite and in some places with barite, celestite and native bearing in places. It probably supplied most of the gold to the
sulphur. The origin of the sulphides and their contained gold placers worked many years ago along the North Saskatchewan
and silver seems to be best explained by the hypothesis that as River (Tyrrell, 1915). Another example of gold-bearing con-
H,S rose from underlying petroliferous layers it came into glomerate and sandstone is found in the basal Carboniferous
contact with groundwaters (or connate waters in some cases) of Nova Scotia in the Gays River area (Malcolm and Fari-
carrying lead, zinc, iron, manganese, silver, gold, etc. in the bault, 1929). The gold content of the richer streaks was said to
region of the cap rocks and deposited the sulphides in the average 5.4 pprn (0.158 oz/ton); our analyses show much
available porous zones. lower values, around 0.03 ppm. Yet another example of
Occurrences of auriferous sandstones and conglomerates gold-bearing limonitic-cemented conglomerate is found in the
are widespread throughout the world, the most famous and Beauceville area of Quebec. This has been mined extensively
productive being those of the Witwatersrand, South Africa, in the past. The rocks may be early Pleistocene in age
Tarkwa, Ghana and Jacobina, Argentina. The Witwatersrand although some investigators have considered them to be of
ores average 8 pprn Au and 0.8 pprn Ag; those at Tarkwa Tertiary age (see also the section on placers in Chapter 111).
contain 10 pprn Au and 0.5 Ag, and those at Jacobina 15 pprn Throughout other parts of the world gold-bearing can-
Au and about 1 pprn Ag. Other less well known occurrences glomerates, sandstones and quartzites are widespread, and
occur in many parts of the world throughout the geological many have been mined or washed for gold. The Witwaters-
column. Only a few can be mentioned as examples. For details rand, Tarkwa and Jacobina deposits have been mentioned
and descriptions of other similar auriferous rocks consult previously. These are the most famous of all of the fossil gold
Chapter 111, especially the section on placers. placers. In U.S.S.R. there are numerous occurrences of gold-
In the United States Devereux (1882) describes the bearing sandstones and conglomerates. One of these in Cam-
occurrence of gold in the Potsdam conglomerate-breccia- brian sandstones is described by Pokrovskii (1968); others are
sandstone of the Black Hills near the famous Homestake mentioned by a number of other Russian investigators, the
deposit. Some streaks near the bedrock are said to run 85 pprn principal publication on their occurrence being that by Iven-
(2.5 oz/ton), but the overall grade of the conglomerate is low, son et al. (1969). In Switzerland, Hofmann (1965) describes
probably of the order of 1 pprn or less. Devereux recognized quartzite-rich conglomerates of the Upper Marine Molasse
two types of gold in the fossil placers - mechanically concen- (Miocene) and coarse Triassic sandstones that carry gold
trated gold and chemically precipitated gold. The fineness of contents of the order of 1 to 2 colours per 100 kg of rocks. In
the placer gold was greater than that of the quartz veins from South Island, New Zealand, conglomerates and quartzites
which it was said to have been derived, a feature that is ranging in age from Cretaceous to Recent have been washed
normal in practically all placers. for gold for many years. These conglomerates are of fluvial
Hastings (1908) described fossil placers near Antelope and glaciofluvial origin. They are discussed in greater detail in
Springs, Park County, Colorado. These placers occur in a Chapter 111.
large area of unconsolidated lake beds that average about 0.01 The fossil gold-bearing placers typified by conglomerates,
oz/ton (0.3 pprn). The nature of the gold could not be sandstones and quartzites are of two types. These are only
determined. Dumble (1913) described somewhat similar de- briefly described-here since more details are given in the
posits from the Eocene of Texas. The gold-bearing beds are section on placers in Chapter 111. The ancient Precambrian
clays and sands with interbedded lignite. The grade is low, but types (Witwatersrand, etc.) are characterized by relatively high
some samples ran as high as 1 oz/ton (34.2 ppm) and upward. gold contents and an abundance of pyrite. The gold is mainly
In Oregon and California, Diller (1914) describes Cretaceous free, but some is contained in pyrite and other minerals.
fossil marine placers formed about an old island. The gold- Uraniferous minerals are common, and in some there are also
bearing rocks are conglomerates derived from an underlying thorium and rare-earth minerals. Iron oxides are rare except in
auriferous slate bedrock series. They contained from 1 to 5 the Tarkwa deposits. The more recent types are often charac-
pprn Au on the average. More recently Antweiler and Love terized by limonite or iron oxide cemented conglomerates in
(1967) have described gold-bearing Cretaceous and Tertiary which the gold is mainly free with only small amounts in
quartzite conglomerate in northwest Wyoming. The gold adsorbed oi other forms. Uranium, thorium and rare-earth
values run from 0.035 to 0.222 ppm. The gold is largely minerals are rare or present in only small amounts; pyrite
confined to sandstone layers and the sandy matrix of the tends to be rare, but in some deposits, it is present in small
conglomerates. Much of it is the particulate native variety, but amounts in the basal parts of the sequences. While both types
some evidently occurs in an absorbed state or in the structure may represent similar sedimentary conditions of formation it
of a variety of minerals. In the Rocky Mountain region of the is obvious that their subsequent history has been much
conterminous United States certain fossil black sandstones of different.
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CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

The writer has extensively investigated the nature of gold (flour gold) or in the small amounts of pyrite, magnetite,
in sedimentary rocks, and while it is often difficult to deter- limonite and other heavy minerals that are frequently present
mine precisely the location of parts per billion gold in some in such rocks. In carbonates and evaporites the gold is
samples, concludes the following from his research: probably largely present in carbonaceous matter or in colloi-
1. In conglomerates, sandstones, quartzites and similar dal pyrite. In all fine-grained sedimentary rocks there is
rocks most of the gold is present in particulate form as the probably some gold present as an adsorbed element.
native metal. The size of the particles ranges all the way from The average gold content of the sediments of the Russian
less than 1 p to nuggets the size of peas. Much of this gold is Platform is given by Nikitin and Yasyrev (1974) as 0.005 ppm.
of detrital or detrital-chemical origin. Some gold is also In the minerals of these sediments the average gold content
Dresent in forms.b the nature of which we have not been able to ranges from 0.0008 pprn in chlorites to 0.0137 in the iron
ascertain with certainty. Where pyrite is present there are oxides; the organic constituents contain an average of 0.0089
small amounts of the element in this mineral as shown by the pprn Au.
results from Elliot Lake (Table 11). Other minerals such as
limonite, magnetite, pyrrhotite, etc. may also contain traces of
gold, the form of which is unknown. Gold in metamorphic rocks
2. In pyritiferous black shales and schists most of the The available data on the gold content of metamorphic rocks
gold is present in pyrite and/or pyrrhotite as shown by the are given in Table 18. The number of analyses in some of the
analyses in Table 11. It is of interest to note that in rocks categories are too few to draw sound conclusions, but the
containing coexisting sedimentary pyrite and arsenopyrite following indications are noted.
gold prefers the arsenopyrite whereas silver is concentrated In metamorphic rocks gold appears to occur in the same
mainly in the pyrite. This feature is particularly clear in minerals as those noted for igneous and sedimentary rocks.
samples from the Meguma slates in Nova Scotia (Ovens, N.S., My research shows that much of the gold occurs in pyrite,
Table 11). In some black shales, oil shales, etc. the gold is pyrrhotite, etc. and in the ferromagnesian minerals, principal-
largely associated with the carbonaceous substance, probably ly magnetite, biotite, pyroxenes and amphiboles. Where pyrite
in an adsorbed form or as some type of organometallic and pyrrhotite are present in the same rocks, gold generally
compound. Where fine-grained pyrite and/or pyrrhotite are prefers the pyrite. If arsenopyrite is present, this mineral is
present, however, the gold tends to be partitioned into these enriched compared with pyrite and pyrrhotite. In certain
mineral phases. The same is true if other sulphides such as quartzites and metaconglomerates the element may be present
chalcopyrite and galena are present. From this it seems to as the native metal. These types of metasediments are dis-
follow that the degree of diagenesis and metamorphism of the cussed in greater detail in the section on auriferous quartz-
black shales and schists more or less determines the location pebble conglomerates and placers in Chapter 111.
of gold (and silver). In black shales that have undergone little Regionally metamorphosed rocks appear to have gold
metamorphism the gold appears to be associated with both contents in the same range as those of the igneous and
the carbonaceous substance and fine-grained nearly colloidal sedimentary rocks from which they were derived. Certain
sulphides. With increase of metamorphism and migration of skarns and other contact rocks, on the other hand, are often
the sulphides into knots or crystals, the bulk of the gold (and enriched in gold (and silver). This appears to be normal since
silver) tends to collect either in the iron sulphides or in such rocks often contain copper deposits and a few gold-silver
chalcopyrite and other sulphides that occur in blebs or in deposits. These are discussed in further detail in Chapter 111.
small fractures in the pyrite and/or pyrrhotite. It is of interest Certain metamorphic rocks seem to be exceptionally high
to note that Kucha (1973) observed that much of the gold in in gold over large areas, an example being those in the Sob
the copper-bearing shale of the Fore-Sudetic monocline in River basin in the Ukraine (Latysh et al., 1974). Certain
Poland is present in minerals containing native silver but also shales, containing high contents of magnetite, report up to 0.3
in organic compounds of the thioaurate and chelate types. pprn Au in this area. Other rocks contain from a trace to 0.02
Legedza (1967) has examined the problem of the accumula- Au. It is not clear whether these are fresh rocks, or whether
tion of gold in sulphides in the sediments of the Russian there is a superimposed mineralization present. Relatively
Platform during diagenesis. He thinks that thiosulphates in enriched quantities of gold are also recorded by Usenko et al.
groundwaters act as collectors and carriers of both sulphur (1973) in the garnetiferous quartzites, crystalline schists,
and gold, and that during diagenesis the metal is largely skarns and magnetite ores from the Sea of Azov region,
precipitated in pyrite (apparently in the metallic state) accord- U.S.S.R. They report gold contents ranging from 0.3 to 1.0
ing to the reactions: pprn in the ferruginous quartzites. Other rocks contain from
traces to 0.2 pprn Au. Certain of the Grenville marbles in the
Adirondacks of New York appear to be enriched in gold in
In lithified sulphide-free sediments, gold apparently remains places. Seeland (1973 a,b) found that 24 per cent of the
in its finely dispersed state. samples he analyzed ranged in gold content from 0.020 to 0.20
3. I have not been able to determine the nature of gold in and averaged 0.053 ppm.
normal shales, carbonate rocks, evaporites, etc. with any The migration trend of gold during metamorphism is
degree of certainty. The amounts of gold are so low that the indicated in a number of investigations:
mineral separation and analytical problems are in many cases Brarnmall and Dowie (1936) noted low gold contents
insuperable. My results suggest that the gold, in some fine- (0.07 ppm) in basic igneous rocks, grey granites, gneisses and
grained sediments such as shales, is present in particulate form schists of the Malvern Hills, England. Higher values (up to
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Table 18. Gold content of metamorphic rocks

Number of Ag* Au/Ag
Rock type samples Range z S G % Sg z
-ratio
(PP~) (PP~)
Quartzites and indurated sandstones 289 0.0002-1.1500 0.0317 0.0836 0.0047 -2.3325 0.9282 - -
Slates, phyllites, meta-argillites 225 0.0009-0.0150 0.0022 0.0022 0.0016 -2.7959 0.3126 0.2 0.0110
Gneisses, granulites 1929 0.0002-0.3000 0.0031 0.0071 0.0027 -2.5682 0.1806 - -
Amphibolites, greenstones 425 0.0001-0.1000 0.0071 0.0110 0.0041 -2.3837 0.4399 0.25 0.0284
Schists 1969 0.0001-3.7000 0.0186 0.1545 0.0037 -2.4351 0.5388 0.2 0.0930
Marble and crystalline limestones 40 0.0002-0.1000 0.0132 0.0224 0.0036 -2.4385 0.7243 0.050.2640
Hornfels and meta-pelites 368 0.0003-0.3000 0.0064 0.0262 0.0018 -2.7341 0.5037 - -
Eclogites 103 0.0008-0.0400 0.0036 0.0045 0.0024 -2.6132 0.3626 0.10 0.0360
Skarns 44 0.0076-0.0220 0.0086 0.0028 0.0083 -2.0789 0.0887 - -
Undifferentiated metamorphic rocks
(porphyroids, chloritized and epidot-
ized tuffs, etc.) 12 0.00044.0084 0.0038 0.0022 0.0029 -2.5308 0.3812 - -
All metamorphic rocks 5404 0.0001-3.7000 0.0109 0.0960 0.0031 -2.5092 0.4703 0.15 0.0727
*The arithmetic mean for silver is taken from a previous compilationby Boyle (19686). It does not refer to the samples quoted in the column - number of samples.

2.06 ppm) were recorded in red granites, red granite pegma- of the sedimentary rocks of the Patom Highlands, U.S.S.R.
tites and mixed rocks affected by the reddened granites. They Gold was lost from the rocks of the amphibolite facies and
attributed the increased amounts of gold to disseminations of accumulated in the epidote-amphibolite and greenschist facies.
hematite attributable to pneumatolytic processes associated Uranium and thorium were relatively inert. Buryak et al.
with the latest phase of granitic intrusion. (1972) also found that the granitization of the Upper Protero-
Boyle (1961~)observed decreases in the gold contents of zoic Patom Series of shales, schists, etc. resulted in sigmficant
chloritized zones and marked increases in carbonatized zones losses of gold. This gold is evidently slightly concentrated in
associated with the formation of quartz in the Yellowknife the youngest pegmatites.
Greenstone Belt, Northwest Territories, Canada. During the autometasomatic amphibolitization of ultra-
Buryak (1964) noted that the gold mineralization of the basic rocks gold is practically inert according to Shcheka and
Lena goldfields, U.S.S.R. is closely related in time, space and Moiseenko (1970). However, during serpentinization processes
possibly genetically to regional metamorphism. much gold is lost from these rocks; granitization and migrnati-
In the Altai and Transbaikalian massifs Anoshin and zation of ultrabasic rocks also results in sigmficant losses of
Potap'yev (1966) found a two- to threefold increase of gold in gold. Li and Kornev (1972) also noted appreciable losses of
an early stage of altered granites compared with the unaltered gold during serpentinization of dunites. In another paper
varieties. The gold content, thereafter, decreased with in- Moiseenko et al. (1970) state that the main sources of gold in
creased hydrothermal alteration. In other words gold was lost the earth's crust are basic and ultrabasic rocks. During the
from rocks that have undergone metamorphism according to metamorphism of these rocks the gold is freed, transferred to
their data. melts and solutions and after migration is deposited in local
Shilin (1968) found that low temperature carbonatization faults and fractures. The same theme, greatly amplified and
processes reduced the content of gold in primary gold- illustrated, is discussed by Moiseenko et al. (1971) and Moi-
enriched magmatic rocks in central Kamchatka. seenko and Fat'yanov (1972).
Voskresenskaya and Zvereva (1968) noted a direct cor- In their study of the Rice Lake Gold Belt of Manitoba,
relation between gold mineralization and the degree of meta- Stephenson (1971), Stephenson and Ehmann (1971) and
somatism in northern Kazakhstan. In weakly propylitized Weber and Stephenson (1973) concluded that the low gold
rocks they recorded an average of 0.006 pprn Au whereas in values recorded for high-grade gneisses was the result of gold
highly propylitized varieties the values were as high as 0.06 depletion during high-grade metamorphism of the belt.
ppm. Roslyakov (1969) noted that gold was concentrated in Finally, Pchelintseva and Fel'dman (1973) examined the
rocks formed at the terminal stages of metamorphism in the gold content of the metamorphic rocks in the Koktchetav
Darasun ore field. uplift and concluded that the gold distribution in these rocks
Chaika and Nezhdanova (1969) examined the problem of is determined by the composition of the initial rocks (sedi-
the migration of gold during the metamorphism of the ments and volcanics), not by the grade of the metamorphism
sulphide-bearing graphitic kyanite shales of the Keyv Series of which ranges from greenschist to amphibolite facies.
the Kola Peninsula, U.S.S.R. They noted that pyrite contained A number of more recent studies suggest that gold is
the most gold (0.006-0.008 ppm), followed by graphite relatively mobile during metamorphic processes. Li and Shok-
(0.004-0.006 ppm), pyrrhotite (0.003 ppm) and muscovite hina (19741) found that during regional metamorphism no
(0.003-0.004 pprn). During the metamorphism of the shales substantial change took place in the Precambrain rocks of the
gold migrated together with silica (quartz) from the shales into Yenisei Mountain Ridge. However, they observed that the
nearby cavities. These contained gold in quantities up to 2.86 deep reformation of the mineral composition of some of the
ppm. In the kyanite schists of the Vitim-Patom Highland, rocks under conditions of high temperature was attended by
U.S.S.R. Kepezinskas et al. (1970) state that a complete an internal redistribution and dispersion of gold. Palandzhyan
redistribution of gold results from metamorphism. Petrov et and Razin (1974) working in the ultrabasic and basic massifs
al. (1972) noted a similar tendency during the metamorphism of the Sevan Ridge, U.S.S.R. observed that metamorphic
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

transformation of rocks of the ophiolite association is accom- constitute valuable deposits of the element; they are discussed
panied by a decrease in their gold content, and Mushkin et al. in the section on placers in Chapter 111.
(1974) found that eclogitization of granulite facies gneisses Relatively little precise knowledge on the migration and
leads to upward movement of gold, together with Si, Na and concentration of gold during weathering is available despite
K, into quartz veins. Gavrilenko et al. (1974) observed that the the importance of the subject. Both physical and chemical
regional metamorphism of Lower Proterozoic rocks in the processes are involved; the importance of each in the migra-
Kolmozero-Voron'ya complex (Kola Peninsula) was essential- tional history of the element depends on numerous factors
ly isochemical, the overall concentrations of petrogenic and discussed below.
ore-forming elements, including gold, being the same as the Soils
concentrations in the parent rocks. The great dispersion of Data on the gold content of soils are limited, and the
gold observed and the anomalous concentrations of the metal calculation of an average value seems unwarranted at the
in hydrothermally altered rocks in fissured zones, at contacts present time. Swaine (1955) does not list an average value, and
between mafic and ultramafic intrusives, and in mineralized Vinogradov (1959) states that the data on gold in soils were
pegmatites and their enclosing rocks were considered to be insufficient at the time of his compilation to give values for
due to redistribution of gold to some degree during metamor- the contents of normal soils.
phism. During the formation of contact-metasomatic zones Nemec et al. (1936) found an average gold content of 0.1
associated with granitic intrusions in the Altai-Sayan Korobei- pprn in some Czechoslovakian soils formed from andesite and
nikov (1976) observed that most of the gold in the original rhyolite, and Nemec et al. (1937) recorded gold values from
rocks was redistributed and concentrated in the hornfels and 0.185 to 0.350 pprn in other soils of Czechoslovakia. Babicka
marbles, particularly in magnetite, epidote, amphibole and (1943) records values from 0.2 to 6 pprn Au in some Czechos-
chlorite. lovakian soils. Goldschmidt and Peters (1933) found 0.1 pprn
Despite all these indications there are still insufficient Au in the humus of a birch forest in Germany.
data to establish unequivocally the migration trend of gold Relatively few data on the gold content of soils well
(and silver) during metamorphic processes. Nevertheless, removed from gold deposits are extant in the literature. One
certain trends seem to be indicated from my research and that particular study, however, camed out in Greece gives consid-
of others. During high grade metamorphic processes and erable information on the content and nature of gold in
granitization gold (and silver) appears to be liberated from the Grecian residual and alluvial soils, including one loessial soil
rocks but is not concentrated in pegmatities despite the fact from Illinois (Yassoglou and Nobeli, 1968). The values record-
that the migration of much silica is involved in the process. ed range from 0.005 to 0.150 pprn Au. The results indicated
The element is, however, markedly enriched in some skam that the silt clay fractions contain much higher amounts of
zones, in various types of veins and in a variety of other gold than does sand. Parent materials, which have undergone
deposits that appear to form during the late stages of the one cycle of soil formation, appear to contain gold in the silt
metamorphic and granitization history of a mineralized belt. in the resistant metallic form. In other cases, the element was
Gold is not a chalwphile element but has certain tenden- found to be associated with easily weatherable minerals and
cies in this direction since it appears to follow sulphur, arsenic appeared to be progressively lost from the silt fraction during
and antimony during regional and contact metamorphic processes of soil genesis. The authors thought that gold could
processes. There is also considerable evidence to suggest that be used as an index of soil weathering, either as a resistant or
the migration characteristics and diffusion rates of gold are as a removable constituent of the silt, depending on the
about the same as those of K, Na, Mo, W, Cu, Ag, Zn, Cd, composition and the origin of the parent material of the soil.
Hg, Pb, As, Sb, Se and Te since these elements are commonly They also felt that gold can be used as an index of the
associated in deposits. The tendency of gold to follow copper lithological continuity of soil profiles.
and silver is common in some skarn deposits (Table 44); in Crocket et al. (1973) record gold values for some Arctic
others it follows arsenic and/or antimony. There is also a Island soils: the Prince Patrick grey soils contain 0.001 pprn
marked coherence in the migration tendencies of silica and Au and the Melville Island grey-brown and red-brown soils
gold, the two constituents being nearly always associated in 0.0003 and 0.0018 pprn Au respectively. The average for the
auriferous deposits. An explanation of these and other fea- Arctic soils is given as 0.001 pprn Au. The analyses were done
tures is resewed for the discussion on the origin of gold by neutron activation methods.
deposits in Chapter 111. The writer has carried out investigations of the gold
content of soils far removed from gold deposits in a number of
As a land surface is worn away in regions Canadian areas, with the results noted in Table 19. Summariz-
where conditions are unfavourable for ing we can say that the general background range of the soils
solution, gold tends gradually to become in most parts of Canada is from t0.0005 to 0.005 ppm. There
concentrated at the surface. is a slight enrichment of gold in the A (humic) horizons
-W.H. Emmons. 1937
compared with other horizons in some soil profiles.
Numerous investigations of the gold content of soils in
Gold in soils and other products of weathering the vicinity of gold-bearing deposits are extant in the litera-
The average gold content of most soils is low, but the element ture. These, together with some of my data, are summarized in
is enriched in certain types of soils and in a variety of glacial Table 20. Enrichment of the element in the A (humic)
and weathered products in the vicinity of gold-bearing rocks horizons of soils is again apparent in numerous places,
or auriferous deposits. Some of these weathered products although in some profiles there is a considerable concentration
 Contents

Table 19. Gold content of Canadian soils well removed from of these studies suggest that gold is bound in the following
gold-bearing rocks and deposits ways in most soils:
Range in 1. As a constituent of flour gold and small flakes and
Description gold content nuggets of native gold. These occur almost universally in the
weathered products of gold deposits, auriferous sulphide
Southwestern Ontario, Port deposits, etc. and in nearby soils, especially those of a residual
Lambton-Wallaceburg area nature. Similar flakes and nuggets have been noticed in glacial
Soils developed on glacial lake clay
A horizon (virgin) t0.005-0.01 till, sand and gravel overlying, or in the vicinity of, gold-bear-
B horizon (virgin) t0.005-0.01 ing deposits. This gold is readily extracted by aqua regia,
C horizon (virgin glacial clay) t0.005 (av.) KCN, and other gold solvents. Frequently, the gold is of much
A horizon (cultivated area) t0.0054.01 greater fineness than that in the underlying deposits. This
B horizon (cultivated area) to.0054.0 1 feature is discussed in greater detail in Chapters 111 and IV.
C horizon (virgin glacial clay) 2. As a minor constituent of a number of partly oxidized
(cultivated area) tO.005 (av.) residuals of primary vein minerals, particularly pyrite, arseno-
Soils developed on glacial sand
A horizon (virgin) pyrite, chalcopyrite, sphalerite, magnetite, etc. These minerals
C horizon (virgin) have been noticed in soils overlying all types of gold deposits
A horizon (cultivated) throughout Canada.
C horizon (cultivated) 3. As a minor constituent of a number of discrete second-
Central Ontario, Minden-Bobcaygeon area ary (supergene) minerals, particularly limonite, wad, beudan-
C horizon (till) tite, bindheimite, anglesite, jarosite, copper carbonates, etc.
Eastern Ontario, Carleton Place-Ottawa area These minerals generally occur in soils quite close to the
C horizon (till) underlying deposits. Most occur in the C horizons; only a few
C horizon (Leda clay)
Eastern Ontario, Lavant Township, have been noted in the A and B horizons, and their presence
Lanark County in these horizons is generally due to solifluction and other
Soils developed on glacial till disturbances of the soil.
B horizon below pine needle mat 4. As a minor constituent of manganese oxide coatings on
Northern Ontario, Cobalt area
A horizon (humic) sand and silt; also in similar material cementing sand, silt, etc.
A, horizon (sand) in the B and C horizons of the soil. It has been noted that
B horizon (sand) some soils enriched in manganese oxides are also enriched in
C horizon (sand) gold (and silver). The enrichment of gold is presumably due to
A horizon (humic) the presence of foreign colloids such as positively charged
C horizon (glacial clay) hydrous iron oxides, alumina, etc., which impart a net positive
C horizon (till) charge to the initially negative hydrous manganese oxide gels.
New Brunswick, Bathurst area
Soils developed on glacial till, sand and These in turn attract and coprecipitate the negatively charged
gravel gold complexes and colloids. (See also the section on gold in
A,, +A, horizon (humic) oxides in the first part of this chapter.) The gold in manganese
A, horizon (reddish loam) oxides is evidently present mainly as an adsorbed phase or in
A, horizon (leached layer) a very finely divided native form. Some wads in oxidized
B, horizon (abundant iron oxides)
C horizon (sand, till) auriferous deposits contain wiry and powdery forms of native
Manitoba, Falcon Lake area gold.
Soils developed on sandy glacial till 5. As a minor constituent of various hydrous iron oxide
A horizon coatings in sand and silt; also in similar material cementing
B + C horizon
Northwest Temtories, Yellowknife area sand, silt, etc. in the B and C horizons of the soil. Hydrous
Soils developed on glacial till, sand and iron oxides in soils in the vicinity of gold-bearing deposits are
gravel invariably enriched in gold, the probable cause being that
A horizon (humic) 0.005-0.10 negatively charged gold complexes and hydrosols are strongly
B horizon 0.008 (av.) adsorbed and precipitated by positively charged hydrous iron
C horizon (sandy till; glacial sand and
gravel; clay locally) 0.009 (av.) oxide sols and gels. The gold in hydrous iron oxides is
Northwest Temtories, Regan Lake area evidently present mainly as an adsorbed phase or in a very
Reeosoils* finely divided native form. Some limonites in oxidized aurifer-
'Data from Cameron, E.M.and Durham, C.C. (1974), Geol. SUN. Can. Pap. ous deposits contain wiry and powdery forms of native gold.
74-1, Pt. A, p. 5 W .
6. As a minor constituent of organic matter (humus) in
soils. We have found an enrichment of gold in some of the A
(humic) horizons of soils in the vicinity of gold-bearing
of gold in the B and C horizons directly over deposits (viz., deposits and also in normal soils. The nature of the gold in
Crestaurum profiles). As a generalization one can say that this material is difficult to ascertain. Some is evidently a
gold is enriched in one or more of the soil profiles in the constituent of the undecayed plant and animal matter (see
vicinity of auriferous deposits. below under gold in plants and animals.) The remainder is
A number of studies have been carried out by the writer probably present as a chelate or some other organometallic
to determine the mode of binding of gold in soils. The results gold compound. Only small amounts of gold (and silver) are
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Table 20. Gold content of soils in the vicinity of auriferous deposits

Locality Material Range or average Reference Remarks
@pm)
Region de l'Afema en Cate d'Ivoire Argillaceous lateritic soils 0.02-5.4
Minerai Banora en Guinke Ardlaceous lateritic soils 0.5-30
Aldan Shield, U.S.S.R. SOL 0.1-5.7 Kuranakh-type (karst) gold
A, horizon 0.1-5.5 deposits
Mont Flotouo (Ity, Cate d'Ivoire) Argillaceous lateritic soil 0->8
Northwest Wyoming Soil on/or derived from Hare- 0.036-0.048 Rock underlying soil con-
bell and Pinyon conglomerate- tains 0.04.43 ppm Au
sandstone formations
Silver Reef, Utah Soil t0.05-0.35 Underlying rocks are sand-
stones, shales, etc.
Southeastern, U.S.A. Near surface soil crs.5 ft deep
Soil from a pit 0-12 ft deep
Ity, Ivory Coast Lateritic ores
British Guiana Laterites and ironstones Precipitated ironstones (li-
monite) are often rich in gold
Mill Canyon area, Nevada Mull (forest humus) 0.8 (av.) Composite of 2 samples
Empire district, Clear Creek County, Mull (forest humus) 1.4 (av.) Composite of 8 samples
Colorado
Empire district, Clear Creek County, Mull (forest humus) 0.6 (av.) Composite of 9 samples
Colorado
Empire district, Colorado Mull layer About 70%of values cluster
in the range t0.04-0.59 and
30%in range >0.60
Soil (6-12 in. depth) About 90% of values cluster
in the range t0.04-0.59 and
about 10%in range >0.60
Auriferous areas in Colorado, Utah, Mull layer
Nevada and Arizona Other soil horizons High concentrations of gold
commonly found near the
bottoms of the profiles
Cros Gallet, Guyane franqaise Soil 0.053-1.10
Rhodesia; near Leopardess Mine Topsoils and subsoils 0.042-0.049 Kalahari sand
Lavant, Ont. (Joe Lake Mine) B horizon below pine needle 0.01-0.05 Podsol developed on till
mat
Falcon Lake, Man. A horizon t0.01-0.025
(Falcon Lake Mine) +
B C horizon (till) t 0.0 1
Yellowknife, N.W.T.
Profile 1 (Crestaurum Mine area) A (humic) horizon 0.85 Arctic brown soils developed
+
B C (rusty till) 24 on till. Permanently frozen in
places
Profile 2 (Crestaurum Mine area) A (humic) horizon 1.1
+
B C (clay) 0.04
Profile 3 (Lynx area) A (humic) horizon 0.04
B horizon (clay ) 0.02
C horizon (reddish till and clay) 9.0
Near and over gossan zone, Regan Soils and disintegrated tO.OO5-0.8 10 Regosoils
Lake area, N.W.T. gossanous material
Bathurst area, N.B. A, (humic layer) tO.O1 Podsols developed on glacial
Profile 1 (Nigadoo vein) 4 (leached zone) t0.01 till
(For geological description see B, (rich in iron oxides) tO.O1
Davies et al. (1969), Geol. Surv. C (till 0.0 1
Can. Pap. 67-49) C (till and disintegrated gossan) 0.045
Gossan 0.41
Sulphide ore 0.01-0.20
Profile 2 (Bathurst No. 6 deposit) & (humic layer) 0.025
(For geological description see 4 (leached layer) 0.015
Boyle and Davies (1964), Geol. B, (reddish loam) 0.120
SUN.Can. Pap. 63-24) B, (yellowish-brown loam-till) 0.220
B, (reddish loam-till) 0.465
Gossan-limonite cemented con- 0.017-0.684
glomerate
Sulphide ore at interface of gos- 2.8
san and orgbody
Sulphide ore 0.30
References: I . Martinet and Cuper (1961). 6. Kinkel and Lesure (1968). 1 I . Lakin et a/. (1974).
2. Razin and Rozhkov (1963). 7. Jones (1%9). 12. Machairas (197Oa).
3. Granier et al. (1963). 8. Harrison (1908). 13. Watson (1972).
4. Antweiler and Love (1967). 9. Curtin et al. (1970). 14. Boyle (unpublished).
5. Cornwall et al. (1967). 10. Curtin et. al. (1968). 15. Cameron, E. M. and Durham, C. C. (1974)
Geol. Surv. Can., Pap. 74-1, pt. A, p. 53-60.
 Contents

THE GEOCHEMISTRYOF GOLD AND ITS DEPOSITS

removed by cyanide leaches of humic material. Ashing is feature has been noted by others earlier (see the next section
necessary to effectively liberate the gold (and silver). on gold in natural waters). Despite the asserted high mobility
Zhukova (1974) found that up to 50 per cent of the gold of gold under tropical weathering conditions much of the
in the organic horizons of soils over auriferous deposits in metal remains behind in the weathered mantle as can be seen
eastern Transbaikal, U.S.S.R. was water soluble. The remain- by perusing Table 20. (See also the section on placers in
der was bonded to organic substances, such as resins, waxes, Chapter I11 and the pertinent discussion in Chapter IV.)
fats, etc., extractable with an alcohol-benzene-chloroform 3. Parent materials: no major differences have been noted
mixture. Only small amounts of gold were bonded to humic in the gold content of soils developed from different rock
and fulvic acids according to the data presented. types in Yukon. In the Canadian Shield and in eastern
7. As a minor constituent of the clay fraction. The precise Canada, where the soils are developed on glacial tills or
mode of binding of the gold in this fraction is uncertain. Small mixtures of tills and residual soils, I have noted no radical
amounts are liberated by aqua regia and cyanide leaches variations in the gold content of the normal soils. There may
indicating that some of the gold is present in an adsorbed be slight enrichments of gold (up to 0.01 ppm or more) in
state. The remainder of the gold appears to be tightly bound residual soils and weathered residuum developed on pyritic
in the clay complex or clay-humate complexes. Roslyakov et graphitic schists, phyllites, quartzites, etc. containing an
al. (1971~)have noted that gold is relatively immobile where abundance of quartz blows and boudins. Evidently, the gold
kaolin-type weathering predominates; on the other hand the derives from the quartz bodies and oxidized pyrite. Some tills
metal is highly mobile in regions of lateritic weathering. record slightly higher than average contents of gold
(0.005-0.010 ppm) for reasons that are obscure.
In addition to the above mechanisms, one can postulate In all of my investigations I have found that the presence
that there is probably a minor amount of gold in the soil of auriferous deposits normally influences the gold content of
solutions of all soils. Roslyakov et al. (1971) found mobile the soils. In Yukon, Canadian Shield areas, New Brunswick
gold in the form of ionic complexes - [AuC12]-,[Au(OH),]- and Nova Scotia the gold content of shallow soils is generally
and [Au(OH),]- - in the pore solutions of soils and weathered increased over or near these deposits. Where deep glacial
debris in the vicinity of gold deposits. There are probably also deposits overlie gold-bearing veins, as in some parts of the
small amounts of gold in bacteria and other organisms in the Yukon, Canadian Shield and eastern Canada, this generaliza-
soil. These occurrences would seem to complete the possible tion does not hold. In such situations, however, the basal
modes of binding of gold in most soils. members of the glacial materials normally report high con-
tents of gold near auriferous deposits.
Our investigations indicate that the mobility and fixation 4. Drainage conditions: well-drained soils tend to have
of gold in soils is influenced by the following factors: lower contents of gold (and silver) cornpared with poorly-
1. Topography: in the mountainous parts of the Yukon drained soils in the same area. This is probably due to the fact
and British Columbia, the soils tend to be consistently that all gold (and silver) compounds are highly soluble and are
disturbed by solifluction and downhill migration. This results gradually removed in time from the various soil horizons.
in poor profile development and mixing of material from 5. Presence of complexing agents: the free ions, Au+ and
different horizons. Both these features make systematic work Au3+,are unknown in aqueous media. Both are highly com-
difficult with respect to the migration and concentration plexed or hydroloysed, and the mobility of gold is hence
tendencies of gold and other elements within the soil horizons. largely dependent on suitable available complexing agents.
It is necessary to carry out the work on a local basis, and I Complexing agents such as (S20,)2-or (CN)- or an excess of
have found that broad generalizations do not apply. On the C1- give soluble complexes of the type [Au(S20,)]-,
other hand in the Canadian Shield and eastern Canada, where [Au(CN),]- and [AuC12]- which render gold highly mobile.
elevations are subdued and where profile development is fair Some organic (humic) complexes evidently have the same
to good, certain generalizations on the geochemistry of gold in facility. Anions, cations and complexes which inhibit the
the soils are permissible. mobility of gold are numerous. Cations and anions such as
2. Climate: my investigations were too restricted to draw OH-, Fe3+,Mn2+,etc. precipate insoluble compounds that
adequate conclusions about the effect that climate may have coprecipitate or adsorb soluble gold thus decreasing the
on the chemistry of gold in the soil. In the far northern regions mobility of the element. The presence of H+ in solution causes
where permafrost prevails, the soils are greatly disturbed by the dissociation of many gold complexes stable only in
frost-boiling, solifluction, etc. This tends to disrupt the alkaline environments; OH- has the same effect on the acid
profiles and brings particles of unweathered material to the complexes. The presence of H2S or S2-, due to the bacterial
surface. This is a favourable feature for geochemical prospect- reduction of protein complexes in organic environments, may
ing, since particles of gold and gold-bearing secondary oxida- precipitate the sulphide or the free metal, thus greatly reduc-
tion products occur near the surface in the vicinity of deposits, ing the mobility of gold.
a circumstance that permits relatively shallow sampling. In the 6. Eh of soils: soluble forms of gold are easily reduced,
more temperate regions where podzols and other types of soils generally to the metal, by practically all substances as shown
predominate, normal chemical conditions prevail, and the in the next section on natural waters. The migration of gold in
chemistry of gold in the soils can be traced with more soluble forms in soils is, therefore, temporal and generally not
assurance. Under conditions of tropical weathering gold extensive. Complexing, however, may increase the mobility of
appears to be relatively mobile in lateritic terranes according the element in some environments. Indirectly, the Eh is also of
to the recent investigations of Roslyakov et al. (1971~).This major importance in the migration of gold in soils since it
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

plays a part in the hydrolysis of iron and manganese, the ticularly the humic substances, adsorb gold strongly and
precipitation of hydrous iron and manganese oxides, the apparently build the element into their structures, perhaps
oxidation of organic complexes, etc., and these exert a major forming chelated complexes with the metal. Whatever the
influence on the mobility of gold as described below. mode of binding, it is evident that much gold is immobilized
7. pH of soils: the pH of soils affects the mobility of gold where abundant organic matter is present in the soil. This is
in many ways, some of them directly and some indirectly. shown by the marked enrichments of gold in the A, (humic)
These are discussed below. Normally, gold is more soluble horizons of many soils, and its presence in relatively increased
under acidic conditions such as where pyrite, pyrrhotite, and amounts in some peat and half bog soils and in decomposed
other sulphides are undergoing oxidation. However, in alka- organic debris in marshes. Soils containing charcoal layers
line environments where suitable complexing agents are (from ancient forest and peat fires) may exhibit marked
present gold is highly mobile. enrichments of gold (and silver) in these layers.
The chloride complex [AuCl,]- and other acid complexes The pH seems to have little effect on the mobility of gold
are stable only under acidic conditions. On neutralization in the organic horizons of soils or in peats, etc. The pH may
these complexes dissociate and the oxide, hydroxide or metal be as low as 3.0 with no particular decrease in the content of
are precipitated. Similarly the alkaline complexes of gold viz. gold in the humic components.
[Au(CN),]- and [Au(S203]- are stable only under alkaline Another point of interest is the fact that as the hurnifica-
conditions, the oxide, hydroxide or metal being precipitated tion processes proceed the large co-ordinated humic groups
on neutralization. Changes in pH are, therefore, important, in dissociate and pass into a soluble (colloidal) form in the soil
the mobility of gold in soluble complex forms in soils. solutions and are ultimately removed by the ground waters.
However, the chemistry of gold in soils is rarely dependent As the soluble groups appear to retain much of their gold
during the disintegration process, the mobility of gold is
alone on the effect of pH on gold ions and complexes since
the presence of iron, manganese, alumina and organic matter increased in the soils. (See also the section on gold in natural
modify the course of events in a number of ways. waters in this chapter.)
Finally, under a high oxidation potential the humic
In an environment where decreasing acidity and a rela- complexes may be oxidized yielding CO,, H,O, etc. and
tively high Eh prevail, iron if present in the ferrous state, is liberating any bound gold. This gold is then in an extremely
oxidized to the ferric state, undergoes hydrolysis and may be mobile state, although in most cases it is generally seized
precipitated as a basic salt or as the oxide hydrate, quickly by the remaining humic complexes. This process
FeO(OH).nH,O. In some profiles where the pH ranges from 3 repeated ad infiniturn leads to the enrichment of gold (and
to 5, jarosite, KFe,(SO,),(OH),, and beudantite, PbFe, silver) noted in some of the organic layers of soils, in peats,
(AsO,)(SO,)(OH),, two complex basic sulphates of ferric iron, etc.
may be present, and these tend to scavenge much gold, 9. Fez+ - Fe3+ content of soil solutions: the acid
rendering the element immobile. In other profiles it is evident reaction~~O*~~
that much of the gold is tied up in the hydrous iron oxides. +
Fez+ Au+ % Au Fe3+ +
Normally ferric oxide hydrate is a good carrier of gold, since +
3Fe2+ Au3+ Au 3Fe3+ +
its colloid bears a positive charge, which tends to coprecipitate are reversible, the direction depending on the Fe2+/Fe3+ratio
the negative gold complexes and the negatively charged gold in solution. Where a high Fez+concentration prevails, gold is
colloids. Where PO,3-, As0,3-, hydrated MnO,, silica, humic precipitated, and the mobility of the element is reduced.
colloids, etc. are Dresent these are attracted to the femc oxide Where a high Fe3+concentration is present gold is retained in
hydrate and may give the combined colloidal complex a the soluble and hence mobile state. It should be particularly
negative charge, a feature which permits the adsorption or noted that the reactions apply only to iron in solution; once
coprecipitation of cationic gold as well as numerous other hydrated oxides of hydroxides are precipitated these no longer
cations. play a part in the oxidation-reduction reactions. Soluble
Decreasing acidity, likewise, causes the precipitation of manganous salts probably also play a role similar to those of
hydrated manganese oxides and since these carry a negative ferrous salts in slightly acid, neutral, and mildly alkaline soils.
charge they adsorb and coprecipitate any available hydrous + +
2Au+ MnZ+ 4H+ + 20, % 2Au + MnO, +2H,O
iron oxides, alumina, etc., which impart a net positive charge
to the gels. These in turn adsorb and coprecipitate the
2Au3+ 6H,O+ +
3Mn2+ 2Au 3Mn0, + + 12H+
negatively charged gold complexes and hydrosols. Clay miner- z0 These reactions are some of the most important as regards the
als have a similar effect. (See also the discussion on adsorption geochemistry of gold (and silver) in near surface processes. The
and coprecipitation of gold complexes and colloids in the first has been discussed in detail by Tananaeff (1925) as re-
section on gold in natural waters and their precipitates.) gards silver.
The oxidation-reduction couples for ferrous, manganous, au-
These features serve to emphasize the fact that gold is rous and auric ions and their potentials as given by Latimer
relatively immobile in soils where the pH lies between 4 and 8. (1952) are as follows:
The mobility of the element is restricted in part by the Fez+= Fe3+ e- + EO = -0.771
dissociation of alkaline gold complexes in an acid medium, the 2H,O = 0, + 4H+ + 4e- EO = -1.229
Mn2+ + 2H,O = MnO, + 4H++ 2e- E0 = - 1.23
dissociation of acidic gold complexes in an alkaline medium, Au = Au3+ 3e-+ EO = -1.50
but mainly by the hydrolytic and colloidal reactions that Au = Au+ + e- EO = -1.68
characterize the chemistry of iron, manganese and alumina in
the soils. Note: Both ferrous and manganous ion can reduce gold from its ionic
8. Presence of organic compounds: organic matter, par- state to the metal.
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

10. Formation of colloids: practically nothing is known close within their caves under the ground, from the parching sun.
Yet not without great danger: for if they happen to wind them and
about natural gold colloids in soils. Gold colloids carrying a catch their sent, out they go, and follow after them in great hast,
negative charge are easily prepared in the laboratory, and if and with such fury they fly upon them, that oftentimes they teare
these occur in nature they would be expected to increase the them in pieces; let them make away as fast as they can upon their
mobility of the element in soils. Because the gold hydrosols most swift camels, yet they are not able to save them. So fleet of
carry a negative charge the precipitation of these colloids pace, so fierce of courage are they, to recover gold that they love so
well."
would take place readily where positively charged colloids and
electrolytes are present in the soil solutions. (See also the As can be imagined various interpretations have been
discussion on colloids in the section on natural waters.) placed on this quaint tale which we cannot pursue here.
11. Influence of organisms: there are no direct data on Evidently the site of these gold-digging ants was the Gobi
the part that organisms such as bacteria and fungi play in the Desert, but there have been various other theories (Adams,
mobility of gold in the soil. Indirectly, one can assume with 1938).
some confidence that the effects are important in two ways-
some bacteria and fungi solubilize and hence mobilize gold, Other products of weathering
whereas others precipitate the element. Williams (1918) noted There are few data on the occurrence and content of gold (and
that Penicillium glaumm and Oidium lactis develop in colloidal silver) in weathered products such as bauxites, laterites,
gold solutions containing tannin and that they remove the bog-iron ores, bog manganese deposits, etc.
metal from solution, but no explanation of the process could Some laterites tend to be enriched in gold especially in
be suggested at that time. Par& and Martinet (1964) noted the vicinity of underlying gold deposits. Some values for these
that Bacillus subtilis, Serratia marcescens and Pseudomonas laterites are shown in Table 20. Normally laterites contain
fluorescens were capable of solubilizing gold to a marked only small amounts of gold, generally less than 0.01 ppm.
degree, the effect diminishing and precipitation increasing There appear to be only limited investigations of the gold
with the age of the cultures. Lyalikova and Mokeicheva (1969) content of typical bauxites.
have also found that many heterotrophic bacteria have the Tenyakov et al. (1970) determined the gold content of
ability to dissolve gold, and that sulphur compounds (thiosul- bauxites from various localities in U.S.S.R. and Hungary.
phates and polythionates) which accumulate during the oxida- They concluded from their results that:
tion of sulphides by sulphur bacteria contribute to the 1. Gold appears to be always present in bauxite since the
solution of gold. A culture isolated from a gold deposit, element was detected in all samples analyzed from all depos-
similar to Bacillus alvei, was found to dissolve 500 to 600 ppb its.
Au in 3 weeks. In an extended study on the solubilization of 2. The gold concentration in bauxite exhibits an extreme-
gold by micro-organisms, Doxtader (in Lakin et al., 1974) ly wide range from 0.0004 pprn to 0.0290 ppm, a variation of
found that the microbial strains utilized showed various two orders of magnitude. The average (arithmetic mean) gold
abilities to solubilize the noble metal. (See also the section on content of bauxite is 0.0045 ppm.
gold in plants and animals.) 3. There is some difference in the average content of gold
Bacteria and other micro-organisms also break down and in geosynclinal bauxite and platform bauxite; the latter is
decompose the various organic complexes and hence would somewhat richer in gold (0.0049 pprn compared with 0.0036
liberate any complexed gold in a reactive and relatively
PP~).
soluble form. The production of H,S by bacteria on the other 4. The gold content of bauxites is clearly related to their
hand would reduce the solubility of gold as mentioned above. parent rock type; the metal is generally enriched in bauxite
Finally, burrowing animals such as gophers, groundhogs presumably formed from igneous or eruptive rocks but is
and ants may physically transport gold particles from depth to much lower in that formed from clay and shale.
the surface profiles of soils. An interesting case of the action
of termites in Kalahari sand, Rhodesia is described by Watson Tenyakov et al. (1970) thought that the gold in bauxites is
(1972). The termites in excavating galleries to the water table probably mainly present in a mechanical form (as native
have evidently brought some particles of gold to the surface gold).
from gold-bearing fissures and deposited them in their The gold content of bog iron and manganese deposits is
mounds. (See also the section on biogeochemical methods in not well known. My analyses of most of the bog iron and
geochemical prospecting in Chapter V.) maganese deposits of Ontario and Quebec show that such
deposits contain only low amounts of gold (t0.005 pprn). A
bog iron-manganese deposit in Canoe Lake, New Brunswick
The above reminds one of the wonderful tale of the gold was found to contain 0.015 pprn Au and 2.2 pprn Ag; another
digging ants that has been passed from antiquity down in Bass Brook, near Walton, Nova Scotia had 0.34 pprn Au
through the generations to modem times. Herodotus had one and 0.68 pprn Ag; and a third near Long Lake, New Brun-
version, Strabo another, Pliny yet another. In his Historia swick had up to 1.4 pprn Au and 0.8 pprn Ag. The last bog is
naturalis (Book 11, Chapter 31) Pliny records: near stringers of quartz that carry a little gold.
"In the countrey of the Northerne Indians, named Dardae, the Ants During the weathering of gold- and silver-bearing rocks
do cast up gold above ground from out of the holes and mines and deposits the two metals tend to concentrate in particles of
within the earth: these are in colour like to cats, and as big as the
wolves of Aegypt. This gold beforesaid, which they worke up in the native gold in the weathered detritus. Such auriferous blankets
winter time, the Indians do steale from them in the extreme heate of or eluvial deposits are common in Brazil, the Guianas,
Summer, waiting their opportunitie when the Pismires (ants) lie Mexico, Africa, Asia and elsewhere. They are composed
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CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

principally of laterite-a mixture of femc oxides, hydrated Au. In general the average gold content is about 0.025 ppm.
ferric oxides, clay and sand. Some wntain essentially gravel, Other types associated with sink-holes in limestone are known
sand and clay and may be partly cemented by caliche and iron in Burma and China (Rundall, 1927-1928; Searls, 1952) and
oxides. The origin of the gold-silver particles in these materials have been worked in the past. Somewhat similar deposits
has been a long-standing problem. It is certain that some of developed in karsts are mined in the Yakutia region of the
the particles are of residual origin and represent the flakes and U.S.S.R. There the deep oxidation of auriferous metasomatic
nuggets weathered from gold-quartz veins. Some of the gold rocks developed in limestones has led to concentrations of
and silver is probably also of chemical origin; that is, the gold in karsts in the limestones. These deposits are called
particles are either enlarged or individually accreted by 'Kuranakh type' by the U.S.S.R. geologists; they are described
additions of gold and silver from solutions that derived the in more detail in Chapter 111.
metals both from the weathered constituents of the rocks and Undoubted fossil gold-silver placers have been described
from various gold- and silver-bearing sulphides in veins and from several wuntries. They occur in conglomerates, sand-
other types of deposits. stones, and arkoses of various ages. Examples are known in
As the weathering cycle proceeds the material in deposits the Black Hills, South Dakota; Gays River, Nova Swtia;
may be further decomposed, eroded, transported and redepos- Indian River, Yukon (Maclean, 1914); and elsewhere. (See
ited. This can be effected by wind, streams, rivers or by the also the section on placers in Chapter 111.) The auriferous
surf of the sea, resulting in aeolian, stream, river, delta and Witwatersrand quartz-pebble conglomerates, the greatest of
beach placers. During these movements the gold-silver parti- all gold deposits, are considered to be modified fossil placers.
cles may be comminuted and reduced to a flour or, as is more These deposits, and others in the same category, are discussed
often the case, especially in an aqueous environment, the small at length in Chapter 111.
particles may be recrystallized, partly dissolved and the gold
reprecipitated on the larger particles. Since silver is more
mobile (more soluble) than gold the chemical processes of Mountains big with mines, whence
solution and reprecipitation generally lead to an increase in many a bursting stream auriferous plays
the fineness of the gold flakes and nuggets with increasing -Thornson, Summer
distance from the source. Furthermore, the outside parts of
nuggets often have a significantly greater fineness than the Gold in natural waters and their precipitates
inner parts, a feature that adds convincing support to the Gold is widely diffused in ground, spring, stream, river and
theory of accretion of gold from solutions as the particles are lake waters, but generally only in small amounts. The average
moved along by mechanical processes. Other evidence of the for all fresh waters is about 0.00003 ppm (0.03ppb) Au.
solution and precipitation of gold and silver in placers is Marked variations above and below this average have been
witnessed by the occurrence of gold crystals in places, wire reported for a number of regions.
gold, sprigs of gold, replacement of deer horns by film gold, Most of the gold in natural fresh waters is derived from
agatelike structures of certain nuggets and the fact that some gold present in rocks, mineral deposits and their weathered
investigators have found increased amounts of gold and silver products. Infinitesimally small amounts of gold (and silver) in
in stream waters in the vicinity of gold veins and polymetallic some fresh waters may arise from industrial and domestic
deposits. (See the section on gold in natural waters.) Further usage.
details on the interesting problems of the geochemistry of the Several investigations of the gold wntent of hot spring,
origin of gold in oxidized zones and placers is given in ground, stream, river and lake waters have been carried out in
Chapters I11 and IV. a number of wuntries. Data from these investigations and
The most frequent associates of gold-silver particles in from my own limited studies are recorded in Table 21.
placers, in addition to the common silicates, are magnetite, Only a few detailed investigations of the gold wntent of
ilmenite, rutile, monazite, garnet, zircon, tourmaline, pyrite, hot springs and thermal waters are extant in the literature.
native bismuth, cassiterite and cinnabar. Nuggets of native Some of the more comprehensive studies are summarized
silver are rare, although they do occur in some of the placers below.
in Alaska and in those of Burwash and Arch creeks (Kluane Koga (1960, 1961) carried out an extensive investigation
and Donjek rivers district), Yukon. Arquerite, the silver-gold- of the gold, silver and numerous other trace elements in 27 hot
mercury amalgam, occurs in the placers of Silver, Vital, Kenny springs in the Beppu area of Japan. The range in the gold
and Kwanika creeks in the Fort St. James area, British contents was 0.0 to 2.2 ppb, and the average for all hot springs
Columbia and in Burwash Creek in the Kluane Lake district, was 0.53 ppb Au and 10.7 ppb Ag, giving an average Au/Ag
Yukon. ratio of 0.05. Ninety per cent of the springs had less than 1
Certain types of eluvial and alluvial fans and similar ppb Au. Hot springs with low pH values (2.0-3.8) contained
deposits, in addition to gold and silver, also wntain galena, the highest amounts of gold, especially those enriched in
anglesite, bindheimite, mimetite and other oxidation products sodium sulphate and sodium chloride. The silver wntent was
of lead-zinc-silver and gold veins. Such deposits are known in low in NaCl springs and high in sodium bicarbonate ones.
many parts of the world, particularly in the unglaciated Gold showed no particular relationship to sodium bicarbon-
regions. Those associated with a mineralized porphyritic ate. The temperature of the springs influenced the gold
granite stock near Guadalcbar in Mexico have received wntent; in general the higher the temperature the higher the
detailed attention (Foshag and Fries, 1942; Fries and Schrnit- gold content. Most spring precipitates were found to contain
ter, 1948). Few of these deposits contain in excess of 0.10 ppm gold, the highest value being 56.5 ppb (0.056 ppm). No
 Contents

Table 21. Gold content of natural waters with manganese obtained in the spring precipitates. The
No. of Au pH positive correlation of gold with chromium is of interest
Description samples (range) (range) Remarks considering the common occurrence of chromium-rich altera-
tion minerals (fuchsite) in certain types of gold deposits.
Hot springs 35 65%of the values Weissberg (1969, 1970) described red-orange amorphous
lie in the range sulphides with opaline silica, precipitating from thermal
0.04-0.7 ppb
Groundwaters 8 H,S carbonate waters along the eastern margin of the Taupo volcanic belt in
and cold springs at Matze- New Zealand; these contained a number of ore elements up to
springs sta (Sochi) the following concentrations:
U.S.S.R. are en-
riched in gold; up As 2% Tl 1000 ppm
to 35 ppb accord- Sb 10% Pb 50 ppm
ing to Zverev Au 85 ppm Zn 200ppm
et al., (1947) W 3%
Groundwaters, 84 84%of the values Ag 500PPm
cold spring lie in the range Hg 2 O P P m Au/Ag ratio 0.17
waters and 0.001-1.0 ppb The transporting waters carry these elements in the following
mine waters maximum values:
in vicinity of
gold deposits As 8 ppm Tl 0.007 ppm (7 ppb)
Stream and
river waters
24 73%of the values
lie in the range
Sb 0.3 ppm .
S (as sulphide) 120 ppm
0.002-0.1 ppb Au 0.00004 pprn (0.04 ppb) Au/Ag ratio 0.06
Stream and 24 91% of the values Ag 0.0006 pprn (0.6 ppb)
river waters lie in the range
in vicinity of O.Oo48-0.15O These thermal waters are essentially alkaline (pH 6-7) Na-K-C1-
gold deposits
Lake waters HC0,-C0,-SO,-SiO, waters, with temperatures ranging from
Fresh 21 Lake Baikal 200 to 290°C at a depth of 1 km.
(Jones, 1970) and Browne (1969) records 0.0001 to 0.001 pprn Au and 0.002
Greek lakes (Gri- Ag in water separated at atmospheric pressure from the
manis et a/.,
1965) Broadlands geothermal drillhole, Taupo Volcanic Zone, New
Saline Great Salt Lake, Zealand. The pH of the water was 8.55 and the type -
Utah and Owens Na-K-Cl-HC0,-CO, - carrying small amounts of As (9 ppm),
Lake, California Sb (1.5 ppm), W (0.03 pprn), Zn (0.015 pprn), Cu (0.012 ppm),
Oceans and 73 71% of the values Tl(O.O1 ppm) and a number of other elements. This water has
seas lie within the range
0.0014.50 D D ~ deposited base metal sulphides (pyrite, galena and sphalerite
Compiled from data by: Albul and Miller (1959) Kaspar et a/. (1972) with silver telluride, cobaltite and Ni-glaucodot) in tuffs,
Baur ( 1942) Koga (1 960,196 1) tuffacwus sediments and rhyolites, which it penetrates.
Borovitskii et a/. (1 966) Kropachev (1935) Goleva et al. (1970a,b) found 0.8 to 1.6 ppb Au in
Brooks (1960) Lincoln (1 9 1 1 b)
Browne (1969) Lombardi (1964) strongly acid (pH t 1, Eh >0.8 V) HC1 fumaroles of the
Chernyayev et a/. (1969) Noddack and Noddack Ebeko volcano on Paranushir Island, Karnchatka, U.S.S.R.
Cushing and Rancitelli (1939)
(1972) Oka et a/. (1 964) They concluded that the gold was present mainly as halide
Fischer (I 966) Popova ( I97 1) complexes.
Gebler and Putnam (1953) Gottfried et al. (1972) report that the gold content of the
Stramkovskaya(1957) Razin and Rozhkov (1963)
Goldberg (1 957) Rosenbaum et a/. ( 1969) thermal waters in Yellowstone National Park, U.S.A. is very
Goleva ( 1 970) Schiller et a/. (1 97 14b) low, generally 0.0044.040 ppb, with a maximum of 0.1 ppb.
Goleva et a/. ( 19704b) Sharma (1 972) The sinters on the other hand, are relatively enriched in gold,
Gosling et a/. (197 1) Stark (1943)
Gottfried et a/. (1972) Talipov et a/. (1 972) 5 to 50 ppb with maximum values up to 5000 ppb. Sinters
Grange (1937) Vorotnikov et a/. (1973) having high gold concentrations also contain correspondingly
Grimanis et a/. ( 1965) Weiss and Lai (1963)
Haber (1927, 1928) Weissberg (I 969, 1970) higher amounts of arsenic, antimony and mercury. The pH of
Hummel(1957) White et a/. (196346) the waters ranges from 2 to 9, but most have a neutral to
Ikeda (1 95546) Yasuda (1927) slightly alkaline reaction.
Jenne eta/. (1968) Zverev et a/. (1 947)
Jones (1 970) Zvyagintsev (1941) Summarizing the available data on hot springs one can
say that the pH of the water seems to have little effect on the
transfer of gold. All springs, including those with acid, neutral
detailed correlation between gold and silver was found in the and alkaline reactions may carry the element, although there
spring water, but there was a positive correlation between the is a tendency for it to be enriched in neutral and alkaline
two elements in the spring precipitates. The average Au/Ag waters. Temperature evidently has an effect, the hotter the
ratio in the spring precipitates was about 0.05, much the same water the higher the gold content in some spring systems.
as the average ratio for the water. Positive correlations of gold Correlations with other elements are difficult to establish with
with chromium and manganese and a negative correlation certainty mainly because of insufficient data. Gold is generally
with titanium were found in the spring waters, and a positive accompanied by silver, and in nearly all auriferous springs
correlation with silver and arsenic and a negative correlation there is a relatively high content of As, Sb and SO,. Nearly all
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

hot springs carry sufficient C1, S2-,As and Sb to complex and bicarbonate and sodium bicarbonate waters); those above-
render mobile the small amounts of gold present. and inter-permafrost in the Lower Cambrian rocks (mainly
There are insufficient data on the gold content of normal calcium bicarbonate waters); and those below the permafrost
groundwaters and cold springs to draw satisfactory conclu- in Lower Cambrian and Archean rocks. The results of the
sions about the transport of the element in these waters. From investigation showed that: the most common companions of
my experience I conclude that the average gold content of gold in the groundwaters were As, Sb and Tl (and to a lesser
most normal groundwaters and cold springs is about 0.005 extent Ag, Ti, Sn and Te); the inter-permafrost waters
ppb. My compilation of the gold content of normal stream contained the highest gold contents; the gold contents in
and river waters shows that the values range from 0.002 to 4.7 groundwaters near the gold deposits fluctuated from 0.03 to
ppb with some 73 per cent of the values in the range from 10.0 ppb; the maximum gold concentrations occur in ground-
0.002 to 0.1 ppb. In my experience most streams and river waters with a high content of dissolved iron (up to 300 ppb)
waters have t0.005 ppb total gold including that dissolved and manganese (up to 100 ppb); and that the gold contents in
and associated with particulate matter. In a recent study stream waters near the gold deposits were generally less than
Cushing and Rancitelli (1972) found that the gold and silver 0.05 ppb. An earlier investigation of the waters associated
contents of the Columbia River water, as determined by with the Kuranakh deposits by Razin and Rozhkov (1963)
neutron activation analyses, varied from time to time as indicated that the more acid the waters the higher the gold
shown below. content. Gold appears to be much more mobile than silver in
Date the area since the ratio Au/Ag in the groundwaters as
Element 1 1-4-68 2- 12-69 4-24-69 6- 1 1-69 8- 14-69 calculated from the data of Borovitskii et al. (1966) is
generally high, in some cases up to 450.
(PP~)
Au 0.030 CO.005 <0.005 (0.005 <0.005 Chernyayev et al. (1969) reviewed the literature on gold in
Ag 0.50 (0.01 CO.01 3.03 CO.01 natural water and carried out work on the natural waters of
northern Kazakhstan and southern Urals. In the near-surface
groundwaters of the Kokchetav uplift gold was found in 40
There are insufficient data on the gold content of fresh- per cent of the analyzed samples (altogether 180 samples were
water lakes to draw any conclusions. Grimanis et al. (1965), analyzed). Its content varied from 0.1 to 4 ppb. The distribu-
using activation analysis methods, reported gold contents in tion of gold in the groundwaters was lognormal. Its average
11 Greek lakes to range from 0.2 to 7.7 ppb (av. 1.5 ppb). The content in the samples for which positive results were ob-
corresponding silver contents were less than 10 ppb. tained is 0.4 ppb, or if all analyzed samples are considered
In salt lakes Lincoln (191 1b) reported up to 32 ppb Au in (including those in which gold was not detected), 0.15 ppb.
Great Salt Lake, Utah; in the Nevada salt marshes the same Little difference was found in the gold content of waters
author reported no gold present. Carpenter (1941) found no circulating through different rock types (e.g., gabbro, 0.58
gold in the salts and other materials of the dry lakes in ppb; granodiorite, 0.5 ppb; shales and sandstones, 0.522 ppb).
Nevada. In the summer brine of Owens Lake, California In the Shalkarsk area the mode was 0.2 ppb and the mean
Lombardi (1964) reports the presence of gold in the 10 to 100 content (all samples) 0.154 ppb. Analyses of groundwaters
ppb range. from one of the Kokchetav gold deposits showed gold con-
Most of the work on the gold content in cold springs, tents ranging from 0.4 to 1 ppb. These waters always contain
groundwaters and stream and river waters has been done in As, Mo, La, Y, Yb, Li, Cu and a number of other elements.
the vicinity of gold-bearing deposits. As shown in Table 21, The content of silver in these waters is low. There was no well
the values tend to be higher than in similar bodies of water defined correlation between the content of gold in the waters
remote from gold deposits. A number of detailed investiga- and any of the trace elements nor between such constituents
tions are extant in the literature, some of which merit brief as carbonate, sulphate, chloride and hydrogen ion (pH). The
reviews. hydrogeochemical profiles plotted across the gold deposits,
Kropachev (1935) seems to have been the first to examine however, show that directly over the orebodies there are peak
the gold content of normal fresh waters as well as those in concentrations of Au, Ag, As and Bi. The peaks for Ag and As
gold belts. He found from 40 to 60 ppb Au in the rivers of are sharp; those for Bi are broad.
nonauriferous regions and some five times as much gold in the Goleva et al. (1970qb) examined both ground and surface
river water of auriferous regions. Still higher quantities of gold waters in the vicinity of a number of gold deposits in various
were found in the drainage waters of gold mines (500-1300 geological and geographical settings in U.S.S.R., mainly in
ppb). While his analytical methods were crude they did show East Transbaikal, Central Asia, Southern Urals and Kamchat-
that the waters in auriferous regions are commonly enriched ka. The contents they found ranged from 0.05 to 10 ppb Au.
in gold. From their studies they concluded that:
Borovitskii et al. (1966) examined the gold content in the 1. The commoner types of natural water (pH 5-8 and Eh
waters of the Kuranakh gold-bearing area of the Aldan massif, 0.1-0.5 V) most probably contain gold as uncharged particles
U.S.S.R. The gold ores are mainly oxidized disseminated and organic complexes. Gold in the presence of thiosulphate
pyritic ores with pyrite, magnetite, hydrogeothite, hematite ions forms the very stable [Au(S,O,),P- ion.
and gold. (See also Chapter 111.) Associated elements are Ag, 2. The halide complexes, [AuCl,]-, [AuClJ and [AuBr,]-,
Cu, Pb, Zn, As, V and Ga. Three types of groundwaters are can be formed only in media with Eh >0.9 V and pH < 1 at
distinguished in the area - those in unconsolidated recent appropriately elevated concentrations of chloride and bromide
materials above the permafrost (mainly organic and calcium ions ( C l - 2 2 mM, Br- >0.6 pM). Such waters are exotic
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

under natural conditions and occur only in the HCl fumaroles (1974) found gold in all saline groundwater samples from the
of active volcanoes (Ebeko, etc.). petroleum fields in the northern Tomsk region, the contents
3. Waters containing H,SO, are unfavorable for the ranging from 0.02 to 0.49 pg/L Shvartsev concluded that all
migration of gold. Thus, waters in rapidly oxidizing zones of the gold in the saline groundwaters was of lithological origin.
gold-sulphide deposits have only 0.1-0.5 pg/L. The available data on the gold content of ocean water is
4. The commonest coprecipitants of gold in natural given in Table 21. The average gold content of the oceans
waters are: iron hydroxides, calcium carbonate, disulphides appears to be about 0.01 17 ppb and the average silver content
and colloidal silica. about 0.3 ppb giving an Au/Ag ratio of 0.04.
5. The gold content of groundwaters can be used as a The French chemist, J.L. Proust (1754-1826) was the first
specific means of prospecting for gold-bearing deposits. to report the presence of gold in seawater, and the Enghsh
chemist S. Sonstadt (1872) carried out the first quantitative
analysis finding less than a grain of gold per ton (about 65
In the Balei gold district of eastern Transbaikal, U.S.S.R., ppb). Many years later Fritz Haber camed out over a period
Goleva (1970) found background contents of t0.07 ppb Au of some 7 years an extensive investigation of the gold content
and anomalous contents >0.15 ppb in the groundwaters. In of seawater. Reviews of these and other investigations are
alluvial and surface waters the background and anomalous given by Mellor (1923), Jaenicke (1935), Gmelin (1950),
contents were respectively <0.05 and >0.1 ppb Au. Most of Purkayastha and Das (1965), Jones (1970) and Wood (1971).
the waters are weakly mineralized calcium, magnesium and The gold content of the oceans appears to be variable as
sodium bicarbonate types with small amounts of sulphate. will be readily apparent from the following short review of
The main indicators of gold deposits in the hydrologic system some of the significant investigations. This variation appears
were found to be Au, Ag, As and Zn and in some areas Bi and to be real, although some variations reported in the literature
Sb. may be due to different methods of analysis.
Gosling et al. (1971) used neutron activation methods to Haber (1927, 1928) found that seawater did not contain
investigate the gold content of stream, spring and mine water nearly as high contents of gold as had been earlier reported.
in both gold-bearing and barren areas underlain by sedimen- His values ranged from 0.003 to 4.8 ppb. He noted large
tary, igneous and metamorphic rocks of the Colorado Front variations in the sea both on an areal and local basis and
Range. The total gold content ranged from nondetectible attributed them to a variety of causes mainly to the presence
(t0.001 ppb) to 0.150 ppb. The 'solute' (dissolved) gold of gold in various forms - as the chloroauric ion, in colloidal
concentrations were generally higher by a factor of 2 to 6 than form and adsorbed by both organic and inorganic matter.
the gold held on or in particulates, and no relationship was Yasuda (1927) found relatively large amounts of gold
found between both these values (solute and particulate) and (3-20 ppb) in the water of bays in various parts of Japan. The
rock or water types. Their data indicated a spring flush-out of equivalent silver content was 20 to 70 ppb.
dissolved gold in groundwater during the snow-melt recharge Putnam (1953) gives an interesting account of the inves-
period. They concluded that direct hydrogeochemical tigation of gold in seawater from Sonstadt and Haber up to
prospecting using gold as an indicator of its deposits is the 1950's. He, himself, carried out a number of investigations
unpromising. of the gold content of seawater and concluded from these and
Talipov et al. (1972) determined the Au, Ag and As analyses in the literature that the concentrations could vary
content of the surface waters of the central Kyzylkum gold through the range of 0.003 to 44 ppb Au.
belt and found the gold content to range from 0.01 to 0.95 Hurnmel (1957) found by radioactivation analysis that
ppb; the corresponding arsenic contents were 10 to 378 ppb. the gold content of the oceans depended on the distance from
The gold content was not related to the chemical composition the shore. He recorded 0.40 ppb Au for Enghsh coastal waters
of the water. and 0.015 ppb Au for water from the northwestern limit of the
Kasper et a[. (1972) found from 0.09 to 0.20 ppb in Bay of Biscay.
waters flowing from old gold mine tunnels in Austria (Irnhoff Brooks (1960) using an ion exchange enrichment tech-
and Bockhart) and Czechoslovakia (Jilovb). They noted a nique obtained 0.009 ppb Au in seawater at Sea Point, Cape
general development of inhomogeneity in the waters after 21 Town, South Africa. Weiss and Lai (1963) used cocrystalliza-
days of storage. tion methods to determine the gold content of seawater 40 mi
Volkov and Shakhbazova (1973) determined the gold due west of San Francisco. Their average was 0.068 t 0.003
content of the surface and groundwaters of the Beskes ppb. Oka et al. (1964) found from 0.006 to 0.429 ppb Au in
auriferous copper ore field. The gold content was found to surface ocean samples and samples taken at a depth of 100 to
range from 0.0 to 5.2 ppb. The distribution of gold in the 200 m off the Japanese coast. Schutz and Turekian (1965)
waters obeyed the lognormal law with a mean gold content of found the gold content of seawater from the Atlantic and
0.09 ppb and a dispersion factor of 0.474. Within these Indian oceans to range from 0.004 to 0.027 ppb with an
parameters the minimum anomalous content was 0.3 and the average of 0.01 1 ppb. The silver content in all oceans ranged
maximum 2.5 ppb, the last value being a positive indication of from 0.055 to 1.5 ppb and the average was 0.29 ppb. The
the presence of gold in the ores. No relation was observed average Au/Ag ratio in the sea as calculated from their data
between the chemical composition and the distribution of gold is, therefore, 0.04.
in the waters although the highest concentration of the Wood (1971) carried out an extensive investigation of the
precious metal was noticed in Ca(HCO,), waters. geochemistry of gold in the marine environment to determine
In the west Siberian artesian basin of U.S.S.R. Shvartsev possible natural concentrating processes which may be used to
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

extract gold. Radioactive gold tracers 19%u and lg8Au were silver in foam and slime of Kara-Bogas-Go1Bay (Caspian Sea)
used in the investigations. The solubility of gold in seawater U.S.S.R. was considerably greater than that in the seawater.
was determined to be of the order of 4pg Au/L (4 ppb) about Dudey et al. (1969) found 7.3 X lo-' pg/m3 Au in marine
the same order of magnitude as previously predicted by SillCn. aerosols over the Atlantic Ocean.
Differences in the ion change properties of Au (I) and Au The investigations of the gold content in ocean water
(111) were determined by experiments with electrolytically indicate that there are major areal variations. The data are not
produced mixed solutions of aurous and auric chloride which extensive enough to draw any conclusions about the variations
were passed through strong anion exchange columns. Approx- with depth. Most studies seem to indicate that nearshore
imately 10 per cent of the soluble gold in equilibrated samples are higher in gold than those in the open oceans, a
seawater solutions was found to be nonionic. The soluble feature that is probably due to the greater amount of inorgan-
character of the gold in these solutions was unchanged when ic and organic particulate matter, and hence more adsorbed
mixed with sulphide waters. This indicated to Wood (1971) and particulate gold, in nearshore waters compared with those
that gold would not be concentrated in anoxic basins. The at a great distance from the shore. Major local variations in
character of the soluble gold was also studied using dialysis the gold content of seawater are probably due to the presence
and electrophoresis. of variable amounts of particulate matter. Future research on
Soluble gold was rapidly adsorbed on several clays the gold content of the oceans should be directed to determin-
followed by a release of gold within about 24 h of the mixing ing precisely the quantity of 'solute', adsorbed, and particulate
time. This is about the time for the equilibrium shift of auric gold in the samples.
to aurous gold to be established. The source of the gold in ocean water is speculative and
problematical. Presumably most of the precious metal is the
result of terrestrial weathering, and there may be a small
Gold was found to be easily reduced and to be adsorbed contribution from the weathering of marine sediments. Along
on many different materials. Most materials used in sampling the ridges and rises of the oceans some of the gold in oceanic
and analysis for gold in aqueous media adsorbed gold least water may be of volcanic exhalative origin.
from acidified solutions. Rubber and cellulose ester fiber The oceans are an enormous reservoir of gold (and
filters were notable exceptions. silver). A calculation using the average gold content of
Neutron activation methods were devised by Wood seawater (0.02 ppb) and the total mass of the oceans (143 X
(1971) to analyze marine samples for gold. Analyses of 1016metric tons) indicates some 28.6 X lo6 metric tons of the
samples from southeast Alaska indicated that gold in seawater metal in the oceanic system. Other estimates in the literature
is predominantly in a soluble nonionic form, with ionic and of the total gold content of the oceans range from 5 X lo6 to
particulate forms making up only about 20 per cent of the 6 X 101° metric tons. The presence of so much gold in the
total. The average gold content in these waters was found to oceans has whetted the scientific interest of many men,
be 3 ng Au/L (0.003 ppb) with a range of 1 to 11 ng Au/L. especially as regards commercial recovery of the metal. Fritz
Analyses of sediment in Gold Creek and Gastineau Channel Haber (1927, 1928), as mentioned previously, had this in mind
at Juneau, Alaska indicate that the transport of gold is mainly and spent some 7 years dealing with the problem, finally
by physical means with the majority of the gold appearing in abandoning any hope during his lifetime of developing a
the 4+ size range in and near Gold Creek. feasible commercial recovery process. Others have taken up
Cationic forms of gold were found by Wood (1971) to be the problem with the hope of alleviating the economic ills of
absent in seawater, and gold was not associated to any great their nations (Purkayastha and Das, 1965). Perhaps in the
extent with dissolved organic matter which is extractable in future a highly specific resin for gold such as that described by
either chloroform or ethyl acetate. Koster and Schmuckler (1967) will form the basis for commer-
\ ,

The gold concentrations in samples from the east Pacific cially extracting the metal from the vast reservoir of the
found by Wood (1971) showed a heterogeneous distribution. oceans. Lancaster (1973), however, considers that the extrac-
The average concentration was 0.004 ppb with a range of tion of gold from seawater by any known method is an
0.001 to 0.025 ppb Au. unrealisable dream.
Wood (1971) estimates that approximately 10 per cent of Many of the natural precipitates from hot springs, cold
the gold in seawater is ionic, probably Au(1)chlorohydroxy springs and groundwaters contain small amounts of gold (and
anions, e.g., [AuClOHI-. Another 10 per cent is associated silver) as shown in Table 22. Some precipitates are greatly
with particulate matter, and the remaining 80 per cent is less enriched in the element, especially those near gold deposits.
than 0.45 p, nonionic, not extractable in ethyl acetate nor Others, such as those probably from submarine hot springs as
chloroform and probably colloidal. in the Red Sea, contain up to 5.6 ppm Au (Table 14).
Ryabinin et al. (1974) determined the gold content in 89 Manganese oxides (wad) frequently concentrate gold and
water samples collected with bathometers from different levels certain varieties of limonite, especially if they are admixed
of the Atlantic Ocean tropical zone at some 19 sites. The with or contain manganese oxides, phosphate, arsenate, etc.,
concentrations ranged from 0.004 to 3.4 ppb. The average tend to carry considerable amounts of the element. Organic
concentration for all samples was 0.202 ppb, a value consider- compounds (humic complexes) also seem to be major concen-
ably higher than that found by other investigators for ocean trators of gold in some areas. Sulphate efflorescences and
water. The distributions were very irregular, and no particular stalactites in the drifts and workings of gold-silver mines of
pattern was discernible. the Tintic district, Utah and Empire district, Colorado were
Polyakov (1959) observed that the amount of gold and found by Morris and Lovering (1952) and Lakin (1969~)to be
 Contents

Table 22. Gold content of natural precipitates (dry matter)

Location Description of precipitate Au Ag Au/Ag ratio Reference

New Guinea Wad and other manganese oxides; man-

genese content 7.15%
Wad and other manganese oxides; man-
ganese content 12.15%
New Guinea Dark brown to greenish, pin point organic
(iron humate) compound along seepages
Guiana (British Guiana) Precipitated ironstones (limonite) on sides of
hills near gold-bearing rocks and deposits
U.S.A.; Tintic Standard Various sulphates such as chalcanthite, ep-
Mine, Tintic district, somite, pisanite, etc. Value given is max-
Utah imum value in chalcanthite. Minerals on
shale walls were highest in gold
U.S.A.; Southeastern Transported limonite
states
U.S.A.; (various areas) Iron oxides and hydroxides (crusts and
stains)
U.S.A.; Empire district, Supergene sulphates of copper and iron
Colorado
U.S.A.; Arkansas Manganese ore leached from country rock
U.S.S.R.; Kwnetski- Ocherous and nodular transported limonite
Alatau gold deposits
U.S.S.R.; Chatkal- Iron hydroxide precipitates from mine
Kurama region drainage
Canada: Holman Mine. Limonite
N.S.
Canada; Keno Hill, Y.T. Limonite, residual
Limonite and cerussite (transported)
Wad and minor limonite (transported)
Limonite, scorodite and other oxidation
products
Scorodite and limonite (residual in part)
Anglesite (transported)
Bindheimite (residual in part)
Pyromorphite and cerussite (residual in
part)
Various sulphates of iron and zinc
Canada; Walton, N.S. Manganese oxides; wad; precipitate from
springs
Iron oxide precipitates (limonite)
Canada; Yellowknife, Limonite, Lynx area (transported)
N.W.T.
Canada; Ross Mine, Limonite precipitate, 450 ft level
Holtyre, Ont. Hydrous manganese oxide precipitate, 150
ft level
Canada; Annapolis Roy- Bog manganese oxides (wad)
al, N.S.
Canada; Bathurst area, Bog iron and manganese, Canoe L.
N.B. Transported limonite and other Fe-Mn-Si
precipitates associated with massive sul-
phide deposits
Canada; Long Lake area, Bog manganese in peat
N.B.
U.S.A.; Ojo Caliente, Calcareous tufa (calcite and limonite)
N. Mex.
U.S.A.; Anaconda Hot Limonite and travertine
Springs, Mont.
U.S.A.; Steamboat Sinters, muds, carbonates, sulphides, etc. 0.2-12
Springs, Nev. Metal-bearing siliceous muds up to 200
Siliceous sinters 0.11
U.S.A.; Casa-Diablo hot Hot spring sinter trace
spring area, Mono
County, Calif.
U.S.A.; Niland, Calif. Residue from high temperature steam well 3.7
U.S.A.; Yellowstone Siliceous sinters 0.005-0.05
National Park, Wy. (up to 5.5)
New Zealand; Rotorua Siliceous sinter 0.855
Sulphurous sinter 1.99
New Zealand; Whakare- Siliceous sinter deposited mainly from alka- 5.3
warewa and other areas line springs; maximum values
 Contents

Table 22. (cont'd.)

Location Description of precipitate Au Ag Au/Ag ratio Reference
(PP~)
New Zealand; Taupo vol- Siliceous and sulphide precipitates associat- 85 500 0.17 14,23
canic zones ed with hot springs
New Zealand; Puhipuhi, Hot spring sinter (opal). Sinter also en- 0.03-1.30 1.6-3.0 0.02-0.43 7
North Island riched in Hg. See paper by Hoggins and
Brooks (1973).
Japan; Motoyu spring, Yellow precipitate 1-10 21
Nasu
Columbia, South Ameri- Native sulfur 0.42-1.71 - - 25
ca; La Sufral volcano
Compiled from databy: 1. Blanchard (1933) lo. Grange (1937) 19. U S . Geol. SUN. (1969c), Prof. Pap. 650-A, p. 12 1
2. Morris and Lovering ( 1952) 1 1. Brannock et a/. ( 1948) 20. Lincoln (191 lb)
3. Knight (I91 1) 12. White (1955) 21. Ikeda (1955a.b)
4. Foley (1960) 13. White et a/. (1%3a,b) 22. ~ i n d k e n(1910)
5. Boyle (1%5a) 14. Weissberg (1970) 23. Browne (1969)
6. Boyle (1 972) 15. Mikov (1970) 24. Harrison !1908)
7. Boyle (unpublished) 16. U.S. Geol. SUN. (1 968). Prof. Pap. 600-A, p. 7 25. Goodchild (1 9 18)
8. Weed (1905) 17. Kinkel and Lesure (1 968) 26. Skryabin (1968)
9. Maclaren ( 1906) 18. Gottfried et al. (1972) 27. H. Lakin (1969a). U.S. Geol. SUN., Circ. 622, p. 4.

gold-bearing. Of the precipitates associated with hot springs, adsorbed or bound form in the hydrous iron, manganese,
the siliceous sinters (usually with some sulphides) deposited aluminum and silicon oxides. Limonite and wad, intimately
from alkaline waters tend to concentrate more gold (and mixed with organic substances, probably hold the element
silver) than the carbonate and limonitic sinters. partly as some form of gold humate or other gold-organic
In the natural precipitates gold is most frequently accom- compound. In precipitates containing secondary sulphides
panied by enrichments of SO,, As, Sb, Cu, Ag, Zn, Cd, Hg, such as pyrite, melnikovite and marcasite, most of the gold is
Ti, Zr, Mn, Fe, B, Al, P, Te and S and less frequently by Li, present in these sulphides in an unknown form. More details
K, Ca, Mo, W, Co, Ni, TI, Bi, Se, V, Cr, Sn, Th and U. These on the form of gold in natural precipitates and secondary
are also the common associates of gold in natural waters. oxides, sulphates, carbonates, etc. are given in a previous
Judging from the data in the literature (Table 22) the Au/Ag section on gold in other minerals in this chapter.
ratio of hot spring deposits such as siliceous sinter, travertine, There are only scattered references to the possible pres-
etc. is generally less than 1. There is considerable variability in ence of gold in the various products of volcanoes and
the Au/Ag ratios of cold spring deposits, precipitates from fumaroles. Recent quantitative data appear to be lacking, but
groundwaters, organic precipitates, etc., but they are common- the element is probably present in the precipitates and
ly much less than 1. The highest contents of gold and silver sublimates associated with these high temperature phenomena
generally occur in the siliceous sinters precipitated from hot since Goleva et al. (1970eb) detected up to 1.6 ppb Au in the
alkaline saline waters. This circumstance is particularly waters of the HCl fumaroles of the volcano, Ebeko, in the
marked at Whakarewarewa and other thermal areas in New Kuril Islands, U.S.S.R., Goodchild (1918) mentions the pres-
Zealand (Grange, 1937; Browne, 1969; Weissberg, 1970). Such ence of up to 1.7 ppm Au in the sublimated sulphur of La
natural data suggest that some gold-silver-quartz deposits Sufral volcano in Columbia. Gold has also been detected in
were probably precipitated from alkaline, saline siliceous traces in the pyrite associated with the sulphur "blowers" in
waters or from diffusion currents in an alkaline environment. the Sulphur Bank at Borax Lake, California (Liversidge,
Numerous other occurrences of gold in spring precipi- 1893~).
tates are recorded in the literature. Many of these are The extremely small amounts of gold in natural waters
associated with pyrite, which partly replaces rotting wood and (circa 0.03 ppb) make the problem of the determination of the
other organic debris in the spring waters. References as far state of the element most difficult. There has been much
back as Sterry Hunt (1879) and Liversidge (1893~)draw theorizing on the state of gold in waters, but as yet we have no
attention to this mode of occurrence of gold and other metals. satisfactory data on which to base solid conclusions, nor have
There are a number of references in the old literature attesting we yet available any experimental techniques to decide exactly
to the solubility of gold in mine waters and its precipitation how gold exists in natural waters. About all that we can
(or plating) on iron particles such as rails, shovels, mine cars, truthfully say is that gold migrates in waters by some process
etc. of natural alchemy as yet undiscovered. This statement
The mode of occurrence of gold in natural precipitates is notwithstanding we can suggest from the known chemistry of
exceedingly variable. In manganese oxides and limonite much gold that the element may be present in natural waters in one
of the gold is probably present in an adsorbed form or as an or all of the following forms:
integral part of the oxide complexes. Some varieties of 1. As finely divided particles of native gold: gold is
auriferous limonites, particularly those associated with sul- slightly 'soluble' in water, especially in a very finely divided
phide and gold-quartz deposits, contain the element in a state. The form of this 'dissolved' gold is, however, unknown.
number of ways: in minute specks, wire and sprigs of native In some cases the particles are probably colloidal in size and
gold; in a great variety of secondary minerals such as jarosite the solution is, therefore, in the nature of a colloid (see 13
(plumbojarosite and argentojarosite), bindheimite, beudantite, below). In other cases the finely divided particles may be
anglesite, pyromorphite, malachite, azurite, etc.; and in an hydrated, coated with a variety of natural substances which
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

stabilize the particles in 'solution' or adsorbed to fine silt, solubility in acid solutions especially those containing the
organic compounds or a variety of colloids such as the +
halogens or halogen acids - 4HC1 Au(OH), = HAuC1, +
hydrous iron oxides. In some surface waters much gold is 3H20 - and in alkaline solutions in which it forms the
transported as fine particles that appear to float or are carried complex ions [AuOz]-, [AuO3I3-and their hydrated equiva-
along as silt. This gold is the familiar 'flour gold' or 'float lents, e.g., [HzAu03]-and [HAuOZl2-.Tyurin and Kakovskii
gold' frequently referred to in the literature. Goni et al. (1967) (1960), from thermodynamic calculations, consider that gold
have shown by experimental methods that gold can be made may be present as the hydroxide or its complexes in some
to form a stable suspension of very fine (colloidal) particles by supergene waters. Vorotnikov et al. (1973) also consider that
prolonged abrasion by quartz grains. This suspension is some of the gold in these waters is present as [Au(OH),]-.
stabilized by the presence of carbonate in small amounts (up Lenher 11918) carried out a number of experiments on
to 1 per cent). Above this concentration the carbonate acts as the hydrothermal transport of gold as the hydroxide. At
a flocculent. The colloidal silica also formed by abrasion, relatively low temperatures and pressures (1 10°C, 1.5 atm) the
assists in maintaining the gold in suspension, probably acting hydroxide is relatively stable in solution; at higher tempera-
as a protective colloid. Machairas (1967, 1970a) refers to tures and pressures decomposition to the metal takes place to
particles of gold in iron oxide stalactites in the Cros Gallet a variable degree. Vilor and Shkarupa (1971) investigated the
Tunnel in France which he thinks have been transported in system Au-Si0,-H,O within the temperature interval 100 to
suspension in groundwaters. These particles have a maximum 400°C and at HzO pressures of up to 1000 atm. Below 200OC
size of 20p. Chernyayev et al. (1969) have also concluded that concentrations of Au and SiO, are equal and independent of
gold migrates in the supergene zone of gold and sulphide pressure. Above 200OC they increase with temperature and
deposits partly as very fine particles in suspension in the pressure. The gold is said to be present as [AuO,]- and
oxidizing solutions. colloidal particles. The colloidal gold system is stabilized by
In a recent paper Goleva et al. (19706) claim that gold in dissolved and polymerized SiO,. Narseev (in Petrovskaya,
the common types of natural waters (pH 5-8 and Eh 0.1-0.5 1974), likewise, advocates the transport of gold in hydrother-
V) is present mainly in the form of Au(0) (uncharged parti- mal solutions in the form of hydroxy complexes and chloroau-
cles) and as organic complexes. rates stabilized by polymeric silica compounds when high
At high temperatures and pressures metallic film gold concentrations of silica are present in the solutions.
precipitated on quartz and porcelain is relatively soluble in 4. As soluble halogen salts and halogen complexes: when
water according to the experiments carried out by Vilor and salts such as AuCl,, AuBr, and AuI, dissolve in water they do
Sarapulova (1971). At 100°C they noted a solubility of 6.6 so with the formation of complex ions of the type [AuClJ,
ppb of the film gold; at 3W°C, 67.5 ppb; and at 350°C a [AuCl,(OH)]-,[AuCl,(OH),] - , [AuCl(OH),]- and so on. There
decrease in solubility to 3 4 4 5 ppb. Lower values were are analogous bromine and iodine complexes whose stability
recorded when film gold precipitated on porcelain was used. increases in the order I >Br >C1. Actually the formation of
They concluded that gold dispersed in sedimentary rocks these complexes is a very intricate matter, but it is apparent
during sedimentation may be leached out by dilute aqueous that the iuric ion can probably form every state of the
solutions in the course of progressive metamorphism, tran- fourfold complex from [Au(OH),]- to [AuCl,]- depending on
sported and then precipitated on encountering a change in the pH of the solution and the concentration of chloride ions.
pressure and temperature in the rocks through which filtration This is evidently because an aqueous solution of auric chloride
of the solutions took place. is in reality a solution of the acid H[AuCl,OH]. There is also
2. As the ions Au+ and Au3+: these states have been an unusual series of addition products of auric chloride with
suggested by some early investigators, but their presence as the halides of P, Se, Si, Sb, etc. These evidently give soluble
ions in any normal natural water appears unlikely. Gold has complex ions but relatively little is known about their chemis-
an extremely high affinity for electrons, hence its character as try. Some, such as those with silicon and antimony, may have
the most noble of metals. The ionization potentials for both geochemical significance in the migration of gold since the
-
ions are (Au+-9.2 eV; Au3+- 30 eV) and hence their
interaction with water is marked. Aurous ion decomposes to
three elements are invariably found together.
Further discussion of the various aspects of the halide
form metallic gold and auric ions in aqueous solutions. It can, complexes of gold is beyond the scope of this book, but four
however, be stabilized by ligands such as (CN)-. Auric ion is recent papers dealing with traces of gold in chloride solution
stable in very acid waters (pH t 2 ) (Fig. 1); at higher pH it is are of interest. Benei (1967) concluded from dialysis and
strongly hydrated or is stabilized in water as the numerous electomigration experiments that traces of gold (10-7-10-8M)
complexes noted in 3 and 4 below. As a rule gold is highly (2-20 ppb) in chloride solutions between the pH range 6 to 13
inert in nature, and strong oxidizing agents such as MnO,, exist predominantly as complex anions or molecules, probably
Fe3+,As5+,Sb5+,CuZ+,O3 or 0, are necessary to oxidize the of the hydroxoaurate type, [AU(OH)~C~J (x+p3)- +
with (x y
metal to the (I) and (111) states. Only when complexing agents 14). In the pH range 0 to4 Benei and Riedel (1967) and
such as (S,03)2-, (CN)- and C1- are present can gold be Benei and Singer (1968) concluded from adsorption experi-
maintained in a mobile (soluble) state in the presence of these ments that the trace amounts of gold in chloride solutions
oxidizing substances. were present predominantly as undissociated molecules of
3. As gold hydroxide, Au(OH),: gold hydroxide is slightly HAuCl, at low pH and positively charged hydrolytic products
soluble in water (Lenher 1918; Johnston and Leland, 1938), of this acid at higher pH. With increasing pH (>4) the
the quantity being about 3.1 X mole/L or approximately negatively charged hydroxo complexes noted above are domi-
600 ppb. Being amphoteric the hydroxide exhibits increased nant. On the mechanism of the dissolution of gold in chlorine
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

water Svistunov (1970) concluded from thermodynamic data supergene waters leaching gold-bearing deposits in temperate
that the gold is present mainly as HAuCl, and that the metal climates confirms the low content of these elements. Only in
reacts with atomic rather than molecular chlorine as is rare cases do the supergene waters contain more than a few, a
generally considered to be the case. few tenths or a few hundredths parts per million respectively
Complex aurous halides, bromides and iodides of the of C1, Br or I. Higher concentrations can be expected in arid
type [AuCl,]- are known, but they are relatively unstable, the regions where some supergene transport of gold may take
aqueous solutions rapidly decomposing with separation of place as halide complexes.
metallic gold and the formation of auric complexes. Transport of gold in hypogene waters (hydrothermal
Numerous investigations have considered that gold in solutions) as chloride complexes has also appealed to a
surface waters leaching gold-bearing deposits is largely present number of investigators, particularly Ogryzlo (1939, Kraus-
as a complex hkde. Lenher (1909, 1912) was one of the first kopf (1951), Helgeson and Garrels (1968) and Rabenau and
to deal with this form of transport in detail, and he summa- Rau (1968). Krauskopf stated that gold may be transported at
rized the earlier literature on the subject. Brokaw (1910) and high temperatures and pressures as the ion [AuC14]- in acid
Emmons (1917) pointed out that gold could be dissolved in solutions provided that reducing agents are absent. He
acid supergene solutions as the soluble auric chloride complex thought that at the temperature and pressure of most hydro-
when a strong oxidizing agent such as manganese dioxide was thermal solutions that the hydrogen ion of the acid was a
present to oxidize the gold to the Au(II1) state. This view is sufficient oxidizing agent to keep the gold in the oxidized
supported experimentally by Miller and Fisher (1974). Chuk- state. Helgeson and Garrels concluded from thermodynamic
hrov (1947) considered that the solution of gold in the considerations that gold is carried in acid hydrothermal
oxidation zone of mineral deposits was due to the formation solutions primarily in the aurous state as chloride complexes.
of soluble alkali gold bromides and iodides. Shcherbina The writer (Boyle 1969c) has criticized this proposed acid-
(1956b), Krauskopf (1951), Kelly and Cloke (1961) and chloride transport mechanism from a number of angles,
Shabynin (1966) have postulated that the auric chloride pointing to the general low content of chloride now present in
complex, [AuClJ-, is one of the important forms in which gold veins and their wall-rock alteration zones, the alkaline
gold is transported in supergene waters. Kelly and Cloke character of the wall-rock alteration associated with gold
(1961) concluded that if an activity of moles/L (2ppm) is deposition, the low transfer percentages of alumina in altera-
chosen as the lower limit of the geological solubility of gold, tion zones associated with gold deposits, the general presence
the element is soluble in acid chloride solutions (pH < 5.9, in gold deposits of carbonates which are difficult to precipi-
oxidation potentials greater than 0.9 V, and chloride ion tate from highly acid solutions and so on. Because of these
activities greater than moles/L. In the waters of the and other features of gold deposits it seems probable that near
southern Enisei region, U.S.S.R. Vorotnikov et al. (1973) neutral to alkaline sulphide solutions also carrying As, Sb and
concluded from dialysis studies that gold migrated in an Ag are the most likely gold-transporting media. Recently
ion-dispersed state in the form of negatively charged anion Weissberg (1970) has shown experimentally and by examina-
complexes, principally as [AuOH,]- and [AuCl,OH]-. Ros- tion of thermal waters precipitating gold in the Broadlands,
lyakov et al. (1972) found that the [AuClJ- complex prevailed Ohaki and Waiotapu areas, New Zealand that the [AuSI-
in the pore solutions of oxidized ores, eluvial layers and soils complex is more than adequate to account for the transport of
overlying gold deposits. It was commonly accompanied by gold in these near-neutral low salinity hydrothermal solutions
gold in the form of the [Au(OH),]- complex. (see 12 below).
The views that supergene waters transport gold mainly as More recent views on the transport of gold as chlorides
[AuC14]-and as other halide complexes has been questioned are found in a number of papers. Vilor and Shkarupa (1971)
by a number of investigators particularly Boydell (1924), examined the system Au-Si0,-NaC1-H,O between the range
Tyurin and Kakovskii (1960), Goni et al. (1967), Goleva 100 to W ° C and at H,O pressures up to 1000 atm. They
(1968) and Goleva et al. (1970qb). They point to the relative found that the gold and silica contents increase with tempera-
instability of the auric chloride complex at a pH greater than ture, pressure and acidity as compared to neutral solutions. At
4 (the normal range of most supergene waters), the relatively NaCl concentrations higher than 50 g/L the disperse Au
easy reduction of the complexes by metallic minerals, organic phase was found to be stable within the whole temperature
compounds etc., the paucity of chloride, bromide and iodide range. They concluded that their data confirmed the possibili-
in most supergene waters, and the general absence or late ty of the formation of gold deposits by the leaching of gold
stage appearance of oxidants such as MnO, in many deposits. from various rocks by metarnorphogenic hydrothermal solu-
Boydell (1924) and Goni et al. (1967) consider colloidal tions. In a further study of the system Au-SO,-H,O-NaC1-
transport more probable, and Tyurin and Kakovskii think HCl-NaOH in the range 200 to W ° C , Vilor and Kazmin
that the effective soluble complex is a thiosulphate one (see 5 (1973) concluded that the basic gold complex in chloride
below). Lakin et al. (1974) stress the relative immobility of solutions is [AuCl,]- supporting the view of Helgeson and
gold chloride in geologic environments because of the easy Garrels (1968) that the oxidation state of gold is low at high
reduction of the various complexes to the metal by most temperatures and pressures.
common geological materials. They also note that while Kolonin and Aksenova (1971) studied the effects of
bromide and iodide form stronger complexes with gold they temperature on complex formation of gold in chloride solu-
are rarely if ever in sufficient natural concentrations to be of tions by spectrophotometric methods. They observed that for
importance as a supergene agent of transfer of the precious [AuCl,]-, hydrolysis was greatly increased with increase in
metal. The writer's observations on the halide content of temperature in the interval 21 to 90°C.
 Contents

THE GEOCHEMISTRYOF GOLD AND ITS DEPOSITS

Henley (1973) determined the solubility of gold in chlo- deposits may be attended by transport of gold in the form of
ride solutions in the range 300 to 500°C. The solutions were halogen complexes. In the sea the soluble gold appears to be
buffered with respect to HC1 by a K-feldspar-muscovite- present mainly as the aurous chloride complex, [AuCl,]-, but
quartz assemblage and to oxygen by the assemblage hematite- at the concentration present (0.02 ppb) it will remain difficult
magnetite. Solubilities were found to increase rapidly with to prove that this is in fact so.
temperature from about 10 ppm at 300°C to 500 and 1000 5. As thiosulphate complexes of the type [Au(Sz03),B-:
ppm at 500°C at 1 and 2 kbar respectively. Based on this both gold and silver are soluble in thiosulphate solutions
evidence Fyfe and Henley (1973) have concluded that water of containing oxidants, gold forming the complex noted above
dehydration (metamorphic water) in which chlorides are and silver the complex [Ag(Sz0,)z]3-.Both complexes are
present could move gold from piles of rocks into available relatively stable in weakly acid, neutral and alkaline solutions
shear zones and faults where it precipitates at lower tempera- (pH 4-9) but decompose in acid solutions. The silver complex
tures and pressures. yields S, AgS and some AgSO,; the gold complex yields a
Rytuba and Dickson (1977) investigated the reaction of variety of indefinite products according to my investigations.
pyrite + pyrrhotite+ quartz + gold with NaC1-HzO solu- Depending on the concentration of thiosulphate these appear
tions within a temperature range 300 to 500°C and pressure to be S, native gold and probably AuzS. The presence of any
range from 500 to 1500 bars. Contrary to previous investiga- reducing substance gives free gold and some sulphur in the
tions they found no evidence of gold-chloride complexing precipitate. The general stability of the two metal complexes is
under the near-neutral and reducing conditions of the experi- also considerably different in my experience. Silver thiosul-
ments. They concluded that the appreciable solubility of gold phate solutions are relatively stable to natural agents of
in their experiments was due to the pyrite-pyrrhotite equilibri- oxidation and reduction, and silver is relatively difficult to
um, which sets the So,Fez+and SZ-activities; the hydrolysis of precipitate from the solutions in any form. Gold on the other
So, which forms HS-, required for complexing; hydrolysis of hand is relatively easily precipitated as the metal both by
C1-, which buffers the acidity; oxidation of gold by So and oxidation and reduction of the complex by a variety of agents.
H+; and the formation of [Au(HS),]-. Genetically, processes In a more general sense thiosulphate complexes of both gold
capable of depositing gold and gangue minerals from NaCl and silver are relatively stable in the presence of ferrous
solutions initially saturated at 500°C and 1500 bars, were sulphate (in gossans, etc.) and are not readily reduced by this
postulated to be: decreased temperature, decreased pressure, compound. This is especially so for silver and less so for gold.
dilution to lower NaCl concentrations or combination of the The varied habit of the decomposition of the thiosulphate
three processes. complexes of silver and gold are important in the oxidation of
Gold chloride is volatile as AuzC1, (Landsberg and gold-silver deposits containing sulphides since with respect to
Hoatson, 1970; Visnapuu et al. 1971), and this form has silver, a soluble sulphate is formed whereas with the gold
appealed to some as a mode of transport during endogenic complex the metal is precipitated. These circumstances permit
processes. Thus, Anoshin and Potap'yev (1966) have conclud- a ready separation of the two metals, and a natural refining,
ed that gold moves in the gaseous phases AuzC1, and AuzC1, therefore, takes place - gold is concentrated mainly as the
said to be stable over a wide temperature interval native metal whereas silver is leached out, a phenomenon
(300400°C). There are also a number of other volatile species consistently found in eluvial and alluvial placers (see Chapter
of gold, e.g., AuFeC1, and AuAlCl,, that could conceivably 111).
occur in nature. These have considerable volatility in the Other oxidized sulphur species can arise as intermediate
range 200 to 500°C (Heinen and Eisele, 1974). products between sulphide and sulphate during the oxidation
A number of early investigators have concluded that the of sulphides according to the scheme: Sz- + [SZO3y-+
dissolved (solute) gold in seawater is present mainly as the [S0,I2- + [Sz_,06y-+ [SO$-. Sulphite and polythionate
[AuCl,]- and [AUOJ complexes, the latter according to form soluble complexes with gold. These can be characterized
Krauskopf (1951) being about 100 times the concentration of as [Au(SO3),I3- and [Au(S,_,O,),]~-.These complexes and
the former. Peshchevitskii et al. (1965, 1970) have investigated other soluble species of the oxygenated sulphur compounds
the problem of gold in seawater carefully from the viewpoint are fairly stable in alkaline solutions. They are not readily
of the thermodynamic stabilities of various complex forms of reduced by pyrite and other sulphides, and hence if formed
gold having regard to the composition of seawater, the redox endow gold with considerable mobility. On long contact with
potentials of the possible gold complexes and the redox sulphides however, alkali species are ultimately reduced to
potentials of seawater. They concluded that gold was present native gold. In acid solutions the sulphite and polythionate
mainly as the aurous complex [AuCl,]- and a few per cent as complexes of gold and silver are decomposed to give the
[Au(Cl,Br)]-. The other relative contents of the complex forms metals, sulphur, the metal sulphides or the metal sulphates
of gold such as [AuCl,]-, [AuBr,]-, [AuBr,]-, [AuIz]-,[AuSI-, (silver only) depending on the Eh and pH of the decomposi-
[AuCl,OH]-, [AUCI~(OH)~]-, [AuCl(OH),]-, [Au(OH),]-, tion process.
[AuOHClI-, and [Au(OH),]- are small. Summarizing the above we see that all of the thio
In summary we are probably justified in saying that the complexes can form only where the solutions are only slightly
transport of gold as chloride complexes in hydrothermal and acid, neutral or alkaline, a condition that may obtain where
supergene oxidizing waters is minimal compared with other oxidizing auriferous sulphide deposits have carbonate wall-
modes of migration. Certain acid chloride thermal springs rocks or gangue.
may transport some gold, but in general these do not seem to Information on the presence of thiosulphates and other
be related to gold deposits. In arid regions oxidation of gold t h o species in waters leaching gold deposits is limited. My
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

observations indicate that these constituents are present in in various parts of the world according to scattered data in the
neutral and alkaline environments but only in small amount literature and personal communications; values up to 37 ppm
(up to 5 ppm), most of the sulphur being present as sulphate. are recorded from hot springs according to the summary given
Thiosulphates are, however, formed in some quantity in by Lakin et a1 (1974). If these values are actually the contents
various metallurgical practices involving oxidation of sul- in the thermal waters and not due to oxidation of the waters
phides (Forward and Mackiw, 1955) and various thiosalts are near the surface, it would appear that some low temperature
produced during the alkaline oxidation of a variety of sul- hydrothermal solutions may carry enough thiosulphate to
phides (Schmidt and Conn, 1971). It can be concluded, complex and transport the small amounts of gold that give
therefore, that thio complexes of both gold and silver may be rise to deposits.
instrumental in the transport of gold where the supergene 6. As the soluble sulphate: gold is said to be soluble in
solutions acting on sulphide-bearing gold deposits are only H,SO, solutions as the sulphate in the presence of an oxidiz-
slightly acid, neutral or alkaline. ing agent such as 0,, MnO,, etc. Gold (111) hydroxide is also
Tyurin and Kakovskii (1960) have postulated that gold said to be soluble in H,S04 probably with the formation of the
(and silver) migrates in the supergene environment mainly as complex sulphate [Au(SO,),]-. These views are reiterated
thiosulphate complexes. They find these complexes to be many times in the old literature (Lenher, 1904) and sometimes
relatively stable and that the dissolution of gold and silver as appear in the newer literature on gold compounds. Mellor
thiosulphate complexes is greatly accelerated by the presence (1923) characterized aurosoauric, AuSO,, and auric,
of cupric ion, which catalyzes the various reactions. Listova et Au,(SO,),, sulphates and mentions complex alkali gold sul-
al. (1966) showed experimentally, using natural Fe, Pb and Zn phates of the type K[Au(SO,),]. These on solution may give
sulphides, that the oxidation of these minerals in the presence rise to the complex ion [Au(SO,),]-. Relatively little is known
of carbonates yielded Ca thiosulphate and polythionate. They about the solubilities or the stabilities of these various
observed an increased solubility of gold when these sulphur sulphates and complexes. They would appear to be relatively
compounds were present, and postulated that they were the unstable, especially in the presence of reducing agents. In
main solvents of gold during oxidation processes in gold water, gold sulphates are extensively hydrolyzed, another
deposits. They concluded that gold could have a marked feature that makes them relatively unstable. On thermody-
migration capacity in the supergene environment when thio namic grounds Roslyakov et al. (1972) consider that the
salts were present. Cherepnin et al. (1973) have also suggested solubility of gold as the sulphate in oxidizing waters is
that the enrichment of gold in the oxidized zones of the infinitesimal, the standard electrode potential for the
sulphide-quartz veins of the Kuznetsk Alatau is the result of [Au(SO,),]- complex being unfavourable.
the deposition of gold from solutions of its thiosulphate salts. It has long been noted that gold exhibits some mobility
~ a k i n - e tal. (1974) concluded that thiosulphate ion may be where sulphides are undergoing oxidation, and it has frequent-
present in enviroments high in sulphur but generally in very ly been postulated that the agent aiding its solution in such
low concentrations. Above pH 5 gold may be transported as environments is femc sulphate, Fe,(SO,),. One also notes that
the thiosulphate complexes in these environments. in some places the content of gold in oxidizing waters of
~ e n h e(1912)
i considered that gold could be transported sulphide deposits is greatest when the waters are acidic and
as soluble thiosalts in hydrothermal solutions, and Tyurin charged with iron, manganese, arsenic and sulphate.
(1963,19653) set out to prove that thiosulphates transport gold Ferric sulphate as an aid in the solution of gold in
in hydrothermal solutions. Shcherbina (1964), however, disa- oxidizing waters has been questioned by a number of inves-
grees with this view pointing out that no thiosulphate minerals tigators in the past, particularly Stokes (1906) and Emmons
are known, that thiosulphate has not been detected in hot (1917) who stated that the solvent action of ferric sulphate
springs, and that liquid inclusions do not contain the com- alone is neghgible. Kreiter et al. (1959), on the other hand,
pound. He also notes that at high temperatures (>100°C) the found by experiment that solutions of ferric sulphate and
thiosulphate complexes are unstable and break down. Kim sulphuric acid are good solvents of gold.
(1972) essentially agreed with this view, stating that the To resolve this problem I have carried out a number of
migration of gold in hydrothermal solutions in the form of the experiments using atomic absorption methods to detect gold
thiosulphate complex [Au(S,O,),]~- is insignificant. Tyurich in solution. The results (Boyle et al., 1975) indicate that
(in Petrovskaya, 1974), on the other hand, maintains that the amorphous gold is weakly soluble in femc sulphate solutions
formation of complex compounds of gold in sulphide solu- alone, and more so when free H2S04 is present. The presence
tions such as the oxygenated species Au,S,O, and [AuS,O,]- of NaCl in the solutions appears in some cases to slightly
must be taken into account during hydrothermal processes. reduce the solubility of the precious metal for reasons that are
Ellis (1967) states that thiosulphate and polythionate ions do not clear.
not persist in natural waters at temperatures of 200 to 300OC 7. As soluble gold arsenate or gold arsenate complexes:
but break down according to the reaction types: gold is soluble in arsenic acid, H3As04or As,O,.H,O, in the
+
S,0,2- +
H,O + H,S SO:- presence of MnO, and other strong oxidants. The nature of
+
2S,0,2- +
8H,O + 5S0,2- + 6Ht 5H,S the solute is unknown, but presumably it is gold arsenate, a
A search of the literature revealed relatively little infor- complex molecule of the type [AuAsO,], or a complex ion of
mation on the abundance of thiosulphate in hot springs. In the type [Au(As0,),13- analogous to the sulphate.
the great memoir on the hot springs of Yellowstone by Allen The common occurrence of arsenic in gold deposits en-
and Day (1935) values for (S,03)2- in the waters range from 0 sures a supply of dissolved arsenic in oxidizing supergene waters
to 21 ppm. A similar range is found in a few other hot springs since the oxidation of arsenic minerals such as arsenopyrite
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THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

yields arsenic acid or some derivative of this acid in solution other hand dissolve small amounts of amorphous gold
asshownby the followingsimplifiedreaction: (Boyle et al., 1975).
+ +
4FeAsS 130, 6H,O -,4FeS04 4H,As04 + Two other mechanisms involving the solution of gold in
There are no detailed investigations to determine the potassium or sodium carbonate solutions concern the presence
extent of migration of gold as arsenate or arsenate complexes of H,S in these solutions. The alkali sulphide or bisulphide
from oxidizing sulphide-arsenide deposits, but we have noted formed are well known solvents of gold (see also 12 below).
that some waters rich in soluble arsenic are, likewise, enriched Na,CO, + H,S =NaJ + H,O + CO,
in gold. NaHCO, + H,S =NaHS + H,O + CO,
8. As soluble gold antimonite or antimonate complexes: These mechanisms may be important in the transfer of gold
relatively little is known about these. By analogy with arsenic during both hypogene and supergene processes as shown by
it appears probable that gold will form complex antimonites our experiments (Boyle et al., 1975).
of the form [Au(SbO,),]- and possibly also complex antimon- Liversidge (1893~)reported that gold is dissolved in a
ates. There are also a number of double complexes of antimo- solution of potassium or sodium silicate at a pressure of 90
ny and chloride which may have geochemical significance in psi. The form in which the dissolved gold was present is not
the migration of gold. The common occurrence of antimony in mentioned. It may have been as a colloid or as some complex,
gold deposits ensures a supply of dissolved antimony since the perhaps an aurate. Cumenge and Robellaz (1898) also refer to
oxidation of antimony minerals such as stibnite or tetrahedrite alkali auro-silicates and think that they play an important part
yields soluble antimonites and/or antimonates depending on in the formation of auriferous quartz deposits. The experi-
the redox potential. We have noted increased amounts of gold ments by Von Veimarn (1913), the result of which led him to
migrating in waters enriched in antimony. suggest the presence of an unstable gold silicate when
9. As soluble nitrates, nitrites and other soluble inorganic NaAuC1, and N%Si03 are mixed, are also of interest in the
species: auric nitrate and a variety of complex nitrates and formation of gold quartz veins. These experiments should be
nitrites are known, but these appear to hydrolyze so extensive- repeated since they have a direct bearing on the transfer of
ly that they are not stable in water. In natural settings, gold and silica during hypogene processes (see also the
however, some of these complexes may be stabilized by the reference to Frondel and others in 13 below).
organic constituents of humus, and gold may migrate in the The writer has experimented with the solubility of gold in
form of combined organic nitrate, nitrite or arnrnine com- various solutions of sodium and potassium silicate (saturated
plexes, especially where a source of nitrates, nitrites or - 10 per cent saturated, pH 10-12). The nature of the gold
ammonium ion is available as in decaying vegetation, humus, used in the experiments was the same as that described in
etc. Boyle et al. (1975). In saturated solutions of sodium meta-
Gold is soluble in phosphoric acid, H3P04,presumably silicate gold solubilities up to 40 pg/mL were noted, but in
with the formation of gold phosphate. The stability of this similar solutions of potassium silicate the solubility was much
compound in water is unknown, and nothing is known about lower (up to 1.2 pg/mL). When H,S was bubbled through the
its occurrence in natural situations. It may occur in some various alkali silicate solutions considerable amounts of gold
natural waters where phosphate is abundant. were taken into solution (>100 pg/mL). On completion of the
Gold is said to be soluble in hot selenic acid, H,Se04, at H,S treatment the solutions gelled but still retained the gold in
high temperatures (300OC) and in hot solutions of telluric acid the gel. It can be assumed that ASH, and SbH, would have a
containing H,S04 or H,P04. The transport of gold presuma- similar effect on the solubility of gold judging from my
bly as selenates and tellurates at high temperatures could previous work noted above.
conceivably take place, but there are no data by which to Stokes (1906) found that gold is dissolved by cupric
judge the efficiency of the mechanism. Transport of gold chloride and HCl, the reaction being as follows:
during low temperature supergene processes as selenates, etc. +
Au 3CuC1, = AuCl, + 3CuCl
would not appear to be important, but again no data are He remarks that addition of a chloride to cupric sulphate
available for judgement. would probably also have the same solvent effect on gold. The
Colloidal gold is said to be soluble in dilute alkalis same author found that femc sulphate has no solvent effect
apparently with the formation of the hydroxide, hydroxide on gold. Addition of sodium chloride to the femc sulphate
complexes or oxide complexes (see 3 above). Colloidal gold solutions, however, led to the solution of some gold. This is
and very finely &vided gold is said to exhibit some solubility the oxidation and complexing effect on gold referred to in 4
in alkali carbonate solutions, although Ogryzlo (1935) found above. Stokes (1906) also found that gold is soluble in a
that sodium carbonate has no solvent effect on gold at high solution of ferric chloride and HCl. Again this is due to the
temperatures and pressures. The reported solubility of gold in oxidation and complexing effect. Experimentally, Miller and
carbonate solutions may be due to the formation of very Fisher (1974) found that.gold exhibits some solubility in FeCl,
slightly soluble alkali aurate species such as KAuO, (see also 3 solutions in a dynamic system when (Fez+)is continuously
above). The reaction may first involve the formation of the removed. The reason for this is obvious, Fez+being a strong
hydroxide or some hydrous complex followed by formation of reductant of gold in solution. The gold dissolved in the femc
the aurate. chloride solutions was completely sorbed by pyrite. The
+
2Au(OH), KCO, = 2KAu0, + CO, 3H,O + presence of bromide in the solution aided the dissolution of
The writer has experimented with gold and various carbonate gold and impeded its reduction and precipitation on pyrite.
solutions and finds that the normal carbonates are poor All of these experiments are of interest in understanding the
solvents of gold. Solutions of alkali bicarbonates on the transport of gold during supergene processes as noted in
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

Chapter IV. Their significance in the hypogene transfer of aldehydes or ketones. I n vivo, enzymatic reactions produce
gold is problematical. similar products. Plants, fungi and insects on their death
Lenher (1909) found that boiling HCl under pressure undergo decomposition during which HCN may be split out
dissolves gold readily, and that hot solutions of sodium of the organic complexes as a result of hydrolysis or bacterial
chloride and HCl under pressure have a similar effect. High action. Interactions of HCN with alkalis in soils, humus, etc.
temperature sodium chloride and other alkali chloride solu- in neutral and alkaline environments may produce alkali
tions under high pressure, even in the absence of HC1, also cyanides and thiocyanates which, as noted above, solubilize
have a solvent effect on gold. These mechanisms for the gold (and silver). From what has been said it is evident that
solution of gold may be significant in hypogene environments. gold may be transported in the exogene cycle as cyanide or
BabiCka (1843) mentions work by J. Barvir and C thiocyanate complexes in an environment where humification
Doelter that indicated that sodium chloride is a weak solvent processes are proceeding. Such complexes would, however,
for gold, but in my experiments I have not been able to seem to be transitory since their stability during humification
confirm this (Boyle et al., 1975). BabiEka (1943) also mentions processes is relatively low as a result of oxidation and
that Egleston found that magnesium sulphate also dissolves bacterial activity which break them down to simpler com-
the metal, but this seems improbable. Vilor and Shkarupa pounds such as CO,, H,S, SO:- and nitrates.
(1971) experimented with the Au-Si0,-NaC1-H,O system at The presence of available cyanides and thiocyanates in or
temperatures between 100 and 400°C and H,O pressures up about oxidizing gold deposits where humification processes
to 1000 atm. They found that the gold and silica contents are progressing is uncertain. Biochemically they should exist.
increase with temperature, pressure and acidity as compared My research on this matter has failed, however, to definitely
to neutral solutions. At NaCl concentrations higher than 50 establish their presence, but work is continuing on the
g/L the disperse gold phase decreased while the ionic form problem. Certain identification of traces of cyanide is difficult
increased. The chloride complexes were found to be stable in natural waters as shown by Goulden et al. (1972).
within the whole temperature range. The Au3+/Au+ratio Lungwitz (1900a,b) thought that cyanide derived from the
increased with increase in temperature in the range from 200 decomposition of plants could be a solvent of gold but
to 400OC. They considered that silicon-chloride complexes dismissed the idea because he thought this active agent could
play a major role in the transfer of SiO,. only be formed at high temperatures. He also noted that CN
Morris and Lovering (1952) noticed an affinity of gold had not yet been found in the decay products of vegetation.
for cupric sulphate solutions as indicated by the presence of Shcherbina (19563) postulated that gold forms soluble com-
the precious metal in chalcanthite and pisanite efflorescences plexes with humic acids, one of the complexes being
in the Tintic District, Utah (Table 22). They also found gold (Au(CNS),)-. Curtin et al. (1970) leached three gold-bearing
in copiapite, which suggested to them an affinity of gold for samples of mull (forest humus layer) from Nevada and
ferric sulphate solutions with iron just commencing to hydro- Colorado with demineralized water, obtaining gold in solution
lyze. Along the same line Lakin (1969b) mentions the fact that in the range 27 to 120 parts per trillion (1 X 10-12). They
gold is relatively soluble in solutions leaching dumps of suggested that most of the gold in the leachates was probably
porphyry copper deposits (femc and cupric sulphate solutions present as extremely small colloidal particles ((0.05 p diam-
at pH 1.5) when sodium chloride and MnO, are added and air eter), with much smaller amounts in the form of gold cyanide
is bubbled through the solutions. Two aliquots of 200 mL and thiocyanate ions.
each, one containing NaCl and MnO, and the other free of In later papers Lakin et al. (197 1; 1974) explained that at
these wnstituents, contained 400 and 4 pg of gold respectively. a pH of 5 to 8, (CNS)- and (CN)- may be expected to dissolve
gold. They found that thiocyanates were relatively sparse in
10. As a soluble cyanide or thiocyanate complex: gold soils, but that cyanides could be abundant as a result of the
forms very soluble cyanide and thiocyanate complexes in an hydrolysis of cyanogenetic glycosides. More than 1000 species
oxidizing environment. The cyanide complexes are [Au(CN),]- of plants yield HCN on hydrolysis; many arthropods produce
and [Au(CN),J-, and there are also a number of multiple HCN; and some animals and fungi also yield appreciable
complexes of the type [Au(CN),Cl,]-. The thiocyanate com- amounts of the compound. Macerated aqueous suspensions of
plex can be characterized as [Au(CNS),]-. The dissolution of 16 species of native plants collected in Colorado, Utah,
gold in cyanide and thiocyanate solution is usually written as: Nevada and Arizona were found to dissolve leaf gold. Lakin et
+ + +
4Au 8CN- 0, 2H,O= 4[Au(CN),]- 40H- + a[. (1974) consider that gold cyanide offers the most feasible
+
Au qCNS]- = [Au(CNS),]- form of soluble gold in soils.
The various gold cyanide and thiocyanate complexes are Cyanide- and cyanate-bearing minerals exist in places. A
stable, but only in mildly acid, neutral and alkaline solutions. number of cyanide minerals are recorded by Povaremykh and
Numerous plants and seed kernels, some fungi and Rusakova (1973) and Rusakova and Povaremykh (1973) in
certain insects contain cyanide in the form of cyanogenic various gold belts of U.S.S.R. One mineral kafehydrocyanite,
glycosides, which are composed of one or more types of sugar K4[Fe(CN),].3H,O, has been characterized. Cyanides were
with CN and other groups bonded through hydroxyl (OH) found in the waters from which these minerals were precipitat-
(Armstrong and Armstrong, 1931; McIlroy, 1951; Kingsbury, ed. According to the investigators, cyanides and thiocyanates
1964; Conn, 1969). A familiar cyanogenic glycoside is amyg- are significant in the migration and redistribution of gold in
dalin, the bitter essence in almonds. I n vitro, cyanogenetic the supergene zone of gold deposits. The source of the
glycosides are hydrolyzed in acidic aqueous solutions and split cyanides is considered to be decaying organic matter. A
out HCN, thiocyanates, sugars and other products generally thiocyanate mineral, julienite, Na,Co(SCN),-8H,O occurs in
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

small amounts at Chamibumba, Katanga, Zaire (Belgian feature would give gold considerable mobility in the hydrolog-
Congo). ic regime and may account for the high contents of gold found
It is usually considered that cyanides and thiocyanates in trees and other plants. Hamson (1908) concurred in the
play no role in the primary endogenic migration of gold. Our view that much of the secondary gold in Guyana was trans-
views in this respect may require reassessment. Recently, ported in organic-rich waters. Freise (1931) experimented with
Mukhin (1974) has authenticated the presence of thiocyanates the solution of gold by humic acids extracted from lignite and
and hydrogen sulphide in the thermal springs in the caldera of black river water generated in virgin forests in Brazil that was
the Golovnin volcano (Kunashir Island, Kuriles). From these rich in dissolved organic compounds. He reported relatively
and other data the author concludes that hydrocyanic acid rapid dissolution of gold as a humate by these compounds
(HCN) is present in volcanic gases. If so, a ready solvent for when oxygen was excluded. Blanchard (1933) found certain
gold is available in deep-seated processes. Similarly, gold may humic materials near gold deposits in New Guinea (see Table
have migrated as a soluble complex thiocyanate in endogenic 22) greatly enriched in gold. He thought that at least some of
processes. the gold was dissolved by and migrated in organic solutions
11. As soluble organic complexes: gold forms a great but that the conditions were complicated by the presence of
variety of organic compounds. Gold (I) alkyls, isonitriles, much dissolved manganese. Shcherbina (19566) suggested that
carbenes and mercaptides have long been known and are quite gold may possibly form soluble compounds with humic acids
stable, and there are also a great number of gold (111) alkyls in organic environments, and Steelink (1963) thought it
and chelated diarsine, phosphine and other complexes. In probable that gold may react with humic acids, in the
addition there are the various cyanide and thiocyanate com- presence of oxygen, to form soluble compounds. He consid-
plexes noted in 10 above. The facility with which gold binds ered the solution and precipitation reactions to be as follows:
with organic molecules is, therefore, well established. Solution: Au + H+ + humic acid + 0, =
In natural environments organic compounds are extreme- [Au humateI3+ + H,O
ly complex especially those occumng as plant and animal Precipitation: [Au humate]3+ + R =
Au + humic acid + R+
residues and in humus. The latter substance is a most
complicated material with no well established composition. In
(R = a reducing agent such as Fez+or organic compounds)
addition to humic acid and fulvic acid components it appar-
ently consists of a great variety of relatively unknown con- Goleva (1968) mentions the fact that up to 70 per cent of
stituents derived from the breakdown of dead vegetable and the gold in certain natural waters is extracted by chloroform, a
animal matter. Furthermore, these constituents are exceeding- feature which suggests considerable organo-metallic binding
ly variable depending upon the degree of humification. Vari- of gold in these waters. Finally, Udodov et al. (in Petrovskaya,
ous types of humus appear to react differently toward the 1974) find that gold exhibits some solubility in humic and
metals, and no one component can be effectively tagged as fulvic acids.
being responsible for the strong binding action on metals Investigations by Garces (1942) and Fetzer (1934, 1946)
displayed by some varieties of humus; thus, the subject can oppose the concept that humic acids dissolve gold. Both have
only be discussed in general terms. found experimentally that gold (and silver) are not dissolved
When available the metals of Group IB are generally by humic acids extracted from peat and lignite.
strongly bound by humus. Copper forms a strong bond with Recent studies have tended to confirm the transport of
humus, a feature that has been discussed at great length by gold as natural organic complexes, often colloidal in nature.
numerous investigators and summarized by Manskaya and Ong and Swanson (1969) have shown that gold is neither
Drozdova (1968), Ong et al. (1970) and Boyle (1977). The dissolved, complexed nor oxidized by organic (humic) acids,
nature of the copper bond to humus is uncertain, but the but rather that the element in solution as gold chloride is
experimental evidence suggests some kind of internal or reduced by the acids to a negative colloid of metallic gold.
chelated complex. Silver, likewise, is strongly bound by humus This colloid is then stabilized by a protective layer of organic
probably as a chelate or some other such organometallic molecules around the gold thus permitting a relatively high
complex (Boyle, 19686). Gold is no exception. The writer's mobility of the element in soil and other natural waters.
observations and those of others (see the section on soils) Curtin et al. (1970) and Lakin et al. (1971) in the papers
show that gold is markedly enriched in the humic horizons of summarized in 10 above noted that gold is mobile in an
some soils, and that much of this gold is bound in the humic organic environment mainly as a colloid and in minor
component. An important question in the transport of gold is amounts as gold cyanide and gold thiocyanate ions.
not whether gold can be bound by humic materials - this A recent study of the interaction of natural organic acids
much seems proved - but whether it can migrate in natural with gold by Fisher et al. (1974) indicates that humic acids
solutions in this manner. The latter has given rise to consider- alone do not dissolve gold, but if the gold occurs in a
able controversy. colloidally dispersed state, containing adsorbed oxygen, the
Lungwitz (19OOa,b) working in Guyana, postulated that humic and fulvic acids solubilize the element. Furthermore,
gold chloride may be formed during the oxidation of gold these acids interact with dissolved [AuCl,]- forming stable
deposits by supergene waters containing chloride ion and auriferous humate and fulvate complexes. Experimentally a
nitric and sulphuric acids derived from the decomposition of gold-fulvate complex was shown to be very stable under most
organic matter. The gold chloride, he thought, could form natural supergene conditions.
double salts with water-soluble organic compounds such as We have carried out a number of investigations involving
those in the brown colouring matter (humus) in streams. This the 'solubility' of gold in humic-rich solutions (Boyle et al.,
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

1975). These show that gold is slowly 'dissolved' in these appealed to a number of investigators as a transport mech-
solutions; the metal is intimately associated with the humic anism for gold during the formation of hypogene deposits.
matter being either chelated, organometallically bonded or Smith (1943) carried out an extensive series of experi-
adsorbed. When the humic matter is removed by ultra filtra- ments involving the solution and transport of gold, silver and
tion the solutions are essentially free of gold. tellurium in alkali sulphide solutions.~He was able to show
There seems to be little doubt that gold is 'solubilized' in experimentally that gold is soluble in, and can be crystallized
one form or another by a variety of organic compounds. In from, such solutions, and that two other common gold
some cases the compounds or complexes actually assist in the minerals, electrum (Au,Ag) and calaverite (AuTe,), can be
dissolution of gold; in other cases they act as protective agents similarly synthesized. His conclusions on the transport and
(colloids) for gold colloids. Such mechanisms are undoubtedly deposition of gold, silver and tellurium merit quotation in full
important in the migration of gold under supergene conditions because of their probable importance in the formation of
in organic-rich terranes. . hypogene gold ores:
Under hypogene conditions there is some evidence to Gold is much more soluble than most of the common metals in
support the contention that gold is often transported as an alkali sulphide solutions. It is included in the group of metals whose
sulphides are very soluble in dilute aqueous solutions of alkali
organometallic complex. The common occurrence of gold in sulphide at ordinary temperature. This group also contains mercu-
thucholite (an indefinite C-H-0-N-S-U-Th compound) as in ry, bismuth, antimony, arsenic, and tellurium. In the group of
the Rand and at the Richardson deposit in southeastern metals whose sulphides are soluble in aqueous solutions of alkali
Ontario suggests that gold may migrate in natural waters sulphide only at elevated temperature, the most soluble metal ap-
pears to be silver. Thus the natural association of minerals contain-
combined with bitumen or other petroliferous substances, ing gold which are deposited late in the ore sequence with minerals
perhaps specifically as a porphyrin which can be synthesized. containing silver, bismuth, and tellurium is explained. When the
(See also the section on biogeochemistry.) Further details soluble double sulphides of gold and alkali are broken down by a
on the association of gold and hydrocarbon substances are lowering of the sulphide concentration, gold deposits as the metal,
given in the section on gold and its associated minerals in since its sulphides are very unstable above 40°C. In solutions
containing both silver and gold, if the sulphide concentration is
Chapter 111. reduced to the point where metallic gold separates, it does so along
12. As complex sulphide, polysulphide, telluride and with considerable silver in solid solution, forming argentiferous gold
or electrum.
sulphide-arsenic-antimony complexes: it has long been known If tellurium is present along with gold in natural alkali sulphide
that gold is soluble in alkali hydrogen sulphide (e.g., NaHS) solutions, gold tellurides may or may not precipitate as the sulphide
solutions at low temperatures and that gold sulphide is soluble concentration is reduced, depending on the state of the tellurium in
in solutions of alkali sulphide and polysulphide in excess at the solutions. If the free sulphur concentration in the polysulphide
form is high, then the tellurium is present as alkali thiotellurites,
low temperatures. At high temperatures gold is also soluble in and when in this form metallic gold precipitates first and much
concentrated alkali sulphide solutions. Egleston (1881), Liver- later the thiotellurite complex is broken down and metallic telluri-
sidge (1893c), Becker (1887), Lenher (1904, 1912, 1918), um is precipitated. If the free sulphur concentration is low, then the
Mellor (1923), Gruner (1933), Ogryzlo (1935), Zviagincev and tellurium is present in part as polytelluride ion and gold tellurides
Paulsen (1940), Smith (1943), Krauskopf (195 l), Kim (1972) are first precipitated, followed later by the excess of metallic gold.
These reactions have been duplicated by experiment, the order of
and Seward (1973) have dealt in one way or another with the solubility in alkali sulphide solutions being found to be, starting
various aspects of the experimental and thermodynamic with the most insoluble - gold telluride, gold, tellurium. This
problems in the various aqueous systems involving gold, gold explains the natural paragenesis of gold tellurides, gold, and telluri-
sulphide and alkaline sulphides. There is some agreement that um, which apparently deposit in the same order.
the principal complex ion is [AuSI-, although some [AuS,]- In recent years Weissberg (1970) has reinvestigated the
may also be present in the systems. In a recent paper Seward solubility of gold in alkaline sulphide solutions and finds that
(1973), determined the solubility of gold in aqueous sulphide the solubility of gold experimentally determined at elevated
solutions from pH 4 to 9.5 in the presence of a pyrite-pyrrhotite temperatures in alkaline Na,S solutions ranges from 1 to 6
redox buffer at temperatures from 160 to 300OC and 1 kbar. ppm Au in solutions containing from 0.25 to 0.9 moles
Maximum solubilit&s were obtained in the neutral region of N&S/kg solution at temperatures between 150 and 290°C. In
pH. It was concluded that three gold complexes contributed to less alkaline solutions, where the HS- ion predominates, the
the solubility: [Au,(HS),S]2- predominated in alkaline solu- experimentally determined solubility of gold ranges from 100
tion, [Au(HS),]- in the near neutral pH region and [Au(HS)IO to 200 ppm Au in solutions containing from 0.2 to 0.3 moles
with less certainty in the acid pH region. The stabilities of the NaHS/kg solution at temperatures between 150 and 250°C, in
first two complexes are much greater than chloroaurate (I) good agreement with earlier workers. Having done the neces-
species, a feature which suggests that the chloride complexes sary calculations he concluded that gold solubility due to the
play only a subsidiary part in the transport of gold in neutral formation of a gold sulphide complex tentatively formulated
and alkaline hydrothermal solutions. as [AuSI- is more than adequate to account for the transport
The sulphide and polysulphide complexes of gold are of gold in some natural near-neutral low salinity hydrothermal
stable in aqueous solutions between a pH of 6 up to at least solutions, such as in the Broadlands, Ohaki and Waiotapu
10. The [AuSI- complex is also relatively stable to metallic areas, New Zealand, where currently forming surface precipi-
sulphides and a number of other reductants. Since many hot tates contain up to 85 ppm Au (see Table 22). This makes a
spring waters are alkaline, and other effects such as certain postulated near-neutral gold sulphide transport mechanism a
types of wall-rock alteration suggest alkaline solutions, trans- particularly effective means for the formation of epithermal
port of gold as soluble alkaline sulphide complexes has gold deposits.
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

One of the problems with the alkali sulphide theory of antimony sulphides in sodium sulphide gives the arsenites,
gold transport is that pyrite, one of the ubiquitous sulphide thioarsenates, thioantimonites and thioantimonates as follows:
minerals in gold deposits, is insoluble or only sparingly As$, + 3 NaJ = 2 Na3AsS, (thioarsenite)
soluble in alkali sulphide solutions. There are a number of As,S, + 3 Na$ = 2 Na,AsS, (thioarsenate)
other sulphides that also show this phenomenon to some +
Sb2S3 3 Na,S = 2 Na3SbS3(thioantimonite)
degree, some of them relatively abundant in gold deposits, viz. Sb,S, + 3 Na$ = 2 Na,SbS4 (thioantimonate)
molybdenite, argentite, pyrrhotite, sphalerite, etc. To circum- The complexes formed in these solutions are of the type
vent these difficulties it is usually said that gold is deposited [AsS3I3-.Complexing of these with gold could yield double
later than pyrite in deposits. This is true in many deposits, but complexes of the type [Au(AsS3)I2-and [Au(S~S,)]~- and others
late pyrite accompanied by gold is common in most deposits. such as [Au(AsSJO, [Au(Sb2S4)]-,etc. depending on the pH
Early pyrite, with gold as a lattice constituent or in a very and other factors. These complexes may be responsible for the
finely divided submicroscopic form, is also common. Perhaps transport of gold (and silver) in typical hypogene environ-
we are not dealing with pyrite as such in alkali sulphide ments. Experimentation with carbonate solutions containing
solutions but with stable species of iron sulphide complexes, various combinations of H,S, ASH, and SbH, has shown that
which are ultimately partitioned out of the solutions or amorphous gold is relatively soluble under these conditions
diffusion currents as the solid phases pyrite and/or pyrrhotite. (Boyle et al., 1975). The soluble species formed in the
The same may be true for the other metals such as Mo, Ag, solutions are evidently [AuSI-, [Au(AsS3)IZ-,[Au(SbS,)]'-,
Zn, etc. With respect to pyrite we may also not be dealing [AuAsI2-, [AuSbIZ-or more complicated polymerized and
with the transport of iron at all, this element being largely hydrolyzed species.
derived from the nearby host rocks as McKinstry (1957) In the supergene environment transport of gold as the
has observed. The derivation of the other metals is more [AuS]- complex or as the complexes of arsenic and antimony
difficult to explain by this secretion hypothesis; they appear mentioned above may be a feature of the lower parts of
to have been transported some distance according to my oxidized zones where the solutions are neutral or alkaline and
investigations. carry sulphide ion, H,S, or dissolved arsenide and stibnide
Gruner (1933) has referred to the problem of the low complexes. The enrichment of gold in the secondary (super-
solubility of gold in hydrosulphide hydrothermal solutions gene) sulphide zones of some deposits suggests this mode of
charged with silica. Zvyagintsev and Paulsen (1940), however, transport.
doubt the earlier data and maintain that silica in fact pro- The complex [AuSI- is stable in seawater, but the general
motes the solution of gold in hydrosulphide solutions. They absence of S2- and HS- ions makes its presence in this
also state that sulphides and quartz are not precipitants of environment practically negltgible (Peshchevitskii et al. 1965,
gold from hydrosulphide solutions as some investigators have 1970).
suggested. On the contrary, hydrosulphide solutions may pass Relatively little is known about complex telluride species
through a sulphide zone without depositing gold and may in and the migration of gold as tellurides. A sodium thiotellurate
fact dissolve gold, which is contained in the sulphides. To (IV), Na,TeS,, is reported to be formed by dissolution of Te in
precipitate the gold they call on decreased solubility as a solutions of Na,S, and Na,S3 but not Na,S. The wrrespond-
result of falling temperature. Gold in the sulphides of gold ing complex is probably [TeS,I2- from which the double
deposits results from coagulation processes involving gold sols complex [AuTeSJ may be derived. In addition there may be a
and the surface properties of sulphides. variety of other complexes such as [Au(Te,)]-, [Au,(Te,)l0 and
Gold may also be dissolved in the oxidized zone of [Au(Te,),I3- derived from the stable reduced ditelluride ion
auriferous deposits principally as [AuSI-. The formation of the (Te,),- as suggested by Seward (1973). The attempts by Smith
H,S necessary to form this complex is most probably provided (1943) to synthesize gold tellurides from alkali sulphide
by the action of sulphate-reducing bacteria active in the solutions suggest that the systems are complex. He concluded
oxidized zones. In most oxidized zones the amount of H,S is that in alkali sulphide solutions, gold telluride is less soluble
minimal but is invariably present. In their study of a number than gold sulphide, which in turn is less soluble than tellurium
of oxidized zones, eluvial layers and soils overlying gold sulphide, and also that gold telluride appears in alkali sul-
deposits in eastern Transbaikal and the Kuznetskii Alatau, phide systems only when the free sulphur concentration is
Roslyakov et al. (1972) found that the sulphide complex of low. For the extension of these data to natural systems see the
gold, [AuSI-, prevailed over all other forms (chloride, hydroxy, quotation from Smith above.
etc.) in the aqueous extracts of the materials in and associated 13. As various colloids or sols: metallic gold readily forms
with the oxidized auriferous zones. From this data they a colloid, the 'Purple of Cassius' being known for centuries,
reasoned that when H,S is present in oxidized zones most of and the red gold sol, obtained by reduction of a dilute gold
the gold migrates as a sulphide complex. solution with tannin and other organic compounds, was
Arsenic and antimony are nearly universal associates of extensively investigated by Faraday. The metallic gold colloid
gold in its deposits, as discussed at length in the section on cames a negative charge in the pH range 4 to 8. The charge
associated elements. These two elements as sulphides are also can be reversed by the addition of ferric chloride and other
readily soluble in aqueous alkali sulphide solutions. These salts (Weiser, 1933). Gold sols are, therefore, similar in most
facts have led the writer (Boyle, 1969~)and others (Seward, respects to the metallic silver colloids. Other gold compounds
1973; Sorokin, 1973) to postulate that arsenic and antimony can apparently also form stable colloids. Beneg (1967) men-
complexes are probably important agents in the hypogene tions positively charged hydrolytic products formed as the re-
transport of gold. The solution of the various arsenic and sult of the hydrolysis of gold solutions in the pH range 1 to 3.
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

These products are apparently hydroxides, e.g. Au(OH),. colloids were formed by prolonged abrasion of gold particles.
Hydrous auric oxide, Au,O;xH,O, and aurous oxide, In both cases the colloids were found to be stabilized by the
Au,O~xH,O,also have wlloidal tendencies. presence of wlloidal iron hydroxide and colloidal silica. A
Gold wlloids may arise in nature in a number of ways, high content of carbonate (as KCO,) depressed the stability
some of which are: by comminution of gold particles by of the gold colloid, but low amounts (up to 0.2%) had only a
repeated abrasion; by reduction of a dissolved (ionic) gold minor effect. The authors postulated that the gold colloids
compound or complex by numerous inorganic and organic could be flocculated in a number of ways, including changes
substances, e.g., Fez+;by hydrolysis of dissolved gold wm- in pH and Eh, interaction with organic matter in swamps and
pounds or complexes; as a result of the dissociation of a bogs, interminghng of waters with different salinities, adsorp-
variety of dissolved gold complexes; and by release of gold tion by clay minerals, etc. Goni et al. (1967) were also able to
held in the lattices of gold minerals such as tellurides and in make small artificial gold nuggets morphologically similar to
solid solution in various,sulphides and arsenides, particularly those found in nature by compaction of colloidal particles due
pyrite and arsenopyrite, as a result of oxidation processes. The to turbulence. (See also the section on placers in Chapter 111.)
gold (mustard gold) so released is extremely finely divided and A number of other investigators have suggested wlloidal
reactive. Stabilization or peptization of gold wlloids is accom- transport of gold under a variety of supergene conditions.
plished by numerous organic and inorganic compounds, Chernyayev et al. (1969) considered that some of the gold in
especially humic compounds, colloidal silica, hydrous iron the natural waters of northern Kazakhstan, U.S.S.R. was
oxides, etc. Gold colloids are stable at least up to tempera- present as a colloid. Curtin et al. (1970) reasoned from their
tures of 100°C or more; at higher temperatures their stability experimental work on the leaching of gold-bearing mull (forest
decreases, but in the presence of suitable peptizers such as humus layer) by demineralized water that most of the mobile
silica they are stable up to relatively high temperatures ('soluble') gold was present in the leachate as extremely small
(350°C) (Frondel, 1938). Sulphide sols probably have a similar colloidal particles (<0.05p diameter). Machairas (1970~)
stabilizing effect at elevated temperatures. Flocculation and thinks that some of the gold in the exogene cycle travels in
precipitation of gold from colloidal solutions is accomplished (colloidal) suspension and gives some natural examples of
by various electrolytes, positive colloids, organic compounds where he thinks this process has been active (see 1 above).
and many other substances, all of which are mentioned Gosling et al. (1971) concluded that some of the gold in the
subsequently. natural waters in Colorado was present in a fine colloidal
Most of the work on gold colloids in the past (Zsigmondy form with an organic acid protective coating, the complex
and Thiessen, 1925) has been done on relatively enriched particles being capable of passing the 0.1 p membrane filter
solutions. More recently some work on traces of gold used in the determination of 'solute' and 'particulate' gold.
(t10-8M;2 ppb) in solution has been carried out by Schweitz- During oxidation processes of gold-quartz deposits Kraft et al.
er and Bishop (1953) who showed by centrifugation studies (1974) consider that gold migrates mainly in colloidal forms
that the gold exhibited colloidal behaviour in the pH range 2 (see also Chapter IV).
to 13. Bene3 (1967) has found, however, that traces of gold Ong and Swanson (1969) and Ong et al. (1970) carried
(10-8-10-5M)form only colloids (pseudocolloids) between pH out an extensive investigation of the effect of organic acids in
1 to 3. Above pH 3 the gold species is present mainly as a stabilizing gold colloids in the surficial environment. To
complex hydroxo anion (see 4 above). The pseudocolloids are summarize their findings they stated that:
evidently positively charged hydrolytic products, Au(OH),(?).
Interactions of various forms of gold, as plates, coarse particles,
The transport of gold as a colloid in surface waters and colloids, and ions [AuCI,]-, with different types of natural organic
supergene oxidizing groundwaters has long been advocated. acids show that gold is not oxidized and complexed by the organic
Maclaren (1908) and Boydell (1924) and others before them molecules as reported by some investigators. To the contrary, or-
considered this mode of transport as probable, and Lindgren ganic concentrations in the range of 3 to 30 ppm have the capacity
(1933) inclined to the view that gold was transported as a to reduce gold chloride solutions to negatively charged colloids of
metallic gold. For the 30-ppm organic acid solutions, the reduction
colloid in certain oxidized zones of gold deposits. process is accomplished by the formation of a protective coating of
Bastin (1915) experimented with gold wlloids and was hydrophilic organic molecules around the hyrophobic gold sol mak-
able to produce the dull brown finely divided gold often found ing the gold very stable for at least 8 months and not easily
in the oxidized zones of gold deposits. He suggested the coagulated by cations. The gold sols so formed are less than 10 mp
in size. This protective layer is also formed when colloidal gold is
possibility of gold being transported in colloidal solution in mixed with organic acids. For the 3 ppm organic acid, the organic
the oxidized zones of gold deposits in the presence of protec- matter concentration is too low to form the protective coating and
tive colloids such as silica sol. the colloidal gold precipitates.
Mering et al. (1953) observed that negative gold sols were Two of the organic acids used in this study were extracted from
fixed by kaolinite as a result of surface cation exchange peat and humate-cemented sand, and one was collected from a
brown lake water. All three are similar in composition and in
processes (Au for Na, Ca, H, etc.). physical properties to organic acids isolated from soils and surface
Goni et al. (1967) investigated experimentally the stabili- waters. These natural organic acids can be considered as hydrophil-
ty, transport and flocculation of gold colloids in the surficial ic colloids having a particle size in the 2.4-10 mp range and having
cycle. They observed that ionic and metallic gold give stable negative charges due to the dissociations of the carboxylic and
phenolic groups.
colloidal suspensions that permit migration over great dis- The significances of this study in geochemical processes involv-
tances. Chemically the colloidal suspensions were formed by ing the mobility of gold are: (1) in a very acidic solution, for
reduction of dissolved gold by both humic and fluvic acids in example near an ore deposit, where gold is soluble as its chloride
acid and alkaline solutions respectively. Mechanically the gold and organic acids are not soluble, the presence of solid organic
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THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

matter causes the reduction of gold chloride, and metallic gold of these particles was 794. Zhirnov concluded that these particles
colloidal size will be precipitated and intimately associated with the initially represented colloidal gold protected by silica sols, and
organic matter; (2) in slightly acidic to basic waters, for example in
the general range of composition of natural waters, gold can only be that they were deposited from solutions by a rapid drop of
transported as stable organic protected colloids; and (3) these temperature at the margins of the veins where pyrite assisted
organic-protected gold colloids are precipitated when they enter a in the coagulation of the gold colloids. Wright (1969) figures
different chemical environment, such as sea water or brackish water numerous textures of ore and gangue minerals in the aurifer-
with their abundant ions or clay colloids, or when they enter an
acid environment (pH<3).
ous Tennant Creek (Australia) deposits, which he thinks
proves that the minerals were at one time in the colloidal
The hydrothermal hypogene transport of gold in a colloi- state. Subsequent to deposition they have crystallized, and
dal form received some attention in the early years of the some have been partly mobilized. He suggests that the
present century, but relatively little work has been done on the mobilization process took place by thixotropic reliquefaction
problem in recent years. Hatschek and Simon (1912) experi- of the gelatinous parent materials of the minerals now present.
mented with silica gels throughout which were uniformly Frondel (1938) seems to have been one of the last
dispersed soluble gold salts in an effort to produce some of the investigators to experiment seriously with colloidal gold under
features common in gold-quartz veins. By using a number of hydrothermal conditions. He found that gold sols were pro-
reducing agents, viz. oxalic acid, ferrous sulphate, sodium tected by silica colloids against electrolytes (NaCl) and
sulphite, graphite, charcoal, bituminous shale and crude spontaneous coagulation by increase of temperature. He also
petroleum, they found that in a gel consisting of silicic acid in noticed an increase in the stability of protected gold sols with
which a gold salt is uniformly distributed, a reducing or increase in temperature, and found that the protected sols
precipitating agent has the following effects: were stable up to 350°C. From the experimental data Frondel
(a) If the reducing agent is hypotonic (undersaturated) in concluded that in acid hydrothermal solutions gold is very
relation to the salts in the gel the whole of the gold will leave probably transported in true solution; part or all of the gold
the gel and will deposit in aggregates, probably of crystalline salt, however, may be carried as an adsorbed electrolyte on
form, at the point or points of contact of the reducing agent colloidal silica. With approaching neutrality or alkalinity of
with the gel. The gel, as a result of losing part of its soluble the originally acid solution, the gold is precipitated out as sol,
gold content, may cause the reducing agent to become protected by colloidal silica. The protected gold sol may be
hypertonic (supersaturated) and the gold still remaining in the coagulated in various ways - by decrease of temperature,
gel would then be precipitated as below. dilution, changes in pH, mixing of the gold sol with other
(b) If the reducing agent is hypertonic in relation to the solutions carrying different kinds and concentrations of
salts in the gel the gold will be precipitated within the gel, not, electrolytes and adsorption of the sol on mineral surfaces and
however, necessarily uniformly throughout the gel, but often gel surfaces.
in distinct layers, the layers being parallel to the surface of the
More recently Vilor and Shkarupa (1971), experimenting
gel in contact with the precipitating agent, and the distance
with the Au-Si0,-H,O system at 100 to 400°C and at H,O
from one layer to the next one increasing with the distance
pressures up to 1000 atm, observed that the gold and silica
from this surface.
contents in the solution were about equal and independent of
From these experimental results they sought to explain pressure up to 200°C. At higher temperatures they increase
the banding and ribbon structure so common in gold-quartz with temperature and pressure, and the gold is present as
veins and to explain the distribution of gold in the quartz of [AuO,]- and colloidal particles. The colloidal particles are
the veins. They concluded that such phenomena could origi- stabilized by dissolved and polymerized SiO,.
nate when a structure such as a fracture was filled with Finally, Fijii and Haramura (1976) have noted that a
gelatinous silica into which or through which gold salts had solution of HAuCl, can be reduced to a gold colloid in silica
diffused, precipitating native gold mainly as a result of solution without adding reducing agents. In their experiments
reduction by a variety of common substances. Goni et al. at room temperature and pressure they used (1) silica solution
(1967) repeated some of the diffusion experiments of gold
chloride through silica gel and obtained gold films and some
+ HAuCl, solution + silica gel and (2) silica solution +
HAuCl, solution. The concentration of the silica solution was
textures frequently present in gold deposits. about 50 ppm SiO,. In the first experiment deposition of
In a classic work on the role of colloidal solutions in the aggregates of wlloidal purple gold and quartz crystals were
formation of mineral deposits Boydell (1924) referred to the observed. Colloidal purple gold was also absorbed in silica gel
occurrence of much fine-grained quartz, chalcedony and opal giving the gel a darker colour. Dissolution of the silica gel by
in gold deposits and to the presence of sulphides and gold in alkali solution revealed the presence of fine purple gold and
many deposits in an extremely fine state of division. He growth of gold and quartz crystals. In the second experiment,
thought that these phenomena indicated colloidal transport of deposition of aggregates of fine purple gold, quartz crystals
gold and silica, flocculation of the colloids to form gels, and and a small amount of silica gel were observed. The wlloidal
finally recrystallization of the constituents of the gels to form purple gold did not adhere to the quartz crystal surfaces. The
the quartz and gold as it is now found. Lindgren (1933) authors concluded that although the experiments were simple
advocated a somewhat similar origin for certain types of and at room temperature and pressure, they suggest that both
gold-quartz deposits. More recently Zhirnov (1972) has de- colloidal and true solution processes are involved in the origin
scribed spherical brownish-coloured colloidal-sued particles of some gold-quartz veins.
of gold (0.1 p and smaller) in colloform bands in the Kaul'da Despite all of the favourable experiments and specula-
gold deposit of the Almalyk ore field U.S.S.R. The fineness of tions indicating the colloidal transport of gold it should be
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

pointed out that no one has yet shown that gold is present in 9.6 ppm, with most of the values falling between 0.1 and 0.7
natural waters as a colloid. My investigations using dialysis PPm-
methods have all been negative, but this is not surprising since 17. As an integral part of or adsorbed to various free
gold in natural waters is present in such low amounts (circa swimming or floating micro-animal organisms and plants:
0.005 ppb) that one can probably not hope to attain success Krauskopf (1956) showed experimentally that plankton ad-
with present day apparatus. I have, however, noted that gold sorbs silver strongly. Gold probably behaves in a similar
travels with other sols, e.g., hydrous ferric oxides, manganese manner. (See also the section on the biogeochemistry of the
sols, humic colloids, etc., but its state is unknown. It is element.)
probably largely present in an adsorbed form.
14. As aerosols and vapours in water gas (steam): the The migration of gold in natural waters can be summa-
constitution of the aerosols would be varied. In some cases rized in the following statements:
they would probably be colloidal gold particles or gold In ground, spring and surface waters gold is present in
compounds of various types; in others the gold would proba- only small amounts generally of the order of 0.03 ppb. Much
bly be adsorbed to hydrated silica, SiO,.nH,O, hydrated of this gold is apparently present as a colloid or adsorbed to
alumina, Al,O;nH,O, etc. Gold aerosols are probably present organic, inorganic or organo-inorganiccolloids and particulate
in volcanic emanations or in steam impregnated rocks near matter. The remainder of the gold is in a soluble form in a
the surface. There are few data on these phenomena: Goleva variety of complexes depending on the environment of migra-
et al. (1970a,b) found from 0.8 to 1.6 ppb Au in the HC1 tion of the metal. In hypogene (hydrothermal) solutions the
fumaroles of the Ebeko volcano on Paranushir Island, Kurile gold is evidently largely present in a complex form mainly as
Islands, Karnchatka, U.S.S.R. They concluded that the gold some species combining sulphide, antimony-arsenic-sulphide
was present mainly as the chloride complex [AuClJ. There or telluride-sulphide. Under acidic condition the metal may
are a number of other volatile compounds of gold that could also be complexed as some form of the chloro complex.
conceivably exist as aerosols or vapows under natural condi- Judging from the elemental associates of gold in its epigenetic
tions, e.g., AuFeC1, and AuAlCl,. These have considerable deposits (see the section on epigenetic gold deposits in
volatility in the range 200 to 500OC (Heinen and Eisele, 1974). Chapter HI), the nature of the wall-rock alteration zones
15. As an integral part of or adsorbed to the various associated with gold deposits (Chapter 111), and the nature of
humic complexes (colloids) that commonly occur in surface thermal waters now depositing gold, a reasonable estimate can
waters and in some underground waters: this is probably an be made of the type of solution or diffusion current from
important mode of transport in regions where decaying which epigenetic gold deposits have been or are being precipi-
organic matter is present. Further details are given in 11 and tated. This solution is probably relatively dilute containing no
13 above. more than 1 pprn Au, generally much less. Its pH is nearly
16. As an integral part of or adsorbed to suspended neutral, and its constitution is varied but in most cases it
particulate matter: in some places this is a major mode of contains the principal elements in the following forms:
transport of gold (and silver) in surface waters and also in Alkalis (Na, K, etc.) as carbonates, bicarbonates and
waters leaching porous deposits undergoing oxidation. We sulphates
have repeatedly found gold (and silver) in colloidal and Alkaline earths (Mg, Ca, Sr, Ba) as bicarbonates
particulate hydrous iron oxides, hydrous manganese oxides Boron as borates and boric acid
and fine silt, and in these substances with an abundant humic Silicon as colloidal silica, alkali silicate or Si(OH),
component in both surface and underground waters. The Arsenic and antimony as As-Sb-sulphide complexes
nature of the gold in these materials is discussed in the section Sulphur as H,S, various sulphide complexes and sulphates
on gold in other minerals in this chapter (e.g., limonite, wad, Tellurium as telluride-sulphidecomplexes
etc.) and in 13 above. The content of gold in these colloidal Fluorine as alkali fluorides
and particulate substances is variable. Where the so-called Chloride as alkali chlorides
'flour gold' is present (see 1 above) the contents are very high; Iron and manganese as bicarbonates
in more normal environments as in the Keno Hill area and Base metals (Cu, Zn, Hg, etc.) as sulphide, bisulphide and
elsewhere the fine silt and other particulate matter in the polysulphide complexes
streams averages about 0.05 ppm. Gold and silver as sulphide, bisulphide, As-Sb-sulphide and
Fischer (1966) reports gold in amounts up to 0.1 pprn in tellurium-sulphide complexes
the suspended silt of the Saale River in Germany. In the
Aldan Shield of U.S.S.R. Razin and Rozhkov (quoted in
Trofimov, 1969) found that 'floating gold' ('flour gold') and The alkali carbonates and H,S appear in many cases to
gold in suspended matter predominates in ground and creek control the migration and solution of gold mainly through
waters. Their values for these materials range up to 0.037 formation of alkali sulphide and hydrogen sulphide complexes
ppm. In their paper on gold migration in the vicinity of the which render gold soluble. The formation of sulphide and
'Kuranakh type' of gold deposit in Yakutia, Razin and bisulphide ion in solutions of alkali carbonates and H,S
Rozhkov (1963) found an average of 0.001 pprn dissolved gold probably follows reaction such as:
and 0.009 pprn in suspended matter in waters rich in dissolved &CO, + H,S =&S + H,O + CO,
iron and manganese. Gosling et al. (1971), in their research on +
KHCO, H,S =KHS H,O + + CO,
the gold content of natural waters in Colorado, found that the When arsenic and antimony are present in the system gold
particulate solids in the waters ranged from nondetectible to may be rendered soluble as complexes of these elements.
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

Changes in temperature, pressure and concentration of or its compounds. Similarly, withdrawal of sulphide and
solutions and gases containing dissolved gold species com- arsenide ions by reaction with iron in the host rocks (forma-
monly lead to the precipitation of gold. In near surface tion of pyrite, aresenopyrite, etc.) leads to the breakdown of
(supergene) processes changes in temperature, pressure, etc. the gold sulphide and arsenide complexes and the consequent
are usually small and hence have only minimal effects, precipitation of gold. Dilution of solutions containing [AuSI-,
although they may be important at the orifices of springs likewise, leads to a reduction of the sulphide ion concentration
where evaporation of solutions takes place, or where sublima- and the precipitation of gold. Oxidation (change in Eh) results
tion phenomena prevail at the vents of fumaroles. Under deep in the precipitation of gold from sulphide, arsenide and
seated primary vein forming conditions, however, changes in antimonide complexes.
temperature, pressure and concentration have marked effects. Decomposition of gold complexes in solution due to
When highly heated water gas under high pressure and changes in pH, Eh and a variety of reactions involving the
charged with K, Na, SiO,, C1, CO,, H2S, As, Sb, Te and gold withdrawal of alkali and alkaline earth metals (the balancing
in the form of various complexes, enters dilatant fractures or cations of the complexes) and sulphide ion are probably the
other structures it undergoes a decrease in pressure with most important modes of precipitation of gold in both
consequent precipitation of various minerals including gold. hypogene and supergene environments.
Similar effects are produced as these gases (or solutions) rise 2. Adsorption and/or coprecipitation of soluble gold
toward the surface where they come into contact with cooler complexes and colloids: this is probably the second most
rocks, where they mingle with cool, circulating groundwaters important mode of precipitation of gold in naturak settings.
or where they react with the wall-rocks. Concomitant with these phenomena there are invariably a
In addition to changes in temperature, pressure and variety of reduction reactions, which lead to the precipitation
concentration there are a number of other mechanisms by of metallic gold in the systems. Flocculation invariably takes
which gold may be precipitated from natural waters and place in the case of the gold colloids.
vapours. These are: In the supergene environment gold (and silver) is strongly
1. Decomposition of gold complexes due to changes in adsorbed and/or coprecipitated by natural gels, particularly
pH and other parameters: most dissolved gold species are hydrous iron oxides (limonite), hydrous manganese oxides
complexes, some stable only in acid solutions, viz. the halide (wad), silica-alumina gels, clay minerals and humic gels. Some
complexes such as [AuCl,]-, others stable only in neutral and of these gold-bearing substances are mentioned in the section
alkaline waters, viz. the thiosulphate complexes such as on mineralogy, and analyses of these materials are given in
[Au(S2O3),I3-and the thioaurite complex [AuSI-. Changes in Tables 12 and 22. Other data are given in Chapter IV.
pH lead to the precipitation of gold from these complexes The reasons for the adsorption and/or coprecipitation of
depending on the availability of complexing ions and other gold by the various natural gels, clay minerals, etc. is a
factors. Considering the acid halide complexes, neutralization particularly complicated problem, mainly because experimen-
of solutions containing these leads to the decomposition of the tation with these natural substances is difficult, the results
complexes and the precipitation of native gold where ions obtained being often strange and nonreproducible. The reason
capable of complexing the element under neutral and alkaline for this is that these natural precipitates, gels and resultant
conditions are absent. Similar conditions prevail during the mineral complexes are never pure, and their composition
neutralization or acidification of alkaline solutions containing varies widely as one can see by a glance at the analyses given
complex ions of the type [Au(S2O3),I3-and [AuSI-.In this case in Boyle (1965a, 1972) and Dyck (1971). In addition to a great
the complexes are decomposed and native gold is precipitated variation in the major constituents such as Fe, Mn, Si, Al, Mg,
where ions capable of complexing gold under acidic condi- Ca, etc., there are also marked variations in the content of the
tions are absent. humic constituents, which are inextricably mixed with the gels
Shifts in the pH of gold-bearing solutions through the of Fe, Mn, Si, etc. Dyck (1971), experimenting with the
neutral region into the acid and alkaline ranges must be adsorption of silver on these natural substances in our
common in nature. Acidic gold-bearing chloride solutions laboratories, found that in general they adsorb much larger
coming into contact with carbonates either under supergene or quantities of silver than do laboratory preparations of hydrous
hypogene conditions generally rapidly and quantitatively oxides of iron and manganese under similar conditions of pH
precipitate their gold as one can readily see by simply adding and equilibrium silver concentrations. He attributes this to the
powdered calcite to a solution of dilute gold chloride in a test presence of ions in the colloidal complexes, which form
tube. The effect in this case seems to involve an initial insoluble compounds with silver. Gold behaves in a similar
precipitate of gold hydroxide or oxide which is unstable, and manner judging from natural and experimental data obtained
which is ultimately reduced to native gold. Similarly, neutrali- by the writer. However, gold does not form many stable
zation of alkaline waters containing dissolved gold in the form compounds, and ions associated with the gels do not have the
of alkaline complexes leads to precipitation of the metal where same precipitating effect as found by Dyck (1971) for silver.
such waters come into contact with acid waters in oxidized On the other hand gold is readily reduced to the metal by
zones or in humic environments whose waters are invariably practically any organic compound and by a great variety of
buffered on the acid side of the pH scale. In hypogene ions such as Fe2+,Mn2+,etc. Once in the metallic form it is
environments loss of alkalis such as K, Na, Rb and Cs by not easily desorbed (dissolved) by natural solutions, except
reaction with wall rocks (sericitization, albitization, etc.) leads where relatively high concentrations of complexing anions
to a shift in the pH toward the acid range, the decomposition such as [S20J2-and [Cl]' are present.
of the alkaline complexes and the precipitation of native gold The metallic gold colloid carries a negative charge in the
 Contents

CHEMISTRY. MINERALOGY AND GEOCHEMISTRY OF GOLD

pH range 4 to 8, which is that found in most natural waters. can see by a glance at Table 22. The reasons for this are
Reversal of the charge is possible by the addition of various complicated and only imperfectly known. The answer proba-
salts (Weiser, 1933). Most of the common gold complexes bly lies in the fact that seldom are these gels found in a pure
carry a negative charge, e.g., [AuCl,]-, [Au(S,O,),P-. Some of state. Most are highly contaminated by hydrous femc oxide
the natural colloids and gels carry positive charges under and alumina gels, and these are probably mainly responsible
certain conditions. Below a pH of approximately 7.5 (the for the adsorption and/or coprecipitation of gold in the
isoelectric point) hydrous ferric oxide carries a positive composite gels. Other possibilites also exist: the hydrous MnO
charge; above this pH the sol is negative. From this it follows or Mn(OH), gel is positively charged and adsorbs anions such
that hydrous femc oxide would adsorb and/or coprecipitate as sulphate strongly. It would be expected, therefore, that the
and carry colloidal and anionic gold extensively in natural gold colloid and anionic complexes would also be adsorbed.
solutions with an acidic and neutral reaction. Under alkaline Hydrous MnO is probably one of the initial manganese
conditions hydrous femc oxides would tend to repel and precipitates in neutral and alkaline environments character-
disperse colloidal and anionic complexed gold. These features ized by a low oxidation potential, such as gossans, stream
seem to account for the common enrichment of gold in many sediments, etc. During maturation of the gels the MnO or
limonitic gossans and for the transport of gold adsorbed to Mn(OH), gel is oxidized, ultimately yielding MnO, and other
colloidal femc oxides in acidic and neutral surface and manganese oxides. The problem is also concerned with the
groundwaters during the oxidation of gold deposits. adsorption of gold by humic substances and the formation of
Aluminum hydroxide and hydrous alumina behave in gold organic compounds. Since humus is invariably a constitu-
much the same way as hydrous femc oxide, the isoelectric ent of the composite sols in the surface environment, this
point being approximately at pH 8.4. Aluminosilicates behave mechanism may also be important in the enrichment of gold
similarly, the isoelectric point shifting to a more acid pH as in gels. Finally, natural sols and gels tend to adsorb a great
silica is substituted in the system Al,03-SiO,. With 57 per cent variety of substances which change their effective surface
A1,03 the isoelectric point is at a pH of 7.0 whereas with 34 charges. Adsorption of a variety of cationic complexes by
per cent Al,03 the isoelectric point is at 5.0 (Johansen and negative sols and gels may give them an effective positive
Buchanan, 1957). Much more complex are adsorption phe- charge, which permits them in turn to adsorb the negative
nomena involving kaolinite and other clay minerals. In kaolin- gold sols and anionic complexes.
ite the negative charge on the 001 face is always greater than 3. Changes in oxidation-reduction potential: gold is the
the positive charge on the edge faces and the aluminum most noble of metals and hence the lowest member of the
mineral invariably carries a net negative charge down to a pH electrochemical series, the potentials in acid solutions being as
of 3.6 (Street and Buchanan, 1956). One would expect, follows (Latimer, 1952):
therefore, that gold colloids and anionic complexes would be +
Cu = CuZ+ 2e- EO= -0.337
repelled by the clay minerals. Such, however, is not the case as Fez+= Fe3+ e-+ EO= -0.77 l
shown by Mering et al. (1953). They found that gold sols were Ag = Ag+ e-+ EO= -0.799 l
extensively adsorbed by kaolinite, particularly on the edge +
2H,O = 0, 4H+ 4e- + EO= - 1.229
faces (i.e., the sites of positive potential). These features +
Mn2+ 2H,O = MnO, + +
4H+ 2e- EO= - 1.23
explain why gold is frequently concentrated in clay mineral +
Au = Au3+ 3e- EO= -1.50
aggregates and mixed limonitsclay mineral-silica aggregates Au = Au+ e- + EO= -1.68
in the oxidized zones of some gold deposits (see also Chapter From a consideration of these and other redox couples it can
IV). The phenomena may also account for the rich primary be seen that all the metals and most of their ions can reduce
shoots of gold in certain highly kaolinized and argdhzed rocks, gold from its ionic state to the metal. The effect produced by
which owe their condition to sedimentation processes or iron and manganese is marked. Thus, an increase in the redox
hydrothermal alteration. Foster (1971~)considers this proba- potential with the consequent production of femc ion and
ble at Carlin, Nevada, but Radtke and Scheiner (1971) MnO, renders gold more soluble and mobile if complexing
disagree and state that there is no apparent correlation agents are available. Alternatively a decrease in the redox
between the amount of gold deposited in these disseminated potential permits greater concentrations of ferrous and man-
orebodies and the total clay or illite content. The reason why ganous ions, which precipitate gold. Increase in the oxidation
certain clay minerals such as kaolinite do not always adsorb potential in solutions containing iron has other effects. Ferric
negative gold colloids or complexes probably has something to iron undergoes hydrolysis and is precipitated as hydrous oxide
do with the fact that as the adsorptive sites of clay minerals gel which cames a positive charge. This results in the strong
become saturated with phosphate, arsenate and other negative adsorption of anionic gold complexes and gold colloids as
anionic complexes they become negatively charged and hence noted in 2 above.
repel the gold species. This has been shown experimentally as Changes in the oxidation-reduction potential are effective
far as phosphated edges are concerned (Marshall, 1964). in precipitating gold from natural solutions in a variety of
Many other gels and sols carry negative charges, exam- supergene environments - in the sea, in freshwater bodies, in
ples being silica, hydrous manganese dioxide, humic sub- manganese and iron bogs, in precipitates at spring orifices and
stances and various sulphide sols. Theoretically these should in the zones of oxidation of gold deposits. Similarly, these
repel and disperse the metallic gold colloid and anionic gold changes greatly affect the mobility of gold during hypogene
complexes. In nature, however, the theory does not in general processes. Where the oxidation potential is high, gold is
apply for we find that many of these substances are avid for maintained in the oxidized (ionized) state, permitting its
gold and tend to precipitate the element extensively as one transfer for considerable distances. Where the oxidation
 Contents

THE GEOCHEMlSTRY OF GOLD AND ITS DEPOSITS

potential is low or where reducing substances are present the pyrite. Limonite, wad, jarosite, scorodite and a veritable host
mobility of the metal is restricted. Finally, changes in the of other supergene minerals precipitate, adsorb or otherwise
oxidation potential have a marked effect on the solubility of incorporate gold from solution. Hydrogen in serpentine
gold as sulphide, arsenide and antimonide complexes. Oxida- (mainly in magnetite) is considered by Coveney (1971) to have
tion of these complexes results in the rapid and nearly been the effective precipitant of gold from aqueous gold
quantitative precipitation of the metal. species in the Oriental Mine, Alleghany, California. The
The effects of various anions in solution may influence stability of the various soluble gold complexes in the presence
the coprecipitation of gold and silver on sulphides as shown of the various earth materials noted above varies widely and
by the researches of Sakharova et al. (1976). They found that depends on many parameters. Generally speaking the halide
the influence of the anions C1-, F-, C0:-, HC0,- and PO:- complexes are the most readily reduced followed by the
upon the precipitation of gold and silver in the system thiosulphate, thiocyanate, cyanide and various S-As-Sb com-
HAuCl, + AgNO, + NH,OH was marked. The presence of plexes in about that order. Considering the great variety of
C1- and F- lowers the overvoltage of the silver reduction natural precipitants of gold one wonders how the element is
reaction and raises the overvoltage of gold reduction leading capable of migrating in any environment.
to a decrease in the fineness of the gold-silver precipitates. The 6. Coagulation of colloids: colloidal gold, colloidal gold
influence of C o t - and HC0,- ions results in a sharper rise of compounds and gold adsorbed to various inorganic and
the overvoltage of the process of silver reduction than that of organic colloids can be precipitated by a great variety of
gold and consequently the formation of precipitates with a chemical changes such as a decrease or increase in pH,
high fineness. The PO:- ion exerts no appreciable influence coprecipitation by other colloids and precipitation by elec-
upon the coprecipitation of Au and Ag. trolytes. Pyrite, arsenopyrite, galena and various other sul-
4. Decrease in H,S, S2- or C1- concentration of vapours, phides, arsenides and sulphosalts also coagulate gold on their
gases or solutions: where gold is carried as the sulphide or surfaces as shown by Zvyagintsev and Paulsen (1940) and a
chloride complexes, reaction of the vapours, gases or solutions number of earlier workers. The coagulating effect of minerals
with the wall rocks or gangue minerals may reduce the like quartz, mica, barite and calcite is less marked than that of
concentration of H,S, S2- or C1- as a result of the formation the sulphides, etc., but is effective over long time intervals.
of pyrite, chloride-bearing minerals, etc. This breaks up the There are no data on the presence of gold colloids in
sulphide and chloride complexes causing the precipitation of natural hydrothermal solutions, and hence the effect of
gold in one form or another. Similar effects probably result coagulation processes in primary vein formation is a matter of
when gold is transported as complex S-Se-Te and S-Sb-As speculation. In natural fresh- and seawater it is probable that
compounds and the S2-, HS- or As ion concentration is much gold is precipitated as a result of the coagulation of
reduced by reactions with iron (formation of pyrite and colloids.
arsenopyrite) in the wall rocks. 7. Sublimation: this process is probably effective mainly
Reactions such as those noted above appear to be partly in volcanic and fumarolic processes. The sublimates incorpo-
responsible for the primary precipitation of gold (and silver) rate the available gold either in their structures or in an
in a number of epigenetic deposits in basic rocks and in adsorbed form.
certain types of sedimentary rocks. These reactions may also 8. Decomposition of organic (humic) complexes due to
operate in a modified way in the zones of reduction (second- oxidation: humic complexes, carrying gold in an adsorbed
ary sulphide zones) of oxidized gold deposits. state or as an integral part of their structure, on oxidation
5. Precipitation of gold as a result of the reaction of yield CO,, H20, etc. and liberate the gold. This gold may then
gold-bearing solutions, gases and colloids with various natural be precipitated by a variety of mechanisms.
materials: the process is evidently one of reduction although 9. Sedimentation of particulate matter carrying gold: this
other mechanisms such as adsorption and colloidal coagula- process acts in all sedimentary basins in lakes, seas and in the
tion may also be involved. Whatever the cause it has been Leans. The gold is incorporated in the sediments in a variety
shown by a great number of investigators (Liversidge, 1893~; of forms.
Rickard 1896; Lenher, 1909; Palmer and Bastin, 1913; Moms 10. Death and sedimentation of gold-bearing plants and
1918; Sakharova and Lobacheva 1967; Radtke and Scheiner, organisms: numerous organisms and plants in natural fresh
1970a; Shabynin, 1970; Zaitseva et al., 1973; Lakin et al., and saline waters absorb gold into their vital parts, or like
1974; Sakharova et al., 1975; and others) that most minerals plankton adsorb the element on their surfaces. On their death
and rocks precipitate gold from its solutions. The most their remains are deposited on the bottoms of lakes, seas and
efficient precipitants appear to be the sulphides, arsenides, the oceans. There, further reactions attendant on the decay of
tellurides, sulphosalts, native metals including gold, calcite, the organisms and plants fix the gold in the sediments. One of
clay minerals, finely divided chlorite, graphite, carbon, car- the most common of these reactions in a reducing environ-
bonaceous matter, organic carbon compounds, pyritiferous ment is the bacterial degradation of the protein complexes of
carbonaceous slate and schist, carbonate rocks, sapropel and the organisms with the consequent production of H,S, which
so on. Charcoal has long been known to be an active precipitates iron and other sulphides which incorporate the
precipitant of gold (and silver) mainly by adsorption (Gross gold. Legedza (1967) considered that sedimentary pyrite
and Scott, 1927). Morris (1918) was able to grow beautiful absorbs gold dissolved as the thiosulphate during sedimenta-
dendritic crystals of gold on calcite in hydrothermal bombs tion and diagenesis in the following manner:
charged with gold chloride. Shilo et al. (1974) have shown that + +
FeO H2S nH,O + FeS.nH,O
gold and silver can be precipitated as a solid solution on + + +
2 FeS-nH,O Au(S,O3),3- + 2 FeS, Au 2S0, + nH,O
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

11. Precipitating action of organisms: certain types of comment on the analyses quoted in the literature since they
bacteria precipitate gold directly from natural waters. (See the have been done by many different investigators and by a great
section on biogeochemistry.) In addition iron and manganese variety of different methods over a period of some 50 years.
bacteria play an indirect part since they oxidize Mn+Zto Mn+4 Table 23 shows the ranges in various types of plants. For
and Fez+ to Fe3+, which then undergo hydrolysis and are particulars the reader should consult the extensive compilation
precipitated as hydrous manganese and iron oxides. During by Jones (1970) and the various references noted in the table.
these reactions gold may be wprecipitated or adsorbed by the
hydrous oxides. Table 23. Gold content of plantsq
Type of plant Au in ash (range)
Gold is elaborated by vegetable growth in Nonvascular
soils where there are no pretended geo- Bacteria no data
logical indications; it is found occasional- Algae (marine) 0.00015-1.7
ly in rain water; it may, for anything I Algae (terrestrial) no data
know to the contrary, exist in the air, va- Fungi (terrestrial) trace-1 1.6
pourized and afloat, as reguline. Lichens 1-1.3
-W.B. Clarke, (Southern Gold Mosses 0-19.2
Fields, Sydney, 1860) Vascular
Herbs
Biogeochemistry of gold Grasses and sedges 0-8.6
Forbs 0-610
Gold is a microconstituent of many plants and animals, Shrubs 0-600
including man. The literature on the biochemistry of the Trees
element is extensive, but is scattered through a great variety of Coniferous 0-6
medical and biological journals, many not readily accessible to Deciduous 0-10
Miscellaneous
the geologist and geochemist. Only a few of the most impor- Honey not detected
tant papers have been consulted during the preparation of the Wine (U.S.S.R.) 0.030-0.758
following compilation. PUL ( P P ~ )
Gold has been used in dentistry and as a medicine for 'Compiled from data by: Aferov et a/. (1968)
Aripova and Prikhid'ko (1965)
centuries. The potable gold known to the alchemists was a Aripova and Talipov (1966)
dilute solution of the metal in aqua regia. Many medicinal Babiaa (1943)
virtues were ascribed to this potion, including those of the Beridze et a/. (1969)
Boyle (unpublished)
elixir of life. In more recent times gold solutions (thiosul- Cannon et a/. (1968)
phates) were used in the treatment of syphilis; today gold Curtin et a/. (1968)
compounds still find a medicinal use in the treatment of Errnets2 (1954)
Fukai and Meinke (1962)
rheumatoid arthritis. Kaspar et a/. (1972)
Gold has long been known to be a constituent of plants Khotamov et a/. (1966)
Korotayeva and PoWrarpochkin ( 1970)
and animals. The Czechoslovakian alchemist Paterson Hain Lungwitz ( l900o.b)
Janos is said to have found gold in Hungarian grapes, and he Razin and Rozhkov (l%3, 1966)
wrote a treatise on the occurrence of gold in vegetation Schiller et a/. (1971a.6, 1973)
Stark (1943)
entitled "De Auro vegetabili et vitibus Hungariae aureis". V.I. Warren and Delavault (1950)
Vernadsky cites the researches of Rouelle and d'Arcet who Zvyagintsev (I 94 1)
found gold in French wines in 1779, and C.-L. Berthollet the
famous-~renchchemist is said to have determined the content There are insufficient data on the gold content of nonvas-
of gold in the ashes of vegetables. In more recent times a cular plants to draw any satisfactory conclusions about the
number of voluminous compilations dealing with gold in capacity of these plants to accumulate gold. Certain species of
plants and animals have appeared. Among these the works by fungi (Boletus) seem to accumulate gold. Fungi (mushrooms)
Berg (1928) and Bertrand (1932) summarize their own work also appear to accumulate silver in places (see the compilation
and that of those before them. Other exhaustive reviews, by Boyle, 19686). Razin and Rozhkov (1966) analyzed five
replete with many references, covering some 10 years of samples of various lichens and found an average of 1.0 ppm
research and about all that was known concerning gold in Au in the ash, about twice that found in their soil substrates.
plants and animals at the time, are the works by Babizka Lichens tend to concentrate copper, silver and other elements
(1943) and Babizka et al. (1945). More recently Jones (1970)
where they are available in the substrate (Lounamaa, 1956;
has compiled most of the data available on the gold content of
LeRoy and Koksoy, 1962), and may well be accumulators of
plants and animals and added a commentary. The reader will
gold where it is available either in the substrate or in surface
also find a valuable discussion on the biogeochemistry of gold
waters.
(and silver) in the recent compilation by Manskaya and
Shacklette (1965) did not detect gold in his study of
Drozdova (1968) on the geochemistry of organic matter.
various liverworts and mosses, but Razin and Rozhkov (1966)
found up to 19.2 ppm Au in various species of bryophytes.
Gold in plants
The amount of gold in the ashes of the mosses generally
The gold content of plants varies over a wide range, and hence exceeded that present in their substrates.
average values are practically meaningless. It is difficult to Fungi and bacteria may have an important role in the
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

cycle of gold in nature. Hatschek (1919) and Williams (1918) bacteria in the mobilization of gold in the oxidized zones of
noted that colloidal preparations of gold produced by the gold deposits containing abundant iron minerals is obvious,
addition of tannic acid tend to become mouldy, and that the considering the fact that the Fe-oxidizing bacteria are of
mould, in the course of time, removed the metal from common occurrence and that complexing substances such as
solution. Williams' (1918) experiments with colloidal gold C1 and organic compounds are, likewise, common in some
solutions and fungi showed the following: environments.
1. Conidia of Penicillium glaucum and Oidium lactis Lyalikova and Mokeicheva (1969) examined the role of
developed in colloidal gold solutions which contained tannin bacteria in the migration of gold during the oxidation of gold
or gum arabic. deposits. They found that numerous heterotrophic bacteria
2. The living fungus, during growth, removed the metal have the ability to dissolve gold, and that various sulphur
from the solution. Retention occurred in such cell walls as are compounds (e.g., thiosulphates) that accumulate in solutions
not cuticularized. during the oxidation of sulphides by sulphur bacteria contrib-
3. The process goes on more irregularly when masses of ute ti the solution of gold,A culture isolated from the Zodsk
dead fungus were introduced into solutions. gold deposit, similar to Bacillus alvei was the most active and
4. Solutions with a higher rate of diffusion coloured the dissolved 500 to 600 pg/L (ppb) Au in 3 weeks. The largest
fungus more quickly than those with a lower rate. In all cases amounts of gold solubilized in the experiments were obtained
the accumulation of gold finally produced a blue coloration. when stibnite was present - an interesting fact and one that
5. No explanation of the process could be given. supports the writer's contention that gold is frequently trans-
There are also a number of other scattered references to ferred in nature as some form of antimony compound. The
the capability of fungi to extract gold from solution. In one authors concluded from their laboratory experiments and
interesting reference (selected abstracts from the technical microbiological examination of the Zodsk gold deposit that
literature on gold by Johnson, Matthey and Co. Ltd. for 1969, bacteria play a sigdicant role in gold migration.
p. 1) it is reported that the Novosti Information Service in In a recent report KG. Doxtader (U.S.Geo1. Surv., Circ.
Moscow states that mould fungi extract gold from solution. 622, p. 13) summ&zed his work involving the testing of the
Active fungi extracted 98 per cent of the metal in 15 to 20 h. ability of various soil bacteria and fungi to grow in liquid
Babiika (1943) mentions that Penicillium glaucum is capable media containing different concentrations of the metals in-
of depositing colloidal gold on its membranes and in its cluding gold, silver, mercury, copper, lead, manganese, cobalt,
vicinity, and suggested that fungi in the surface parts of gold chromium, molybdenum, tin, cadmium, uranium, vanadium,
deposits and mines probably have a great influence in the tungsten, zinc and palladium. He found that one fungus could
transition of gold from the ionized to the colloidal state. The grow in a concentration of 25 ppm Au, and 12 species of
same author cites a number of references, which bear on the bacteria and fungi could grow in cultures containing 10 ppm
deposition of gold mainly as a colloid by various micro-organ- Au. On the other hand, cultures containing >5 ppm Ag or Hg
isms. Barbieri (1935) describes various gold-bacterium com- were found to be lethal to all organisms tested; some organ-
plexes, which are formed when bacteria are treated with isms could grow in saturated solutions of copper, manganese,
solutions of AuCl,. molybdenum, lead, uranium, tungsten and zinc. Two bacteria
Parts and Martinet (1964) carried out an extensive species (not named in the report) previously reported to be
investigation of the role bacteria can play in the cycle of gold. capable of solubilizing native gold (up to 1.5 ppm in solution)
They found that gold from laterites and other gold-bearing were also tested for a period of 3 weeks, with negative results.
materials could be solubilized by autotrophic bacteria, such as In a more detailed account of his work Doxtader (in
the nitrogen fixing species, and to a much smaller extent by Lakin et al., 1974) concluded as follows:
various heterotrophic bacteria existing in the soil, water and In the microbiological studies, elemental gold was added to liquid
air. The solubilization of gold by bacteria can be marked, but nutrient media which were then inoculated with pure cultures of
several factors influence the phenomenon, such as the pH, the bacteria and fungi either obtained from stock collections or isolated
from soil. In a glucose-peptone medium containing colloidal gold,
age of the cultures, the quality of inoculum, the concentration significant gold solubilization occurred. In other media or with
of gold in the medium and the nature of the nitrogenous and powdered gold, metal solubilization was slight. The microbial
carbonaceous nutritive substances. These and other factors strains showed various abilities to solubilize the noble metal. In
discussed by the authors should be referred to in the original sterile glucose-peptone medium gold solubilization occurred, but, in
paper. It is of particular interest to note that the solubilization the same medium inoculated with various microorganisms, the
solubilization of gold increased.
activity of the various bacteria was strongest with strains
obtained from soils over gold-bearing deposits. Doxtader (in Lakin et al., 1974) also tested soils and
In a Canadian patent, A. A. Mayling (Chemical Ab- stream sediments from Cripple Creek, Colo., to determine
stracts, v. 66, 13120b, 1967) describes the use of bacteria to whether specific bacteria or fungi occurred in materials
keep aerated femc chloride solutions oxidized for leaching containing gold. No significant differences in numbers or
ores containing Au, Ag, Cu and Pb. Suitable bacteria are kinds of micro-organisms present were found between gold-
Ferrobacillus ferrooxidans and Thiobacillus ferrooxidans. At bearing and barren samples.
acid pH (1-3) and temperatures ranging from 15 to 40°C During recent investigations of the effect of organisms
these Fe-oxidizing bacteria depress the normal reduction of on the geochemical cycle of gold Mineev (1976) concluded
ferric chloride resulting from reaction with the metals or that the dissolution, colloidal formation and precipitation of
sulphide in the ore. Presumably the gold taken into solution is gold take place in nature with the participation of various
complexed as chloride. The implication of the action of such micro-organisms.
 Contents

CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

Of the vascular plants the herbs have received the most corresponding silver value was 2.4 ppm. Equisetum growing on
attention with respect to their gold content. Razin and old tailings piles on the Hollinger property at Timmins,
Rozhkov (1966) analyzed a number of samples of various Ontario contain considerable amounts of gold according to a
grasses and sedges, including entire plants and the sterns, personal communication to the writer from Mr. C.D. Mac-
leaves and fruit of the plants. Their values range from 0.005 to Kenzie, Chief Geologist of Hollinger Gold Mines (1970). The
8.6 pprn in the ash. Over some of the placer deposits in the gold content of the ash of these plants ranged from 0.01 to
Beauceville area of Quebec the writer has found an average of 0.25 oz Au/ton (0.3 to 8.5 pprn).
2.4 pprn Au in the ash of various grasses (whole plants, The gold content of shrubs ranges from 0 to 600 ppm.
excluding roots; 9.3% ash, mainly silica). This compares with Babitka (1943) found 600 pprn in the ash of the seeds of
an average of 9.2 pprn Au in the ash of Equisetum in the same Clematis vitabla (virgins' bower) in the andesitic region of
area (whole plants, excluding roots; 26% ash, mainly silica). It Oslany, Czechoslovakia. The soil and weathered debris wn-
would appear from these values that there is a relationship tained 0.2 pprn Au. In the wood and fruit of the same shrub
between the gold and silica content of plants, the higher the and of Corylus avellana (hazel nut) and Rosa Canina (dog
silica the greater the gold wntent, all other things being equal. rose) from Oslany and other areas in Czechoslovakia the same
This feature is also mentioned by Babitka (1943) and author found gold contents ranging from trace to 110 pprn in
Thyssen-Bornemisza (1942). the ash. It is interesting to note that relatively large amounts
The gold contents of grasses and maize (Zea mays) have of gold occur in seeds. This is also true for silver as pointed
been investigated recently by Schiller et al. (1973) using out by the writer (Boyle, 19683). Warren and Delavault (1950)
neutron activation analysis with a view to determining the found only small amounts of gold (nil and t0.03 ppm) is the
influence of seasonal variations of samples in a gold-bearing ash of Juniperus communis (dwarf juniper) in the North Fork
area. The contents in the ash of maize ranged from 0.008 to of Watson Bar Creek in the Clinton Mining Division of
0.103 pprn Au; in the ash of grasses the values were 0.009 to British Columbia. Gold occurs in quartz veinlets in this area.
0.040 i p m Au. Marked seasonal variations were noted be- Razin and Rozhkov (1966) analyzed a number of shrubs in the
tween the three seasons, spring, summer and autumn. These vicinity of the Kuranakh gold deposits, Yakutia. Their values
are important data for biogeochemical prospecting purposes. range from 0 (not detected) to a maximum of 10 pprn Au in
The investigators recommend that sampling should be done the ash; this can be compared with a maximum of 8 pprn Au
preferably in the spring since this is the time when the in the soil. However, they found that in some 65 per cent of
maximum amount of gold is taken up by the plants due the soil and shrub ash samples that the maximum gold
probably to higher rainfall and movement of elements in soil contents in the soil exceeded those in the ashes of the shrubs.
waters, etc. Aripova and Talipov (1966) investigated the gold content of a
Considerable work on the gold wntent of various forbs number of shrubs and herbs in the gold belts of Uzbekistan.
has been done in the last 40 years. The range in the values is The species sampled were wormwood (Artemisia terrae-alba),
from 0 (not detected) to 610 pprn Au. Babitka (1943) and his salsola (Salsola sp. and ferula (Ferula sp.). The largest
colleagues carried out investigations on the gold content of a amounts of gold were found in the ash of wormwood (up to
variety of forbs for some 10 years, paying particular attention 125 pprn Au). The average gold wntent in the plants over
to plants such as corn, beans and horsetails (Equisetum). In auriferous zones ranged from 20 to 50 pprn Au and greater.
the ash of Equisetum palustre (marsh horsetail) he found 610 The largest amounts of gold were found in the plants during
pprn Au in the andesitic region of Oslany, Czechoslovakia, springtime and early summer (May-June), the blooming and
where the gold content of the soil averaged about 0.2 ppm. In fruiting period. Khotamov et al. (1966) used neutron activa-
two other samples of Equisetum arvense contents of 16 and 63 tion methods to determine the gold content of a number of
pprn Au were reported in the ash. These results seemed to shrubs and their organs in one of the ore fields of the
indicate that Equisetum is a gold accumulator. However, gold-bearing Kyzyl-Kum district, U.S.S.R. Their values
Cannon et al. (1968) found that Equisetum averages only 0.17 ranged from 0.3 to 36 pprn in the ash. The soil substrates
pprn Au in the ash in the samples they investigated from a contained from 0.2 to 1.5 pprn Au. The leaves of some shrubs
number of mineralized areas in the conterminous United contained more gold than the stems and roots, whereas in
States; in samples from Alaska they found up to 0.5 pprn Au other plants the gold content was relatively uniform in all
in the ash. These values are about the same as those reported organs. The largest amounts of gold (and arsenic and antimo-
by Warren and Delavault (1950) and Razin and Rozhkov ny) in the plants were observed during the period of intensive
(1966) in various varieties of Equisetum. Cannon et al. (1968) growth and the smallest amounts in dried (dead) plants. No
concluded that the high values quoted by Babitka and other relationship was detected between the ash content and the
workers may be erroneous since a study of the analytical overall content of gold (and arsenic and antimony). Arsenic
procedures that were used suggest that other metals in the and antimony were-alsodetermined by activation methods on
plants, some of which are relatively high (e.g., zinc, copper), the vegetation and soil. A direct correlation between gold and
may have been measured and reported as gold. antimony was found in the soil and plant ash, whereas a
Our research on Equisetwn seems to indicate that horse- correlation between gold and arsenic in the soil and plant ash
tails may be accumulators of gold. Over some of the placers of was not always observed.
the Beauceville area, Quebec the ash of horsetails contained The gold wntent of trees ranges from 0 (not detected) to
up to 9.2 pprn Au (whole plants, excluding roots; 26% ash). 10 pprn in the ash. Lungwitz (1900qb) appears to have been
Equisetwn ash from the Ramore area of Ontario, well removed one of the first to report the presence of gold in trees,
from gold mineralization, contained 0.095 pprn Au; the specifically in what he called 'iron wod' from the Omai Valley
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

in British Guiana. The work was done mainly to prove that over the Kuranakh (karst) type of gold deposits in Yakutia
gold migrates in surface waters. BabiEka (1943) records up to showed that there was a direct relationship between the
10 ppm Au in the ash of the blossoms of Tilia parvifolia content of gold in the ashes of the plants and the content in
(linden). Warren and Delavault (1950) found from 0 to 1.02 the soil substrate.
ppm Au in the ash of Pinus contorta (lodgepole pine), Pinus The uptake and translocation of gold by plants has been
ponderosa (western pine), Pseudotsuga taxifolia (Douglas fir), studied by a number of investigators including Zvyagintsev
Salix sp (willow) and Populus tremuloides (aspen) in the North (1941), Babizka (1943), Razin and Rozhkov (1963), Shacklette
Fork of Watson Bar Creek, British Columbia. In areas et al. (1970) and Schiller et al. (1971~).
unmineralized with gold (negative areas) the gold contents in Zvyagintsev (1941) speculated that the solutions secreted
the ash of these trees ranged from nil to 0.03 ppm. In the by the root hairs of plants were capable of solubilizing gold in
vicinity of quartz veinlets carrying gold (positive areas) the their vicinity, and that the gold entered the plant in an ionized
contents in the ash ranged from nil to 1.02 ppm. Silver was form.
also determined in the ash of the trees. Calculations based on Babizka and his colleagues after more than 10 years of
the values given indicate that the Au/Ag ratio in the ash is study on the gold content of plants concluded the following:
about 0.06. Other investigations of the gold content of trees 1. Only a few plants can take up gold in large amounts.
include those by Zvyagintsev (1941), Razin and Rozhkov 2. The concentration of gold is characteristic for certain
(1963, 1966), and Khotamov et al. (1966). Their values range plants; it is not, however, definitely known whether gold has a
from 0 (not detected) to 6 ppm in the ash of various species. favorable effect on the growth and the life functions of these
Concerning plant products Berg (1928) did not detect plants.
gold in honey. In wines from the U.S.S.R., Beridze et al. 3. The gold taken up by the roots of a plant spreads
(1969) by activation analysis found from 0.030 to 0.758 pg/L throughout the plant and becomes concentrated in certain
(ppb) Au. The level of the gold content in red wines was organs. In the case of seed-bearing plants, this is usually in the
considerably higher than that in white wines. Most of the gold seeds. With increasing age of a plant there is a progressive
was thought to have come from the soil with minor contribu- increase in the gold content.
tions from the apparatus used in the processing of the vineous 4. Plants absorb ionized gold derived from solid particles
spirit. of gold, particularly when the metal is in the colloidal state. In
Seasonal variations in the gold content of plants have nature, colloidal gold is concentrated mostly in the rhizo-
been noted by some investigators, but the data are insufficient sphere (root layer), perhaps by the actions of plants and
to draw adequate conclusions. Aripova and Talipov (1966) organisms generally. If gold occurs in the soil in the form of
report that the ash of Artemisia (wormwood) contains from 10 small nuggets, tablets, fine wires, etc. it is practically unavail-
to 20 times more gold (and copper, lead and chromium) in able to plants.
May than in October, and that these metals tend to be highly
concentrated in plants in desert regions. Khotamov et al. Razin and Rozhkov (1963) concluded from their data on
(1966) found that the largest amounts of gold (and arsenic and gold in plants and soils over the Kuranakh (karst) type of gold
antimony) occur in plants during the period of intensive deposits in Yakutia that the gold is assimilated by plants in
growth and the least in plants that have died and dried up. As the ionized form.
noted above Schiller et al. (1973) noted marked seasonal Shacklette et al. (1970) experimented with the uptake and
variations in the gold content of plants, the maximum concen- translocation or radioactive (lg8Au)and nonradioactive gold
trations being present during springtime. (19'Au) by impatiens (Impatiens holstii), garden balsam (I.
With respect to the content of gold in the various organs balsamina) and onion (Allium cepa). They found that colloidal
of plants, Khotamov et a[. (1966) state that the largest gold was not absorbed by the roots of these plants, and that of
amounts of gold are concentrated in the above ground the solutions of gold used (chloride, cyanide, bromide, iodide,
portions of plants, particularly in the leaves of some species. thiocyanate, thiosulphate and gold cyanide solution via flax)
Seeds may be concentrators of gold in a manner similar to the gold cyanide is the most readily absorbed by roots and
that found for silver (Boyle, 1968b). transported in largest amounts to the leaves. They concluded
There appears to be no particular relationship between that if gold is present in the soil and if cyanogenic plants are
the gold content and the ash content of plants. There may, rooted in this soil, a mechanism is present for the entrance of
however, be a relationship between the silica content of plants gold into the biogeochemical cycling process.
and their gold content, but more work is required to confirm Schiller et al. (1971~)experimented with the uptake of
this. Khomatov et al. (1966) found a definite direct correlation radioactive gold by barley from solutions containing in one
between gold and antimony in the ash of plants, a correlative case aurothiomalic acid-Au- 198-sodium salt and in another
feature that also holds in most gold deposits. The correlation case colloidal gold (Au-198) (particle size range up to 200 A)
with arsenic was less definite. stabilized with gelatin. In both cases the uptake of gold was
The data with respect to the ratio - Au in soil/Au in almost quantitative, from which the authors concluded that
plant ash - are conflicting. Some investigators have found this gold accumulation by plants, both in wlloidal and ionized
ratio to be less than 1 whereas others have found the reverse. form, is possible.
It is well known that this ratio depends on a veritable host of In recent papers Talipov et al. (1975, 1976) have noted
factors, and one would expect wide variations and reversals to that the accumulation of gold (and a number of other
be general, even locally, as some of the data in the literature elements) in plants in the Karamin Range, U.S.S.R., depends
clearly show. A detailed study by Razin and Rozhkov (1963) to a large degree on the concentration of the element(s) in the
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CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

groundwaters and soils. In particular they noted a linear (central Kyzyl-Kum) concentrate large amounts of gold,
correlation between the Au, Ag, Cu, Zn and Pb contents of including Lagochilus intermedius (36 ppm in the ash), some
plants and that of soils and waters. They also observed that Salsola (saltwort) species, Artemisia and Stipa grasses. Certain
some elements have an antagonistic effect on the uptake of plants such as Spiraea and honeysuckle accumulate large
certain elements in plants; thus high calcium contents in amounts of gold when growing on or near auriferous deposits
groundwaters decreased the migration of gold and hence its in the Chatkal-Kurama region of U.S.S.R. (Talipov et al.
accumulation in plants. 1976). In India Dekate (1971) has noted that plants producing
The nature of gold in plants is not known. It may be hydrocyanic acid such as Sorghum saccharatum are capable of
present largely in the chlorophyll (a porphyrin), since a gold preferentially absorbing gold from the soil over auriferous
(111) porphyrin, which is relatively stable, has been synthesized deposits, at times, to the extent of depleting gold in the soil in
(Fleischer and Laszlo, 1969). It may also be present as an the proximity of plant roots. (See also the section on biogeo-
organometallic compound, perhaps as a protein complex, chemical prospecting in Chapter V.)
since the metal, like silver, is apparently concentrated in seeds Direct gold indicator plants appear to be rare if in fact
which are especially high in protein. The role of gold, if any, such plants actually exist. Dorn (1937) says that "Gold
in plant metabolism is unknown. indicator plants are up until the present only known from
According to Babicka (1943) small quantities of gold Brazil where Cecropia laetivirens Hub., C. palmate Wilki, C.
stimulate the growth of plants and micro-organisms, whereas lyratiloba, AIpinia speciosa Schum., Typha dominguensis Kunth,
large amounts are toxic. He cites a number of researches to and Typha latifola L not only contain gold in their ashes but
support this contention. Felippe and Martins (1926) found also according to F. Freise are reliable indicators of gold
that native gold had an oligodynarnic (growth inhibiting) placers." Babicka (1943) mentions that prospectors searching
action on B. dysenteriae Flexner, and Nadson and Stem (1934) for gold and silver deposits in Queensland, Australia, looked
observed that native gold placed at a distance of 2 to 3 mm for the shrub Lonicera confua DC, which grows preferentially
from white mustard seeds retarded the germination of the on gold- and silver-bearing soils. A shrub in California is also
seeds and the growth of the sprouts. Shacklette et al. (1970) said by R.H. Stretsch to indicate the presence of gold, but no
found that concentrated solutions of radioactive gold cyanide details of this plant are given.
were extremely toxic to all Impatiens whereas low concentra- It is interesting to note that the early Chinese considered
tions of the compound were not toxic. Radioactive gold some plants to be indicators of gold and silver deposits.
bromide solutions were very toxic to Impatiens, and radioac- Needham (1959) quotes Tuan Chleng-Shjh in the Yu-Yang
tive gold iodide solutions were found to be extremely toxic to Tsa Tsu written circa 800 A.D. as saying:
all plants experimented with. Radioactive gold thiocyanate "When in the mountains there is the tshung plant (ciboule
was toxic to unrooted cuttings of Impatiens, whereas the onion; Allium fistulosum), then below silver will be found.
nonradioactive solutions were less toxic. Gold thiosulphate When in the mountains there is the hsiai plant (shallot; Allium
solutions were only slightly toxic to all Impatiens. The toxic bakeri), then below gold will be found."
effects manifested by gold solutions on plants are principally There are numerous other similar statements pertaining
wilting of leaves and stems, necrosis and chlorotic symptoms. to gold in the old Chinese literature on geological and mining
None of these effects have been observed by the writer in subjects, but space precludes their mention here. One is of
plants growing in soils and placers rich in gold in Canada, nor interest, however, namely that the Chinese noted the presence
are there any references in the literature to such effects of the chhi (essence) of gold in the rape-turnip (Brassica
attributable to the presence of gold in other countries. The rapa-depressa) (Needham, 1959).
writer has also not observed any stimulative effects on plants It is worth noting that the coincidence of occurrence of
that could be related to the presence of small amounts of gold the onion species (Allium sp.) and the precious metals, silver
in soil and soil solutions. and gold, is probably an indirect one, the relationship being
Some plants appear to be gold accumulators. The case for more dependent on the presence of sulphur. The writer has
Equisetum needs verification, and further careful studies noted that various species of wild onions and the meadow
should be camed out on this plant, especially where it grows garlic (Allium canadensis) often proliferate where an abun-
on gold-enriched soils. Grasses also appear to accumulate gold dance of sulphate is available from the oxidation of sulphide
in places. Fungi and lichens are probably accumulators of deposits, some of which may be auriferous. It is also well
gold where the element is readily available, and some mosses known that the Alliwn species, especially garlic, is generally
also appear to concentrate gold according to the data provid- rich in sulphur, and some species seem to take up more than
ed by Razin and Rozhkov (1966). Khotamov et al. (1966) state average amounts of arsenic, an element universally associated
that Lagochilus intermedius, Artemisia terrae-alba and Cousinia with gold and silver. The turnip is likewise rich in sulphur.
hamadae are concentrators of gold in the Kyzyl-Kum region According to a recent report (Engineering and Mining
of U.S.S.R. Certainly some of the wormwood shrubs (Arte- Journal, v. 177, p. 32, 1976) (Chem. Abstr., v. 34, 111234h) the
misia) are greatly enriched in gold (up to 125 ppm Au in the water hyacinth (Eichhornia crassipes) is an accumulator of
ash) in the arid regions (Tamdynsk Mountains) of Uzbek, gold and silver. If experiments are successful it is planned to
U.S.S.R. according to the data of Aripova and Talipov (1966). use the plant to recover the two precious metals from solu-
The average for these shrubs over gold-bearing zones in many tions leaching old Cripple Creek mining tailings. In the article
cases ranges from 20 to 50 ppm Au. According to a later it is stated that "under a regular harvesting program, an acre
communication by Talipov and Khotamov (1974) a number of of hyacinths can yield silver at a rate of a pound every four
desert and arid land plants in the Tamdynsk Mountains days, and similar results are anticipated for gold."
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THE GEOCHEMISTRYOF GOLD AND ITS DEPOSITS

Gold in animals carpenter ant (Camponotus vagus) but found 400 ppb Au in
Gold has been determined in only a few animals, the data the ash of a bee (Vispidae sp.).
available being shown in Table 24. Reviews of the gold Razin and Rozhkov (1966) analyzed a number of birds,
content of animals have been published by Babilka (1943), including crossbills, buntings, pipits and a thrush in the
Vinogradov (1953) and Jones (1970). vicinity of the Kuranakh gold deposits, southern Yakutia. The
Noddack and Noddack (1939) found from 7 to 30 ppb gold contents in their ashes ranged from 0 (not detected) to
Au in the dry matter of a number of marine organisms, 1.5 ppm. There are numerous references to the occurrence of
contents similar to those found by neutron activation methods gold nuggets in the crops of birds.
in a variety of sea animals by Fukai and Meinke (1962) and Gold has been detected in a number of animals and in
Bowen (1968). Their values range from 0.0012 to 126 ppb Au man. Babizka (1943) and his colleagues detected relatively
in the dry matter. The average gold content for all marine high contents of gold in the ash of the antlers of deer and in
organisms done by activation methods is 23.84 ppb. Com- the hair. Contents from 0 (not detected) up to 68.6 ppm Au
pared with the average gold content of the sea (0.02 ppb) the were found in the antlers and other parts of deer in the
enrichment factor of gold in the dry part of marine organisms gold-bearing Oslany region of Czechoslovakia. The highest
is 1200. Enrichment factors similar to this figure are not contents of gold were found in the tips of the antlers. No gold
unusual in marine organisms. was found in the antlers of deer from the barren Malacky area
Babitka (1943) and his colleagues analyzed june bugs in western Slovakia or in the eastern Carpathian Mountains.
from the auriferous Oslany region of Czechoslovakia finding A wild boar bagged in the Oslany area contained no detecta-
an average of 25 ppm Au in their ash. In another location, ble gold. Jones (1970) found only 0.5 to 28.3 ppb Au in the
which is nongold bearing, near Stfibma' Skalice (Bohemia) ashes of the antlers of 15 mule deer (Odocoileus hemionus)
they found no gold in the ash of these insects. They reasoned harvested from four gold-mining regions in the United States.
that the june bugs feeding on the leaves of gold-bearing plants The largest amounts of gold occurred in the tips of the antlers.
accumulate gold, whereas those feeding on nongold-bearing The contents found by Jones are much less than those
plants do not have the opportunity of concentrating the metal. recorded by Babilika; they approximate the contents found in
To prove this they starved the gold-bearing june bugs for a common rocks.
time, then fed them on leaves which contained no gold. A Bertrand (1932) detected gold in cow liver and brains,
reduction of the gold content from 25 to 18.5 ppm was and in human blood, feces and urine. His values range from
observed in their ash. Razin and Rozhkov (1966) did not 0.2 to 14 ppm Au, the largest amount being in the cow brains.
detect gold in the water beetle (Dytiscus sp.) or in the In wet human liver Parr and Taylor (1963) found from 0.013
to 0.79 ppb. In human blood and its components the gold
content ranges from 0.06 to 0.8 ppb (Bagdavadze et al., 1965).
Table 24. Gold content of animals Human hair appears to be enriched in gold according to the
data given by Bate and Dyer (1965). They recorded means
Refer- ranging from 2.7 to 43 ppb Au in people from Tennessee and
Type of animal ence Remarks
New Zealand.
Marine animals
Sponge In the dry matter The data on the gold content of animals is inadequate,
Sponge (various) In the dry matter scattered, unsystematic and often conflicting. Conclusions
Sea urchin In the shell seem unwarranted except to note that marine animals seem to
Starfish In the dry matter have slightly lower amounts of the element than terrestrial
Sea cucumber In the dry matter animals. Gold seems to be concentrated in relatively large
Jelly fish In the dry matter
K. fische (Lippfische) In the dry matter amounts in the proteinaceous substances of animals (hair,
Clam (Tapesjaponica) In the dry matter of brains, muscle of fishes), which suggests that the element may
the soft parts be largely present as gold-protein complexes in animals,
Prawn (PandaIus sp.) In the dry matter of probably bound to the thiol groups in the complexes. In this
the soft parts
Mackerel (Pneumato- In the dry matter of respect gold behaves much like mercury, its adjacent element
phom japonim) the muscle in the periodic table. The role of gold, if any, in animal
Terrestrial animals metabolism is unknown.
Crustaceans (crab) In the shell There appears to be no auriferous animals as far as the
Insects data goes. Animals in gold-bearing regions may contain larger
June bugs In the ash amounts of the metal, but the data provided by Babilka
Bee ( Vispidae sp.) In the ash
Water beetle In the ash (1943) and Jones (1970) are conflicting with respect to the
Carpenter ant In the ash antlers of deer. The subject should be further investigated.
Buds It is interesting to note that the old literature is replete
Various In the ash with references of unusual occurrences of gold in animals.
Animals
various 614000 4.6 In wet and drv matter Gold nuggets and particles of auriferous quartz have been
Reference: I . Noddack and Noddack (1939.) found in the crops of partridges, hens, ducks and geese in
2. Bowen (1968). many gold-bearing regions of the world, but particularly in
3. Fukai and Meinke (1 962). Rumania and Hungary. Gold, plating the teeth of goats, sheep
4. Babizka (1943).
5. Razin and Rozhkov (1%6). and cattle grazing in auriferous regions, is also recorded in
6. Jones (1 970). some old manuscripts. Buried human skulls in certain aurifer-
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CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

ous streams have been observed to contain particles of and 10.8 oz Ag/ton (624.5 and 369.3 pprn respectively). He
attached gold. concluded that the carbonized wood had precipitated the gold
Homo sapiens is a concentrator of gold and silver but in from circulating solutions.
ways other than biochemical. Since the beginning of early gold In U.S. Geological Survey, Circular 560, p. 17 (1968) it is
mining (circa 4000 B.C.) man has accumulated an estimated reported that 12 samples of peat, muck and driftwood from
hoard of some 3 billion (3 X lo9) oz in his vaults, a small streams and wet areas near the Front Range mineral belt in
amount (0.00008%),however, compared with the total amount Colorado were analyzed for gold on a dry sample basis. Muck
of gold in the earth's crust (3.8 X 1015oz). By contrast man from Elk Park and peat from Rudolphs Bog contained 0.3
has won about 35 billion (35 X lo9) oz of silver from the pprn gold; driftwood from Clear Creek and soft peat from
earth. The ratio of extraction of Au/Ag is, therefore, 3/35 or Caribou Peat Bog contained 0.2 ppm. All other samples had
0.08, a value near that for the ratio found for the two elements less than 0.1 ppm.
in the earth's crust (0.1). Bensusan (1942) records data on an interesting wncen-
Gold in humus, peat bogs, muskegs and marshes tration of gold in Lower Burma, which is probably at least
Gold, in common with many of the metals, tends to become partly due to organic agencies. He states:
enriched in humus and humic deposits. The reasons are the
Between Tenasserim and Mergui, and impinging on the latter,
strong adsorptive and absorptive capacity of humus for metals there exists a very remarkable auriferous deposit in which it is
and the presence in humic deposits of various reducing estimated there is upwards of f200,000,000worth of gold in one
substances and H,S. concession alone of about 120 square miles. This statement might
Goldschmidt (1935) found 0.2 pprn Au in the ash from appear to be exaggerated, but it is a fact, nevertheless. The writer
beech humus in the Sababurg area near the Weser River in had to investigate this occurrence as well as the deposit at Tenas-
serim and he was asked to find a means of recovering the gold.
Germany. Deul(1958) noted the presence of gold in the ash of Research work was carried out both in Burma and in London with
humic acid fractions separated from peat. He did not detect the help of skilled chemists, metallurgists and geologists for nearly a
the element in plant ashes, in the whole peat ash, nor in any year working on a ton sample sent for the purpose. While hundreds
other fraction separated from the peat. This suggests that gold of assays on large samples show without any doubt that the materi-
al carries an average of about 4.0 grains of fine gold per ton (0.285
in the peat is mainly associated with the humic components. pprn Au), no means could be found for recovering it by any strak-
Curtin et al. (1970) and Lakin et al., (1974) found from t0.04 ing or amalgamation method. The gold appears to be in colloidal
to 5.1 pprn Au in samples of mull (forest humus layer) taken form as repeated examinations of sample and concentrate under
from gold-bearing areas in U.S.A. (see Table 20). They were high power microscope failed to show any free gold. In spite of all
that was done the tailings from the tests alwajrs assayed as much as
able to leach small amounts of gold (27-120 parts per trillion, the heads. No satisfactory theory has yet been put forward as to the
lo1*)from the mull with demineralized water and concluded origin of the gold nor as to the form in which it exists.
that much of the gold in the leachates was present mainly in It has been shown that the deposit, which is mangrove swamp
the form of extremely small colloidal particles (t0.05 p mud, could be exploited by means of a suction dredge at a cost of
diameter) with minor amounts of gold in the ionized state as 3d. or 4d. per cubic yard, i.e., as far as excavation and delivery of
alluvium to strakes or other appliances used on dredges for alluvial
thiocyanate and cyanide. My research on gold in soil profiles gold recovery are concerned: and since the average value of the
indicates that gold is commonly enriched in the humic layer of mud can be very conservatively taken at 1/6 per yard, there is a
the soil (see Table 20 and the section on gold in soils in this fortune waiting for anyone who can devise an economical method
chapter), and I think that much of the gold in the humic of extracting the gold.
horizon of soils is bound mainly as a humate, perhaps in a A number of boreholes were put down in the mud in various
places to depths of about 30 ft. and every sample taken showed
chelated or other organometallic configuration. gold by fire assay. One borehole was put down to 90 ft. without
The organic matter in bogs, muskegs and marshes is meeting bed rock and samples roughly taken from the bank of the
enriched in gold in certain areas. The copper bog near river always showed values.
Sackville, New Brunswick, which contains up to 4 per cent In all the straking experiments a small amount of concentrate
was recovered which consisted of pyriticised foraminifera, very
copper, is also enriched in gold in amounts up to 2.3 pprn and beautiful microscopic shells of innumerable shapes, but this concen-
in silver in amounts up to 5 pprn in the dry matter (Boyle, trate yielded only a few grains of gold per ton as well as traces of
1977). Bog manganese in peat in some places in New Bruns- platinum and iridium.
wick carries from 0.01 to 1.4 pprn Au and from 0.8 to 2 pprn
Ag in the dry matter (Table 22). The manner of occurrence of gold in humic deposits is
Other types of humic deposits also seem to be high in relatively unknown. In some deposits a small part of the gold
gold and silver in places. Blanchard (1933) mentioned organic appears to be in an adsorbed form, since it can be removed by
(probably humic) substances with relatively large amounts of weak cyanide and aqua regia solutions. The remainder,
manganese near seepages in New Guinea that carry up to generally the greater part, is tightly bound in the brown humic
27 920 pprn Au and 15 660 pprn Ag (Table 22). Decaying complexes. Ong and Swanson (1969) consider that gold is
wood tends to concentrate gold from solution. There are present mainly as a colloid stabilized by a protective layer of
numerous references in the older literature to the occurrence organic molecules around the gold in an organic environment
of relatively high amounts of gold in pit props and mine (see also the section on natural waters in this chapter).
timbers. Babitka (1943) also refers to the facility with which Shabynin (1970) observed experimentally that gold is ab-
decaying wood concentrates gold from solution. Palmer (1935) sorbed by peat in about the same amounts as by quartz. He
found marked enrichments of gold and silver in petrified concluded that organic gold compounds are formed, part of
(silicified and carbonized) logs in the Aspen district of which remain in the peat and part of which are soluble and
Nevada. Samples taken of one log contained 18.26 oz Au/ton render the gold mobile.
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THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

Gold in coal less than 0.1 pprn Au. Some western coals, however, were
Gold is a frequent microconstituent in a number of coal found to contain small amounts of gold, particularly in coal
seams, but is generally present in amounts less than 0.05 pprn from Kemrnerer, Wyoming and Wales, Utah. No values are
in the ash (Table 25). Certain coal seams, however, appear to given for these coals since the analyses were nonreproducible,
be greatly enriched in gold and silver. Lock (1882) and suggesting that the gold may be particulate. In U.S. Geol.
Maclaren (1908) mention the presence of gold in the pyrite of Survey, Circular 622, p. 10 (1969) it is further stated by J.D.
coal, in coaly matter or in sandstones and conglomerates of Vine that 100 samples of coal ash from U.S. Appalachian and
coal measures in Borneo; Gippsland, Victoria; Tallawang, interior coal fields all showed less than 0.05 pprn Au.
New South Wales; New Zealand; Tasmania; Deadwood, In Canada, Tyrrell(1915) mentions the presence of traces
South Dakota; and the Witwatersrand. The last is probably of gold in the coal of the Cretaceous Edmonton Series on the
not coal but thucholite which carries abundant gold in the North Saskatchewan River.
Rand (see the section on the Witwatersrand in Chapter 111). At the Tyozin Mine in Japan Tertiary coal beds inter-
Rose and Newman (1937) mention the presence of a rich calated with sandstones are exceptionally rich in gold (Wata-
deposit of gold in lignite in Japan but give no details. There is nabe, in Newhouse 1942). Similarly in the Coromandel Penin-
also a reference to gold in coal in the Batrina Mine in sula, New Zealand, thin coal seams are rich in gold where the
Verespatak, Transylvania in the old literature but again no auriferous Tertiary veins cross them. In these cases, the gold is
details. In a summary on gold in coal Lincoln (1911b) and apparently hydrothermal in origin.
Gibson and Selvig (1944) mention the presence of the element The gold content of the Carboniferous coals of the
in a number of Cretaceous coals in the western United States. Maritime Provinces of Canada is relatively low. The codified
The ashes of some of these contain up to 0.5 oz Adton. plant fragments in the Carboniferous sandstones are greatly
Details are given in the papers by Chance (1900), Jenny enriched in silver in places, but as a general rule the gold
(1903), Parsons (1907) and Stone (1912). Jones (1969) men- content rarely exceeds 0.08 pprn Au, despite the presence of
tions, however, that more recent analyses have not confirmed abundant pyrite, chalcocite and other sulphides.
these high figures. Thus, it is reported in U.S. Geol. Survey, There seem to be no detailed investigations on the gold
Circular 560, p. 17 (1968) that some 400 samples of coal and content of the different ranks of coal or of the different
associated rocks from Colorado, Wyoming, Utah and Idaho components, viz. fusain, vitrain, clarain and durain. Analyses
contain t0.020 pprn Au. Samples from the Cambria coal field for gold of specialized types of coal such as torbanite, camel,
near Newcastle, Wyoming reported in the early literature to boghead, jet and natural coke are lacking as are also those for
contain up to 0.5 oz Au/ton (17 ppm) were found to contain the various resinous substances such as amber associated with

Table 25. Gold content of coal

Refer-
Locality Remarks Au (range) Au/Ag ratio ence

Germany and England In ash -0.1

U.S.A.; Wyoming and South Ashes of Cambria coal -
Dakota Sandstone roof of Cambria coal
bed (pyritiferous) 0.1 -
Coke made from Cambria coal 4.2 (av.) 14.7 (av.)
Western U.S.A. Coal t0.020 -
Eastern U.S.A. In ash c0.05
Yugoslavia; Timok Basin In ash of lignite, bituminous and
semianthracite coals
Canada; Gaspereau River area, In ash; Pennsylvanian coal
Cape Breton Island, N.S.
Canada; Harbour seam, In cod, Pennsylvanian coal
Sydney, N.S.
danada; Stonehaven, N.B. In the ash; Pennsylvanian coal
Canada; Shubenacadie, N.S. In the coal; pyritized Cretaceous
lignite
Canada; Walton, N.S. In the coal; pyritized coal fragments
near faults in Mississippian sandstones
Canada; Walton, N.S. Pyrite and other sulphides separated
from pyritized coal fragments near
faults in Mississippian sandstone
Canada; Port Hood,N.S. W t e : Pennsylvanian coal
Canada; Dorchester Mine near coal fragments containing chalcocite
Sackville. N.B. in Pemsvlvanian sandstones
Canada, Shippegan Island, Coal fragments containing chalcocite
N.S. in Pennsylvanian sandstones
References: 1 .'Goldschmidt and Peters (1933).
2. Stone (1912).
3. US. Geological Survey Circular 560 (1968).
4. U.S. Geological Survey Circular 622 (19696).
5. Popovic (1 954).
6. Boyle (unpublished).
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CHEMISTRY, MINERALOGY AND GEOCHEMISTRY OF GOLD

coal or derived from it. These substances would seem to coal plants, and these in turn contributed the elements to the
provide an interesting field of investigation. humic substances that are the mother of coal: we have seen in
The occurrence of gold in coal.seams is generally erratic. the section on the biogeochemistry of the element that gold is
Judging from the writer's experience with silver (Boyle, 19683) a microconstituent of numerous plants, and hence it seems
and the limited analyses for gold in coal, the distribution of logical to conclude that some of the gold in coals came
gold in the seams can be summarized as follows: directly from the accumulated plant material.
1. Higher contents of gold (and silver) are generally 2. Precipitation of gold from surface waters flowing into
recorded from coal seams low in ash and rich in other trace or through the ancient coal swamps: humus in bogs and
elements such as copper, lead and zinc. swamps tends to adsorb and absorb the available gold from
2. Higher contents of gold (and silver) often accompany surface waters and thus becomes relatively enriched in the
parts of the coal seams or their overlying or underlying rocks metal. Some gold may also be precipitated by bacteria. During
that are enriched in sulphides particularly pyrite. Splits humification and codification processes this gold is incor-
containing abundant pyrite are sometimes greatly enriched in porated in the coal.
silver and gold as well as in various other chalcophile 3. Precipitation of gold from circulating groundwaters
elements. that course through the coal seams during and after coalifica-
3. A parallel enrichment of the following elements has tion processes: in this case the source of the gold may be the
been noted in some coal seams in Nova Scotia: gold, silver, coal itself, and the element is simply redistributed within the
copper, zinc, lead, cobalt, nickel, tin, molybdenum, arsenic, seam. More generally, however, much of the gold probably
antimony and barium. This relationship is marked in coalified comes from the enclosing sedimentary rocks. Some investiga-
fragments in the Walton area in Nova Scotia. tors maintain, however, that the gold is of hydrothermal
4. Higher gold and silver contents tend to occur in the origin, especially where the element is precipitated in zones
coal near the top and the bottom of individual seams. There containing coal fragments in sandstones.
are also a number of references in the literature to higher In coal seams and zones of coalified fragments gold
contents of silver, gold and other trace elements in the rocks circulating in aqueous systems is precipitated by adsorption
immediately overlying the seams. processes, probably by chelation and other organometallic
5. In some coal seams, and in sandstones containing coal binding processes, and by reduction of the complex gold ions
fragments, higher gold and silver contents tend to occur in the to the metal. Gebler and Stramkovskaya (1957) experimented
coal or in coalified fragments near faults, fractures or crushed with the adsorption properties of lignite for Cu, Ag and Au.
zones. For copper and silver they found a 4.31 and 5.2 per cent
The mode of occurrence of gold in coal and coalified copper and silver ion absorption by weight of lignite. For gold
fragments has not been extensively investigated. Some general they found no absorption but a strong reduction of the gold in
observations from the literature and the writer's research solution to the metal.
follow: The enrichment of gold in most coal seams and in
1. In some coal seams the gold is present as macroscopic coalified fragments in sandstones seems to be best explained
and microscopic forms. Much of this gold is commonly of by the circulating water hypothesis.
hydrothermal origin. Gold in organic shales, petroleum and other natural
2. Some gold is probably associated with the coaly hydrocarbons
substance of coal and may be bound as an organometallic Shales and other rocks containing organic matter, bitumen,
complex. BouSka et al. (1963) concluded that gold is bound kerogen and their degradation products tend to be slightly
principally to the organic part of the coal. enriched in gold compared with normal shales. The distribu-
3. A very small amount of the gold in coal may be tion of gold in these rocks is, however, commonly erratic.
adsorbed to the coaly substances. Commercial recovery of gold and silver from oil shales and
4. Much gold (nature unknown) is present in or associat- tarry residues is suggested in a patent by Petty (1968). For
ed with pyrite (Tables 11 and 25), and some gold is generally further details see the section on gold in sedimentary rocks.
observed in the small amounts of galena, chalcopyrite, arseno- There are relatively few data on the gold content of
pyrite, bornite, sphalerite and marcasite that are found in petroleum. Colombo et al. (1964) and Shah et al. (1970)
some coal seams. Popovic (1954) noted that the noble metal determined the gold content by neutron irradiation methods
content of the coals he studied varied with the sulphur in oil and asphalt samples from a number of fields in Italy,
content, especially the chemically bound sulphur - the higher U.S.A. and Libya. Their values range from t 0 . 1 to 3.012 ppb
the bound sulphur content the higher the noble metal content. in the oil (Table 26). In the asphalt the values ranged from 0.1
5. The gold in coalified fragments in most sandstones and to 1.0 ppb. Al-Shahristani and Al-Atyia (1973) report the
shales is either in or associated with pyrite, chalcocite, bornite presence of gold in some Iraqi crude oils but give no
and galena. Its nature is unknown. quantitative data.
6. In the weathered parts of coal seams gold (and silver) Hitchon et at'. (in Yen, 1975) report the presence of gold
may occur in jarosites and iron oxides; also in the native form. in four samples from a total of 88 crude oils from the Alberta
fields of Canada. The average concentration of gold in these
Gold may be concentrated in coal by one or all of the samples was 0.438 ppb; the maximum was 1.32 ppb.
following processes: The mode of occurrence of gold in petroleum is un-
1. Goldschmidt (1933a, 1935) originally suggested that known. It seems probable, however, that the'element is
gold and other trace elements were first concentrated by the combined as some type of organo-gold complex or as a
 Contents

THE GEOCHEMISTRY OF GOLD AND ITS DEPOSITS

chelated complex, perhaps a porphyrin, since the element is The gold in petroleum may be derived from the following
capable of forming porphyrins easily (Fleischer and Laszlo, sources.
1969). Shah et al. (1970) also analyzed the 10 crude samples
shown in Table 26 for Sc, Ni, Fe, Co, Zn, Se, Sb, Cr, As, Eu, 1. From the original plants and animals whose remains
Hg and U. A study of the correlation coefficients between gave rise to the petroleum: in the present section on biogeo-
these elements and gold indicates a significant correlation chemistry we have reported that many marine plants and
between Au and Sb and also between Au and Sc, Fe, Co and animals concentrate gold, and it seems logical to suppose that
Cr. some gold in petroleum came from this source.
Table 26. Gold content of crude oil and asphalt 2. By adsorption and absorption processes from sedimen-
Sample number tary rocks: petroleum migrating through sedimentary rocks on
and type Locality Gold content its way to reservoirs probably adsorbs and absorbs some gold
from these rocks.
Data from Colombo et al. (1964)
Crude oil Alanno, Italy 3. By contact with connate and other waters: these waters
Crude oil Chieuti, Italy probably carry small amounts of gold, which may be absorbed
Crude oil Cercemaggiore, Italy by petroleum when the two solutions come into contact.
Crude oil Avanella. Italv
Asphalt Gela,ltaly '
Asphalt Noto, Italy There are relatively few data on the gold content of the
Asphalt Vittoria, Italy natural bitumens and asphalts and the various solid hydrocar-
Asphalt Ragusa, Italy bons such as gilsonite, ozokerite, graharnite, anthraxolite,
Data from Shah et al. (1970) thucholite, etc. Thucholite is commonly greatly enriched in
Crude oil, 010 California, U.S.A. gold in the Witwatersrand quartz-pebble conglomerates of
Crude oil, 01 1 California, U.S.A. South Africa (Liebenberg, 1955) (see also Chapter 111). The
Crude oil, 012 California, U.S.A. thucholite in the skarn-type gold deposits of the Richardson
Crude oil, 013 California, U.S.A. Mine near Madoc, Ontario is also phenomenally enriched in
Crude oil, 014 California, U.S.A. gold. Other solid hydrocarbons and bituminous materials
Crude oil, 015 Libya
Crude oil. 016 Libva analyzed by the writer vary widely in their gold content as
Crude oil; 017 ~ibia shown in Table 27. With respect to the possible migration of
Crude oil, 018 Louisiana, U.S.A. golb as a complex hydrocarbon species see the section on the
Crude oil, 019 Wyoming, U.S.A. origin of the Witwatersrand in Chapter 111.

Table 27. Gold content of bituminous materials and solid hydrocarbons

Au/Ag
Description Location Au Ag ratio Remarks
@P@
Thucholite* Richardson Mine, >1000 >2 -500* In the solid hydrocarbon
Eldorado, Ont.
Thucholite Witwatersrand >1000 >10 12 In the solid hydrocarbon (see
also the discussion on the Rand
in Chapter 111)
Albertite Albert County, N.B. t0.005 t0.3 -0.01 In the ash of the solid
hydrocarbon
Vanadium-bearing Quadra Island, B.C. 0.25 47 0.005 In the solid hydrocarbon and
hydrocarbon-shale shale
Antraxolite Sudbury, Ont. 0.03 2.5 0.012 In the ash of the solid
hydrocarbon
*By electron probe the ratio Au/Ag of the visible native gold is 99.8/0.2. See the papers by Boyle and Steacy (1973), Steacy era/. (1973) and Steacy et a/. (1974a.b).

Gold in the atmosphere organic compound arising from microbiological activity. The
source of the particulates of which gold is either an integral
Relatively little data are available on the gold content of the constituent or present in an adsorbed form is probably
atmosphere. The element is mentioned as being present in multiple and includes: terrestrial aerosols raised from the
rainwater in the old literature, but no quantitative data are surface of the land and ocean by winds; volcanic aerosols;
given. Peirson et al. (1973) have measured the gold content of industrial pollutant aerosols; and extraterrestrial particles
rainwater and air by neutron activation at various sites in the (meteoritic dust) from sources unknown. There are no data on
United Kingdom. They give values of 0.01 pg/L for rainwater the contribution, which each of these makes to the gold
and an average of less than 0.003 ng/kg for air. content of the atmosphere.
Nearly all of the gold in the atmosphere is present in Gold is a constituent of certain terrestrial gases and
particulates; some may be present as volatile methylgold as aerosols, especially in volcanic areas. These are discussed in
Wood (1974) has suggested, or as some other volatile gold- the section on natural waters.