PROCESOS HIDROTERMALES Y
GEOQUÍMICA DE DEPÓSITOS MINERALES
(5. Asociaciones mineralógicas y su interpretación
geoquímica)
Orlando Bazán
[email protected]
Definiciones
• Asociación
• Grupo de minerales que ocurren juntos pero que no están necesariamente en
contacto ni necesariamente depositados al mismo tiempo, y no implica
condiciones de equilibrio. Van separados por comas. (Bendezú y Fontboté 2009)
• Ensamble
• Grupo de minerales que se encuentran en contacto directo y no muestran
evidencia de reacción entre ellos, implica un equilibrio químico. Van separados
por el signo + o –
(Bendezú y Fontboté 2009, Einaudi et al., 2003)
• Paragénesis
• Asociación mineral característica que connota la formación contemporánea y/o
relación temporal de los minerales. No necesariamente implica condiciones de
equilibrio.
(Hemley y Hunt 1992)
• Zonación
• Relación espacial de una asociación de minerales y/o de ensambles
mineralógicos, puede connotar condiciones de equilibrio químico o superposición
de múltiples eventos a través del tiempo.
(Einaudi et al., 2003)
Definitions
Porphyry indicator minerals (PIM):
• Minerals that can be used to potentially help to identify the presence of,
or potential for, porphyry and other styles of mineralisation (fingerprints)
Porphyry vectoring and fertility tools (PVFT):
• Minerals that can be used to predict the likely direction and distance to
mineralized centres, and the potential metal endowment of a district (footprints)
Cerro Casale district, Chile Hollings et al
Gemmell. J.B.
Telescoping
Cooke et al (2014)
Gemmell. J.B.
Kouzmanov, 2015
Gemmell. J.B.
Cooke et al. (2014)
az
hm ten
ten
→ hay asociaciones mineralógicas - a pesar de que son
“sencillas” - que nos indican mucho sobre su génesis y
las fuentes de componentes…por ejemplo:
chr
mal
Longfellow Limestone, Morenci District, Arizona
Chávez,2014
¿Qué importancia tienen las asociaciones
mineralógicas y su interpretación de la
geoquímica de un sistema hidrotermal?
Ejemplo: Sistemas de Fe-Cu
Calcopirita – Pirita - Calcita
Common Phase Diagrams
ƒS2 – ƒO2
Native Sulfur
cv
cc
Orp (Zn.9999Fe.0001)S Fmn
Rej Ttr cc
En
Tnt bn
py + bn
Log ƒS2
ccp
(Zn.99Fe.01)S Pyrite
Rej
As (n) (Zn.9Fe.1)S Py + As
Aspy
Pyrrhotite Hematite
Magnetite
log ƒO2
Geoquímica de Sistemas Cu-Fe-S
¿Representa equilibrio la asociación:
Pirita – Magnetita – Calcopirita ?
Pirita – Magnetita - Pirrotina – Calcopirita ?
Mina Atacama Kozán,
Distrito Punta del Cobre, Chile Chávez,2014
Cal
Cpy
Py
Mgt
Cuál es la paragénesis?
10
Chalcocite
8
Magnetite
6
Log a(Fe2+) / a(H+) 2
Chalcopyrite
2
Pyrite Bornite
0
-2
-4
300°C
Covellite
Log a(H2S) = -3
-6
-10 -8 -6 -4 -2 0
Log a(Cu+) / a(H+)
Modified from Knight, 1977 2 Fe2+ + FeS2 + 4 H2O = Fe3O4 + 4 H+ + 2 H2S
¿Se puede emplear reacciones
entre sulfuros a determinar el nivel
geoquímico de un sistema
hidrotermal?
enargita…¿qué significa con
respecto a tennantita?
El Guanaco, Chile Chávez,2014
Maydagán, L.
10 CuFeS2 + 2 H2S + 4 Cu+
Chalcopyrite Bornite Cu5FeS4 + 4 H+
8
6
Pyrrhotite
Log a(Fe2+) / a(H+) 2
2 Pyrite Tennantite
-2
-4 100°C
Chalcocite Log a(H2S) = -3
Enargite Log a(H+)*a(As(OH)4-) = -12
-6
-14 -12 -10 -8 -6 -4 -2
Log a(Cu+) / a(H+)
Modified from Knight, 1977
300 Magnetite
Bornite
Pyrite
Temperature (°C)
200 Pyrite
Chalco-
pyrite
Tennantite
Tennantite
100
Chalcocite Chalcocite
A B
0
300
Covellite
Pyrite
Pyrite Bornite
Temperature (°C)
200
Tennantite Tennantite
100
Chalcocite Chalcocite
C D
0
-14 -10 -6 -2 -14 -10 -6 -2
Log a(Cu+) / a(H+) Log a(Cu+) / a(H+)
Modified from Knight, 1977
Nótese la paragénesis del ensamblaje
mineral.
(Porque es esto importante?)
“py”
Py > En
Chávez,2014
Paragenesis: “py” → Oropimente → S…
Chávez,2014
Diagrama general de características Eh-pH de As
vetillas de qtz + K-spar
rejalgar
Vetillas “BQ”
(“cuarzo negro”)
Chávez,2014
Heinrich &
Candela, 2014
Heinrich &
Candela, 2014
Mineralogical Zoning
cc
cpy
Butte Zoning
Hemley & Hunt (1992)
Modelo de zonación de metales de sobre un pórfido Cuprífero (Jerome, 1927)
Morochocha
Catchpole et al (2011)
Kouzmanov & Pokrovski (2012)
Jianping et.al. 2019
Halley et al. (2015)
Halley et al. (2015)
Dilles (2012)
Principal pit
Pocobamba Formation
Cu±(Ag) in enargite-pyrite with alunite
200 m
Cu±(Ag-Bi) in chalcopyrite ± (tennantite,
bornite, Bi sulfosalts) with dickite ± alunite
Zn-Pb-Ag in sphalerite-galena-kaolinite
-dickite-alunite and sphalerite-galena-
hematite-carbonates in the external parts
Mercedes-
Choccayoc pit
Bendezú, R.
"Stages" and metal zoning:
A "simple" case
py A possible interpretation would be to postulate
cp
- stage I fluid rich in Fe and Cu and poor in Zn and Pb
sl
- stage II fluid rich in Zn and Pb
gn
time But, in fact, in most cases, this interpretation will
be wrong...
let us consider other possibilities
© L. Fontboté (2003)
Corbett & Leach-1997-
Corbett , 2019
Sistemas Hidrotermales: Carácterísticas Claves (Procesos)
Baja Sulfidación (LS) Alta Sulfidación (HS)
Adularia-Sericita) (Ácido-Sulfato)
Forma • Predomina relleno y stockwork • Diseminaciones predominan;
• Menor diseminaciones y mineral reemplazo común
de reemplazo • Stockworks son menores, vetas
variables
Mineral • py, electrum - Auº, sl, ga, • py, en, cv, cp-tn, Auº, Te, Hg,
sulfosales; aspy; cp (no?) Sb, electrum
Sleeper, Nevada
MINERALES
MENA GAS / FLUIDO EH
En / Luz HCl-
OXIDADO
Cv
SO2-
Py
Tenn / Tetra
SEMIOXIDADO
Cpy
Sph (- - Fe)
Gn
Py
Apy CO2
REDUCIDO
Po
Sph (+ + Fe) H2S
Gn
Py
1 2 3 4 5 6 7 pH
ÁCIDO INTERMEDIO NEUTRO
Qz Crustif. / Colof.
MINERALES
Qz Vuggy, Mss Qz Crustif. / Comb
GANGA
Carbonatos (Mn) Calcedonia
Baritina Silicatos (Mn) Celestina
Baritina Fluorita / Baritina
ALTERACIÓN
Qz-Alunita Sericita – Adularia Illita / Sericita
Qz-Pyrf/Dik Qz Crustif. Adularia
© O. Bazán (2017) Diaspora Qz Crustif. Colof.
<= not always!
White (1995)
High Sulfidation Epithermal Au
El Indio, Chile FX-230-5-2
enargite Cu3AsS4
High Sulfidation Cu-Au
Smelter, Colquijirca District, Peru, FPE-129, 1
© L. Fontboté (2003)
Coarse enargite-alunite
assemblage in rhyolite tuff
La Coipa District, Chile
Chávez,2014
White (1995)
Veta epitermal de Au-Ag formada Mineral epitermal de Au-Ag
por relleno de fisura (falla) con bandeado de adularia-sericita con
adularia-sericita bandeadas y cuarzo en bandas bien definidas
brechas marginales con fragmentos y bandas oscuras de cuarzo con
flotantes (soportados por matriz), con sulfuros diseminados y Au
Hishikari, Japón. Golden Cross, Nueva Zelanda.
Mineral epitermal de Au-Ag de
tipo adularia-sericita mostrando Veta bandeada con calcedonia
buen desarrollo de cuarzo bandas de cuarzo con sulfuros
formando pseudomorfos de diseminados con oro y adularia
calcita en placas, rosada, Cracow, Australia
Vera Nancy, Australia.
Sinter de San Quentin
McLaughlin, USA
Sinter silíceo con cinabrio
500 °C, 1 kbar
Effect of T
decrease in the fS2-
fS2 diagram
In general: fS2 and FO2
decrease, thre triple points
move, but the topologic
relationships remain the
same
Example: transformation mt-
> hm (martitization)
Hemley et al. (1992)
unta del Cobre IOCG
500 °C, 1 kbar
Effect of T increase
in the fS2-fS2
diagram
In general: fS2 and FO2
increase, the triple points
move, but the topologic
relationships remain the
same
Example: transformation hm-
> mt (mushketovite) in
several IOCG deposits
Hemley et al. (1992)
Punta del Cobre IOCG
Marschik & Fontboté (2001)
Early, felty biotite with vein-hosted
chalcopyrite and late, lavender anhydrite
Chávez,2014
Effects of magmatic sulfide saturation on
trapping or providing metals in magmatic–
hydrothermal systems. (A) Aqueous fluid
saturation occurs before sulfide saturation in
the magma. Metal content in residual melt
increases because metals are not significantly
sequestered by the crystallizing silicate ± oxide
minerals (a1 → a3) and metals are optimally
transferred to the magmatic fluid when
saturation occurs. (B) Sulfide saturation occurs
before aqueous fluid saturation in the magma.
Metal concentrations initially increase until
sulfide saturation occurs (b1→b2) then
sharply decrease (b3). Transfer of metals to
fluid is not optimal because significant
proportions of metals have been sequestered
by sulfides. (b4) Magmatic sulfides may be
destabilized by aqueous fluids exsolved from
the same magma in which sulfide saturation
previously occurred. (b5) Magmatic sulfides
may be destabilized by aqueous fluids
exsolved from an underplated mafic magma.
(b6) A sulfide-undersaturated mafic magma
may recycle the sulfides and release the
metals contained therein once the mafic
magma becomes saturated in an aqueous
fluid.
Fontboté, 2017
Sulfide Minerals in Hydrothermal Deposits
Characteristic ore textures in some of the main types of hydrothermal sulfide deposits.
(A) Sulfides in stockwork quartz veins or disseminated in the wallrock. From the Atlantida porphyry Cu–Au deposit (Chile).
(B) Banded sulfides as open-space filling with gangue minerals, indicating episodic precipitation. From the Laki epithermal
polymetallic Pb–Zn vein deposit (Bulgaria).
(C) Sulfides associated with quartz, carbonates, and retrograde calc-silicate skarn minerals that replace prograde skarn
pyroxene. From the Madan distal Pb–Zn skarn deposit (Bulgaria).
Abbreviations: bar (barite); bn (bornite); carb (carbonates); cp (chalcopyrite); gn (galena); px (pyroxene); py (pyrite); sp
(sphalerite); qtz (quartz).
Fontboté, 2017
Sulfide Minerals in Hydrothermal Deposits
Characteristic ore textures in some of the main types of hydrothermal sulfide deposits.
(D) Sulfide minerals in the form of fine grained layers and showing syn-sedimentary features. From the Navan sediment–
hosted Zn–Pb deposit (Ireland).
(E) Fine grained, layered sulfides commonly associated with barite and anhydrite. The base metal sulfides usually postdate
the Fe-sulfides. From the Rammelsberg sediment-hosted massive sulfide deposit (Germany).
(F) Pyrite and chalcopyrite replacing the host rocks (preserving their original textures) or locally occurring as open-space
filling in late veins. From the Punta del Cobre iron oxide–copper–gold (IOCG) deposit (Chile).
Abbreviations: bar (barite); bn (bornite); carb (carbonates); cp (chalcopyrite); gn (galena); px (pyroxene); py (pyrite); sp
(sphalerite); qtz (quartz).
Fontboté, 2017
USING SULFIDE MINERALS TO RECONSTRUCT PHYSICO-
CHEMICAL PARAMETERS OF ORE FORMATION
(A) Log fS2 versus temperature diagram, illustrating various sulfidation states (in green) of the hydrothermal fluids,
based on stable sulfide mineral assemblages (from Einaudi et al. 2003). FeS (mol%) content of sphalerite is also plotted
(in red; from Barton and Toulmin 1964); sphalerite is a common mineral in many hydrothermal ore types and its FeS
content can indicate the temperature or sulfur fugacity. (B) Log fS2 versus temperature estimated for various
hydrothermal ore deposits. Colours are visualization aids only. Abbreviations: asp (arsenopyrite), bn (bornite), cp
(chalcopyrite), cv (covellite), dg (digenite), lo (loellingite), po (pyrrhotite), py (pyrite).
Fontboté, 2017
1285 g/Tn Ag
