THE AMERICAN MINERALOGIST, VOL.

50, OCTOBER, 1965

AN EARLY POTASSIC TYPE OF WALL-ROCK ALTERATION

AT BUTTE, MONTANA
Cnnnr.nsNlnvnn, Departmentof Geologyand Geophysics,
University
of California,Berkeley.
AssrnA.cr
Deep mine ievels at Butte, Montana, have recently erposed narrolv but ll'ell-defined
envelopes of lvall-rock alteration adjacent to molybdenite-bearing quartz veinlets. Within
the envelopes the feldspars and micas are altered to a fine-grained assemblage of muscovite,
biotite, alkali-feldspar (0176), and quartz, together rvith anhydrite, carbonate, magnetite,
hematite, pyrite, and chalcopyrite. The quartz-molybdenite veinlet itself may also contain
small amounts oI any of the foregoing minerals except biotite. At their outer edges the al-
teration envelopes grade into fresh quartz monzonite. There is no marginal argillic zone.
These veinlets and alteration envelopes are cut and ofiset by white quartz veinlets which
contain no molybdenite and have no alteration envelopes around them. And both types of
veinlets are cut and offset by still later fractures of all sizes, which control the concentric
sericitic and clay mineral alteration envelopes of the "main-stage" p1'rite-rich copper and
zinc veins.

INrnooucrroN
ProfessorKerr is one of the foremost students of hydrothermal wall-
rock alteration and has long shown friendly and helpful interest in
Anaconda'sstudy of the ore depositat Butte, Montana. So it is a pleasure
to contribute in his honor this brief description of a type of wall-rock
alteration which has been exposedby deep mine workings at Butte in
recentyears.

DrstnrnuuoN AND Srnucrun,q.l RBre,rroNs

The deepestmine workings in the Butte District are near the geo-
graphicalcenter of the District, west of the "CentralZone" of pervasive
sericitization and pyrite-chalcociteores (Sales,1913). Here mining has
penetrated to depths of about 5000 feet on the great chalcopyrite ore-
bodies of a number of large "Anaconda" and "Blue" veins. These large
veins are encasedin normal "main-stage" sericitic and argillic alteration
envelopessimilar to thosedescribedin an earlierpaper (Salesand Meyer,
1948).'Thelarge veins are far enough apart, however, that envelopesof
argillic alteration from adjacent veins do not overlap, and unargillizej
Butte quartz-monzoniteis preservedbetween them. In this otherwise
fresh quartz monzonite, dark gray alteration envelopes have recently
been observed along quartz-molybdenite veinlets. Most of the veinlets
are lessthan 1 inch thick, discontinuous along strike, and variable in dip.
The envelopesrange in thickness up to about 8 inches, with the veinlet
at the center. There is no megascopicallyvisible zoning in the alteration
envelopesbetween veinlet and fresh rock except a slight darkening of the
t717
l 71 8 CHARLDS MEYER

color at the outer fringe of the envelopeowing to an increasein propor-

tion of biotite relative to muscovite.
The veinlets and their alteration envelopesare cut and offset by similar
veinlets of white qrartz which contain no molybdenite and show no
alteration against fresh quartz monzonite. Such white qtartz veinlets are
common elsewherein the district. Like the quartz-molybdeniteveinlets,
they fill simple cracks,show Iittle or no evidencefor replacementof the
wall-rock, and frequently appear to fill in betweenjagged dilated walls.
They are also discontinuous in strike and variable in dip, and they rarely
exceedabout 2 inchesin thickness.
Both types ol qlartz veinlets are cut and offset by any vein or veinlet
qhich carries"main-stage" copper,zinc or manganesemineralizationand
is borderedby concentricsericiticand argillic aiteration envelopes.Thus
there is indisputable structural evidence that the quartz-molybdenite
veinlets and their dark-coloredalteration envelopeswere formed in the
deep levels of the district before the beginning of the faults which sub-
sequently guided the main h1'drothermai inundation.

MrNBnar AssBMsrecns
The early dark micaceous(abbreviatedEDM) alteration is character-
ized by potassium fixation in biotite, muscovite and aikali-felospar.
Chlorite, anhydrite, calcium-bearingsidero-magnesite, magnetite,hema-
tite, pyrite and chalcopyrite are also quantitatively important, and
fluorite and molybdeniteare presentlocally in small grains.

Biotite. Fine-grained (co. 0.01-0.10 mm.) light-brown and light-green

biotites are conspicuousin thin section and give the dark olive-gra1'color
to the hand specimen.They replace hornblende,darker brown Ti-rich
biotite, oligoclase-andesine and, near the veinlets,even K-feldspar in the
original qtartz monzonite. They are intimately mixed with colorless
mica, particularly where they replacethe feldspars.
Both the brown and the greenbiotites are low in TiO2, but they have
only slightly higher Mg/Fe ratios than the biotite in the original rock.
Both are fully trioctahedraland show no 14 or 7 A spacings.Possiblythe
greencolor is consequentfrom an increaseIn ps2+/psa+ratio, but it is not
clear at presenthow the chargedifferenceis compensated.Infrequently,
color transition from green to brown can be seen in a single grain of
alteration biotite, but usually domains of green a millimeter or more in
diameter are dispersedin brown. If both plagioclaseand K-feldspar are
biotitized, there is more green in the K-feldspar and more brown in the
plagioclase.The green biotite also tends to concentrateat the conracrs
between an altering biotite plate and adjoining feldspars,the center of
the biotite plate altering to a mosaicof tan Ti-free biotite.
 POTASSICWALL-ROCKALTERATION I7I9

Muscoaiteand,Alhali-Feldspar. Muscovite (mostly 2M polytype) is the

dominant phase replacing the feldspars. Plagioclaseis attacked farther
from the veinlet than K-feldspar, and the muscovite which replaces it
commonly shows little or no preferred orientation along the plagioclase
cleavage. Biotite, qvattz and untwinned alkali-feldspar (0176) are all
present with the muscovite.
Muscovite replacing the K-feldspar of the original rock shows a very
unusual textural relationship to associatedquartz and new alkali feld-
spar. The muscovite is separatedfrom the qtt'attz by uniform thin rims of
new untwinned alkali-feldspar which looklike reaction rims between the
muscovite and the qrartz. Either the muscovite and the feldspar grew
together at equilibrium, with the feldspar tending to be stabilized by
higher activity of silica adjacent to the quartz grain, or the reaction to
feldspar was accomplished after initial crystallization of a muscovite-
qtartz assemblage,probably because of an increase of temperature or
activity of potassium. Such rims of alkali-feldspar are found at Butte
only in the early dark micaceous alteration assemblage-never in the
alteration zonesof the main hydrothermal stage.There is no evidencefor
changein volume during the reaction.

Sulfates, carbonates,oxiiles anil sulfd'es. Anhydrite is a very important

wall-rock alteration product as well as vein constituent in the EDM en-
vironment. It is present in contact with all other mineral phasesof the
alteration assemblage.Locally it is abundant in replaced plagioclaseand
biotite(?) grains, poikilitically enclosing micas and other alteration
minerals. The EDM environment is the only place where anhydriteis
found in the Butte District. It is also interesting to note that where
EDM veinlets and alteration envelopesare exposedto later main-stage
hydrothermal mineralization and alteration at Butte, the anhydrite is
usually removed, Ieaving cavities and vugs. Anhydrite is apparently a
soluble phase during main-stage hydrothermal activity.
Carbonate is also present in the EDM envelopesand veinlets. Usually
it is present in volumes once occupied by hornblende or plagioclase,but
it may also be found as isolate grains in the replacement mosaic of any
other wall-rock constituent. As mentioned earlier, it is sidero-magnesite,
with a Ca/Mg*Fe ratio about 1to 4.
Magnetite is present in nearly all samples of the EDM alteration en-
velopes, and locally is an abundant constituent in the quartz veinlets
which are central to the envelopes.Usually there is a bit of oxidation to
hematite in grid patterns or along the margins of grains.
In addition to molybdenite, pyrite and chalcopyrite are the only
sulfidesfound in the EDM environment. Both are more abundant in the
alteration envelopesthan in the veinlets, and they seemto be clustered in
I72O CHARLESMEYER

places once occupied by the mafic minerals of the original qttartz-monzo-

nite. By significant contrast, in main-stagemineralization,virtually all
of the copper is in the veins and veinlets, and the only abundant sulfide
i n t h e u ' a l l - r o c k si s p _ r i t e .

Chemi,calgoins and losses.Between the well-definedenvelopesof ear11-

dark micaceousalteration, the Butte qtart-z-monzoniteshows less horn-
blende and andesine,more K-feldspar and biotite and sometimesalso
more quartz than is normal in other parts of the district. rt is alsostudded
with dispersedgrains and tiny veinlets of sulfide-chieflv p1,1i1sbut also
some chalcopyrite.The distribution patterns of these variations are not
yet sufficientlywell known to review svstematicall_v, but they necessitate
caution in evaluatingthe chemicalgainsand lossesin the EDM envelopes
with respectto the immediate rock around them. Is this rock itself an
alteration product b1-action of epigeneticsolutionsfrom a deepersource,
or are we nearing a "collecting zo\e" or t'sub-hoodcupola,' as postulated
by Reno Salesin his Jackling Lecture of 1954?
The EDM envelopeshave onlv a slightlv higher specificgravit)' (2.78)
than the surroundingrock (2.70) owing to the abundanceof biotite and
muscoviteand the small amount of disseminatedsulfide.Taking this into
account (assumingno volume change)the constancyof alumina at about
350 mg./cm3 prevailsin the EDM alteration just as it doesin the argiliic
and sericitic zonesof the subsequent"main-stage,'alteration. Magnesia
is alsoin near-balancein the EDM envelopeswith respectto surrounding
qtartz monzonite,but a small amount of silica and I to J of the CaO and
Na2O are lost. KzO shows a gain of more than 50/6, total Fe a gain of
a"bout l0/o, and, of course,HrO, S, COz and SO+are all substantially
higher in the altered envelopes.
In balance,there appearsto be slight base-extractionfrom the EDNI
envelopes,evidently by hydrolytic reactionsbetween the original wall-
rock mineralsand solutionswhich permeatedaiong the veinlets.But this
base-extractionis much more selectiveand far less profound than the
baseleaching which accompaniedmain-stage mineralization along the
later large veins of the district. The ,,main-stage',solutions removed
nearly all the iime and soda and f of the magnesiumfrom the wall rocks
in the alteration zonescloseto the veins, and added no potassium.Also
silica was heavily extracted from the argillic envelopeand onl1.slightll'
added to the sericitic envelope.Much sulfur was added to form pyrite
from all the iron in the sericitic envelope,but nearlv all the copper re-
mained in the veins. The only insolublesuifate in ,,main-stage,'minerali-
zationand alteration is barite, and this is in verv small amounts.carbon-
ate is present in main-stage alteration onlv in the outer argillic zorTe
 POTASSICWALL-ROCRALTI'RATION I72I

even adjacent to rhodochrositeveins, and here it is calcite rather than

sidero-magnesite.

Eaaluotion of mi'neral assemblages.The most significant mineralogical

differencebetweenEDM and "main-stage" aiteration at Butte is the fact
that the plagioclaseof the quartz-monzoniteis immediately convertedto
the potassicmineralsmuscovite (Kerr, 1951),biotite and K-rich feldspar,
plus quartz, rather than progressivelyleached to montmorillonite and
kaolinite. Excluding the biotite-sulfide equilibrium momentarily, three
parametersare most significantto equilibria among the feldspars,micas
and clays; activity ratios of K+/Na+/H+ (Hemley and Jones, 1964), ac-
tivity of silica, and temperature.At equivalentactivities of silica,higher
temperature andf or higher aK+faH+ would favor the EDM assembiage
over the argillic assemblage(Hemiey, 1959).The crystallizationof quartz
with the muscovite in EDM alteration suggeststhat the activit.v of
silica in that system was maintained in equilibrium with quartz, whereas
in the argillic alteration at Butte there is neither precipitation of quartz
nor dissolutionof quartz, even though silica is extensivelvremovedfrom
the argillic zone bv argillization of the plagioclase.In the argillic zone,
then, the solubility of silica may have soaredmetastabiy far above its
equilibrium value, with consequent tendency to preserve K-spar in
metastableassociationwith kaolinite (Fournier, 1964).
The partitioning of iron betweengreen and brown biotite (where it is
probably in two oxidation states), magnetite-hematite,carbonate,and
the various sulfides is difficult to treat except in a verv general way. As-
suming an aqueous s1'stem,the EDM assemblagecertainly suggests
lower sulfideion activity than doesthe pyrite-bornite-chalcocite-sericite
assemblageof Butte's Central Zone. The presenceof anhydrite in the
EDM alteration and its removal by "main-stage" solutionsis consistent
with this estimate. But before it is concluded that EDM and ,,main-
stage" solutionswere essentiallydifferent in bulk chemicalcomposition,
it must be rememberedthat the equilibria in question are unquestion-
abl1.temperature dependent.The complex biotite-rich assemblage, with
intermediate sulfide ion activity, is favored by higher temperature,
though this relationshipis difficult to quantifl'at present.
As we have seen,the grossalteration effect of both EDM and "main-
stage" solutionsis to leach basefrom the wall-rocks,substituting hydro-
gen ions hydrolytically. Of course,the fact that the amount of basein a
given incrementof solutionis rising doesnot necessarilymean that the pH
of that solution is also rising, since the pH will depend on the relative
ratesof generationof H+ by dissociationand the loss to the wall-rocksby
reaction. If the hydrogen ions are furnished continuously through in-
1722 CEARLES M]JYER

creaseddissociationin the solution owing to cooling,then the EDM and

"main-stage" solutionscould merely be at different stagesin their evolu-
tion during the cooling process.If this were true, a geologicmodel is re-
quired which perrnits the "cooler" effects to be superimposed,in later
structures, on thr: "hotter.tt A classical graduaillt retreating "source
zone" is an obvious suggestion,with hydrothermal fluids evolved by
crystallization differentiation over a long period of time-long enough
for the batholith to have cooled through at least 100' C. at the point of
reference. Of course, the foregoing model presumes a sufficiently high
pressureto maintrain a dense gas or liquid fluid'
Evidently geochemicalevolution of the granodiorite-copper svstem at
Butte missednone of the essentialstepsof the porphyries (seeMeyer and
Hemle-v, 1959), but the effects are spread out over a greater vertical
distance owing to the different structural history during crystallization
of the parent magma.
AcxNowTBIGMENTS

The writer is indebted to Mr. V. D. Perry, vice-presidentand chief

geologistof the Anaconda Company, for permissionto publish theseob-
servations,most of which are taken from a private report to the Com-
pany in 1959.Someof the data on mineral compositionswereobtained on
equipment provided by the University of California and the National
ScienceFoundation.
Rrnnnnxcns
Fournron,R. O (1964) manuscript.
Unpublished
equilibriain the systemK:O-AhOr-SiOrHzO.
Hr:nrr.rv,J. J. (1959)Somemineralogical
Am..f our.Sci.257,241-270.
--- AND W. R. JoNns (1964) Chemical aspects of hydrothermal alteration with em-
phasis on hydrogen metasomatism. Econ. Geo|.59,736-569'
Knnn, P. F (1951) Alteration features at Silver Bell, Arizona. Geotr.Soc. Am. Bul'|. 62,
451-480
Mevrn, C. evo J. J. I{EMLEY (1959) Hydrothermal alteration in some granodiorites.
NatI. Conf. Aay ,Winero)s,6th, Bukeley 7957,Proc.,89-100.
S.rr,s, R. H. (1914)Ore depositsat Butte, Montana.Am. Inst. Min. Met. Engrs.Trans.
46, 3-106.
-- (1954) Genetic relations betweengranites, prophyries and associatedcopper de-
posits.,4ru.Inst. Min. and.Met. Dngrs.Trans 199'499-505.
- ANDC. Movr:n (1948) Wall-rock alteration at Butte, Montana, Am. Inst. Min.
and.Met. Engrs. Trans.l78. 9-35.