Gold in solution

Gold complexes
• Typical Au valence: Au +

• Complexes in solution:
- (Au(CN)2)- - strongest
- (Au(S2O3)2)3-
- (Au(HS)2)-
- Au(OH)0
- (AuCl2)-
• If very oxidizing conditions (e.g., acidic &
saline groundwater): Au 3+

• Complexes in solution:
- (AuCl4)-

Hough, et al. (2009)

Gold complexes Gold complexes

•How to
•Total S=0.01 m precipitate 500 bar (50 MPa), 250°C
•fO buffered by
2 Au?
hem-mgt
•How is Au
carried?

•Total S and fO 2
buffered by py-
po-mgt
- more reducing
- total S <0.1m
•What is
different?
 Low-T (<350°C) Gold Epithermal Deposits
•-Primary reaction:
Ausolid + 2HS- + H + + 0.25O2 (Au(HS)2)- + 0.5H2O
• effect of pH?
• effect of [HS-]?
• effect of fO2?
•-Effect of boiling (vapor exsolution)? Oxidizing; fixed S
HS- + H+ H2S
• What is the valence of sulfur here?
• This is “low-sulfidation” (sulfur as S2-) Reducing; buffered S
•-Loss of S to wall rocks
Switch from (Au(HS)2)-
- to Au(HS)0
- to (Au(Cl)2)-
• Cooling?
• Fluid mixing?
• Other interaction with wall rocks? From Heinrich (2005)

Epithermal Deposits
epithermal •-Environment: •-Ore bodies:
Shallow hydrothermal veins, stockwork, breccias,
- subaerial (+ subaqueous) disseminations
volcanic arc •-Small but high-grade:
•- Conditions: <500 to ~2000 m long/
100 – 320°C (mainly 170 – wide; <500m thick
280°C) - Au:2–100 g/t; Ag:100-500 g/
- <1km below water table t
•-Metals: •-Importance:
Au, Ag (Hg, Cu, Pb, Zn) ~6 % of gold
- ~16 % of silver (Singer,
1995)
 Epithermal Deposits Epithermal Deposits

Au grades versus tonnage for Canadian and

foreign porphyry deposits. Diagonal lines
indicate tonnes of contained Au.

Hedenquist et al., 2000 Hedenquist et al., 2000 (Gold in 2000) & Sinclair, 2007 (Min. Dep.Can)

Magmatic-geothermal link Magmatic-geothermal link

Epithermal mineral deposits
Au (Ag, Hg, Cu, Pb, Zn)
Magmatic(volcanic)-hydrothermal
system

Geothermal system

Volcanic fumaroles, acidic condensates and acid

alteration produced by the injection of
magmatic fluids and rich in acid gases (SO2,
H2S, HCl, HF) into shallow meteroic
groundwaters, with dynamically variable ratios
of fumarolic steam/meteoric water.
Hedenquist et al., 2000 (Tongariro stratavolcano, NZ)
 Magmatic-geothermal link
Hot springs / geothermal systems, Taupo Volcanic Zone,
NZ
Champagne pool,
Wairakei, N.Z.
Geyser
Whakarewarewa, NZ

Silica sinter, Orakeikorako,

NZ

13

Types of epithermal deposits

• High-sulfidation (acid-sulfate) class:
- Oxidized; sulfur present as S0, S4+, or S6+
- Sulfide-rich
- Acidic
- Minerals:
• pyrite, bornite, covellite, enargite, luzonite.
• Low-sulfidation (adularia-sericite) class:
- Reduced; sulfur present as S2-
- Less sulfur
- Less acidic
- Minerals:
• arsenopyrite, pyrite, Fe-rich sphalerite
Hedenquist (2005)
 • Sulfidation state defined by redox (based on Cu-As-Fe-S mineral Types of epithermal deposits
equilibria)
• Sulfidation state NOT related to sulfur abundance!

Magmatic(volcanic)-hydrothermal
system
2+ S 2
Fe AsS 4 Geothermal system
Cu 3 S
ni te Cu S
o Zn

Fe 2 +A 2
Fe +S
Fe 2 +S sS
e z
rit ite-lu

2
HS

Fe
y ite

2
p
arg

Fe 2 2
le r

S
)S
en ellite spha

(Z +Cu

+
v
co w Fe LS

n,
Lo

gh opyr te te
alc ti ri
ar rite
ch rrho opy

e
rit
py
py n

Fe ite
ale
s e

sph
hi

from Einaudi et al. 2003 Hedenquist et al., 2000

Tectonics of epithermal deposits Tectonics of epithermal deposits

• Extensional (regional or very local)
• Low-sulfidation Au ± Ag deposits
- continental & island arcs
- Analogue to modern geothermal areas (e.g., Taupo
Volcanic Zone in NZ; Yellowstone, USA)
• High-sulfidation Au-Ag deposits
- Volcanic arc setting
Groves et al., 1998

- Some related directly to porphyry deposits

• Others likely

Epithermal = volcanic arcs associated with subduction zones, usually in places of

mild extension

Sillitoe and Hedenquist (2003)

Epithermals are younger - why? High-sulfidation epi. deposits
• Schematic cross-
section showing
position of High-
sulfidation system
above magmatic
center
•

Number of deposits
Deposits near vent
• Metals from magma
• Oxidized & mod.
briny (4-20 wt% NaCl
equiv.)
• Acidity due to
absorption of
magmatic vapor
(highly dissociated
SO2, HCl & HF) by
ground water
• Acid leaches rock
(forms vugs and
Age (Ma) alteration)
Kesler & Wilkinson, 2006

High-sulfidation epi. deposits High-sulfidation epi. deposits

•Ore deposition
due to: fluid
mixing
- magmatic
• acidic, metal-
rich, hot
(possibly
vapor), briny
- meteoric
• neutral, dilute
•Forms very acidic
fluid (pH 1-3)
• Magmatic • Condensing
gas fumaroles gases
• White produce acid
Island, New alteration
Zealand Photographs from R. Herrington
 Low-sulfidation epi. deposits Low-sulfidation epi. deposits
•Schematic cross- •Located on fringe of
section that shows the volcanic edifices
position of a Low- - And in areas without
sulfidation system coeval volcanism
•Hot springs - Most geothermal
- geothermal systems system driven by
intrusions (5-6 km
•Fluids have depth)
equilibrated with host
rocks •Near-neutral-pH
•Meteoric water source •Reduced
- possible mixing with •Low-salinity (0-10, but
usu. <2 wt% NaCl)
evolved magmatic
fluid •Fluid boiling is
probably responsible
for most ore deposition

Ore minerals in HS & LS epithermal Au-rich ores Gangue in HS & LS epithermal Au-rich ores
! ! ! ! low-sulfidation high-sulfidation
7S06!T3&#0!(:/!R0/0:9-&,#B!OUUV
! ! ! ! "#$%&'())$!)*+!,-)./0!1*)2! "#$%&'())$!3&43!,-)./0!1*)2 ! ! ! ! low-sulfidation high-sulfidation
! ! ! 50-#6()!! ! ! 7'&/ ! ! ! ! 50-#6()! ! ! 7'&/
! ! ! 8609-0:'$!"(;-:/(:'02!! 8609-0:'$!"(;-:/(:'02 ! ! ! ! 8609-0:'$!"(;-:/(:'02!! 8609-0:'$!"(;-:/(:'02
<$6&#0!=!>0?@! ! -;&9-&#*-,!"(;-:/(:#2! -;&9-&#*-,!"(;-:/(:#2 ! W-(6#J!=!?&P@ ! ! -;&9-&#*-,!"(;-:/(:#2! -;&9-&#*-,!"(;-:/(:#2
?%3()06&#0!!=!">0@AB!C:2?! '*DD*:!"1(6&(;)02! ! '*DD*:!"106$!D&:*62
! F3()'0/*:$!=!?&P@ ! '*DD*:!"1(6&(;)02! ! -:'*DD*:!"D&:*62
E()0:(!=!<;?! ! '*DD*:!"1(6&(;)02! ! '*DD*:!"106$!D&:*62
F3()'*%$6&#0!=!F->0?@ ! ! '*DD*:!"106$!D&:*62! '*DD*:!"D&:*62 ! F()'&#0!!=!F(FPK ! ! '*DD*:!"1(6&(;)02! ! (;,0:#!"0X'0%#!*106%6&:#2
G:(64&#0HI-J*:&#0!H!F-K7,?L!! 6(60!"106$!D&:*62! ! -;&9-&#*-,!"1(6&(;)02 ! 7/-)(6&(!=!Y7)?&KPZ!! '*DD*:!"1(6&(;)02! ! (;,0:#
M0::(:N#0HM0#6(30/6&#0! '*DD*:!"106$!D&:*62! '*DD*:!"1(6&(;)02 ! [))&#0!! ! ! '*DD*:!"(;-:/(:#2! ! -:'*DD*:!"D&:*62
F-O@7,L?OK!H!F-O@?;L?OK ! "YB!R27)@"?&B!7)2LPO\"PR2@!H!XR@P!!!
F*10))&#0!H!F-?! ! -:'*DD*:!"106$!D&:*62! '*DD*:!"D&:*62 ! Y(*)&:&#0!=!7)@?&@PV"PR2L!! 6(60!"0X'0%#!*106%6&:#2! '*DD*:!"D&:*62
?N;:&#0!=!?;@?K ! ! -:'*DD*:!"106$!D&:*62! 6(60!"106$!D&:*62
! <$6*%3$))&#0H/&(,%*60! (;,0:#!! ! ! '*DD*:!"1(6&(;)02
P6%&D0:#!=!7,@?K! ! 6(60!"106$!D&:*62! ! 6(60!"106$!D&:*62 ! 7)@?&LPO\"PR2@!!H!!7)P"PR!2
Q0()4(6!=!7,L?L! ! 6(60!"106$!D&:*62! ! 6(60!"106$!D&:*62 ! 7)-:&#0!=!Y7)K"?PL2@"PR2]! (;,0:#!"0X'0%#!*106%6&:#2! '*DD*:!"D&:*62
76,0:*%$6&#0!=!>0@A7,?! '*DD*:!"D&:*62! ! 6(60!"106$!D&:*62
! ^(6&#0!=!^(?PL!! ! '*DD*:!"106$!D&:*62! '*DD*:!"D&:*62
F&::(;(6!=!R4?! ! -:'*DD*:!"D&:*62! ! 6(60!"106$!D&:*62
G)0'#6-D!=!"7-B!742! ! -:'*DD*:!"1(6&(;)02!! '*DD*:!"D&:*62
5(N10!E*)/!=!7-! !! '*DD*:!"106$!D&:*62! '*DD*:!"D&:*62
M0))-6&/0,H?0)0:&/0,!=!"M0B!?02!! '*DD*:!"106$!D&:*62! -:'*DD*:!"1(6&(;)02
7S06!T3&#0!(:/!R0/0:9-&,#B!OUUV
 Mineralization Style HS systems – origin of acid-sulfate conditions
1. Magmatic-hydrothermal
• condensation of magmatic vapor plume rich in acid gases (SO2, HCl, H2S, HF)
• most closely associated with high sulfidation mineralization
• 200 ! 350° C
Low-sulfidation, neutral pH, High-sulfidation, acid-pH, • pH ~ 1 ! 1.5; Al & Fe leached, silica little solubility – no veins, no sinters
meteroic magmatic 2. Steam-heated
• condensation of magmatic volatiles and oxidation of H2S gas
! open space veins dominant ! veins subordinate; locally
dominant • 100 ! 120° C
• pH ~ 2 ! 3; Al not leached
! disseminated ore = minor ! disseminated ore = dominant • forms in vadose zone above the paleo-water table (e.g., lithocap) alunite +/-
kaolinite, native sulfur, opal, cristobalite
! replacement ore = minor ! replacement ore = common
3. Supergene
! stockwork ore = common ! stockwork ore = minor
• surficial oxidation of sulfides; unrelated to primary (sulfide) ore
• alunite +/- jarosite, Fe-oxides or hydroxides, kaolinite,
halloysite (Al,Si, H2O)
• 30 ! 40° C
Hedenquist et al., 2000 White and Hedenquist, 1995 • can remobilize metals and Au

HS systems – Genesis

• Cooling also causes H2SO4 & HCl to dissociate to produce highly
acidic fluids
• HCl = H+ + Cl-; H2SO4 = 2H+ + SO42- (sulfate available)
(zone of fully saturated pores)
• Rising vapour condenses into meteroic water, heating and
acidifying that water.
• Cooling promotes SO2 disproportionation in fluid to
sulfuric acid (strongest) and H2S (promotes sulfide ppt) at
<350-400° C
! 4SO2 + 4H2O = 3H2SO4 + H2S
• Boiling - phase separation produces HCl, SO2, H2S & HF, CO2
rich, salt poor (e.g., NaCl, KCl) vapour
• HCl, SO2, H2S & HF in H2O fluid derived
from magma
• Fluids causing acid-sulfate alteration
! acidic, oxidized, not overly saline
• Fluids responsible for transporting later, overprinting, ore stage
! more saline (up to 20 wt%), less acidic and more reduced
• Gold precipitation thought to a product of
! fluid mixing causing cooling, reduction, pH increase that
destabilizes Au-bearing chloride complexes)
and/or
! boiling (loss of H2S gas and destabilizing of Au-bearing
hydrosulfide complexes)

Sillitoe, 1993
 HS systems – Genesis HS systems – Genesis: Lepanto

1. Early alteration:
Hot HCl, SO2, HF-rich
vapour travel along faults,
dissolve in meteoric water to
produce acidic fluid; results in
“barren” argillic and vuggy
quartz alteration and increased
porosity/permeability

2. Mineralization:
Au is transported in a
condensed vapour phase or as a
dissolved Au-Cl complex in a
magmatic brine

Hedenquist et al. (1996) Hedenquist et al. (1998)

Size (advanced arg) matters (much of the time, cf. El Indio) Genesis: LS systems

• Magmatic heat source?

(plus volatiles?)
chloride waters
acid sulfate steam-heated
boiling springs, silica sinter • Magmatic-derived(?) fluid
waters mud pools, fumaroles
equilibrates with distal
CO2-rich steam- countryrock and mixes with
250°C
heated waters
C METEORIC water to
200°
cold groundwaters
300ºC produce a neutral pH,
recharge reduced ore fluid that
convects in upper crust
El Indio 8 Moz • Forms zoned alteration
Neutral chloride • Fluid boiling precipitates ore
LS waters minerals as H2S gas is driven
400°C
off destabilizing Au-bearing
bisulfide complexes
2 km

2 km
Magma
Cooke and Simmons, 2000
(Arribas et al., Gold in 2000 – Slide Courtesy J Hedenquist)
 Genesis: LS systems

• Peripheral bicarbonate waters

! boiled off CO2 and H2S
chloride waters
acid sulfate steam-heated
boiling springs, silica sinter gas condenses in
waters mud pools, fumaroles
groundwater
CO2-rich steam- and dissociation occurs
250°C
heated waters
C H2CO3 = 2H+ + CO32-
200°
cold groundwaters
300ºC
H2S = H+ + HS-
recharge
! Weak acidity causes
illite/smectite, calcite + pyrite
• Stages 2 and 3 abundant boiling textures but
• Steam-heated acid sulfate barren = low salinity fluids (<1wt% NaCl)
Neutral chloride waters in vadose zone !meteroic fluids with no metals
LS waters
! from oxidation of H2S
400°C • Stage 1 and Stage 4 main ore stages with less
released by boiling like in HS textural evidence for boiling = higher salinity
systems (4-10wt% NaCl)
2 km

! magmatic origin carrying metals?

2 km
Magma
Cooke and Simmons, 2000

Genesis: LS systems Alteration comparison: LS & HS systems

• Crofoot-Lewis, LS epithermal not obviously associated with magmatism,
Nevada; Ebert & Rye, 1997

Low sulphidation Steam-heated overprint High sulphidation

(neutral pH, reduced) H2 S + 2O 2 H 2SO 4 (acidic, oxidized)

~170°C smectite
cristobalite - kaolinite ~170°C
- alunite smectite
kaolinite
- alunite ore-
ore illite / smectite kaolinite +_ smectite vuggy
vein illite / smectite quartz
illite +_ adularia

~280°C propylitic propylitic illite ~280°C

CO2 , H2 SO4 , H2 S, HCI
Boiling (Not to scale)
CO 2 , H2S
Meteoric water
NaCI
circulation
3H2 SO4 + H2 S
Equilibration
with rock
4SO2 + 4H 2 O
H 2 O, CO2 , H 2 S, HCI, metals

magma

Hedenquist et al., 2000

Hedenquist et al. (1996)
• HS deposits are
Strongly
Acidic
Weakly
Acidic
Weakly
Alkaline
Strongly
Alkaline Summary: LS & HS systems
-26

alun
kaol
related to acidic

Ca+2
anhy
oxidised

calcite
HSO4-

anhy
SO42-
Acid, Oxidised
fluids
• LS deposits -28 kaol H S O4-
associated with reduced H2 S Hematite
near-neutral pH -30 an
h
Ca 2 y
fluids Pyrite +
S O4 2 -
H2 S oxidised
-32
log f(O )
2
HS -
reduced
-34
Magnetite
-36 Near-
Pyrrhotite neutral ca
lc
Ca + it e
-38 T = 300ºC
2

HS -
H2 S
kaol

ms
ms

Kf
Sal = 0.5 eq. wt. %
!S = 0.004 molal
-40
0 1 2 3 4 5 6 7 8 9 10
pH

Summary: LS & HS systems Bibliography

Arribas, A., Hedenquist, J.W., Itaya, T., Okada, T., Concepcion, R.A., Garcia, J.S., 1995. Contemporaneous Formation of Adjacent
Porphyry and Epithermal Cu-Au Deposits over 300 Ka in Northern Luzon, Philippines, Geology 23, pp. 337-340.

Begbie, M.J., Sporli, K.B., Mauk, J.L., 2007. Structural evolution of the Golden Cross epithermal Au-Ag deposit, New Zealand,
Economic Geology 102, pp. 873-892.

Christie, A.B., Simpson, M.P., Brathwaite, R.L., Mauk, J.L., Simmons, S.F., 2007. Epithermal Au-Ag and Related Deposits of the
Hauraki Goldfield, Coromandel Volcanic Zone, New Zealand, Economic Geology 102, pp. 785-816.

Dong, G., Morrison, G., Jaireth, S., 1995. Quartz textures in epithermal veins, Queensland - Classification, origin, and implication,
Economic Geology 90, pp. 1841-1856.

Ebert, S.W., Rye, R.O., 1997. Secondary precious metal enrichment by steam-heated fluids in the Crofoot-Lewis hot spring gold-silver
deposit and relation to paleoclimate, Economic Geology 92, pp. 578-600.

Hedenquist, J.W., Arribas, A., and Gonzalez-Urien, E., 2000, Exploration for epithermal gold deposits: Reviews in Economic Geology,
v. 13, pp. 221–244.

Muntean, J.L., Einaudi, M.T., 2001. Porphyry-epithermal transition: Maricunga belt, northern Chile, Economic Geology 96, pp.
743-772.

Sillitoe, R.H., Hedenquist, J.W., 2003, Linkages between volcanotectonic settings, ore-fluid compositions, and epithermal precious
metal deposits, in: S.F. Simmons, I. Graham, (Eds.), Volcanic, geothermal, and ore-forming fluids; rulers and witnesses of
processes within the Earth, Special Publication of the Society of Economic Geologists 10, Denver, Colorado, pp. 315-343.

Simmons, S.F., Browne, P.R.L., 2000. Hydrothermal minerals and precious metals in the Broadlands-Ohaaki geothermal system:
Implications for understanding low-sulfidation epithermal environments, Economic Geology 95, pp. 971-999.

Simmons, S.F., Brown, K.L., 2007. The flux of gold and related metals through a volcanic arc, Taupo Volcanic Zone, New Zealand,
Geology 35, pp. 1099-1102.

Simmons, S.F., White, N.C., John, D., 2005, Geological characteristics of epithermal precious and base metal deposits, in: J.W.
Hedenquist, J.H.F. Thompson, R.J. Goldfarb, J.P. Richards, (Eds.), Economic Geology One Hundredth Anniversary Volume,
Society of Economic Geologists, Littleton, Colorado, pp. 485–522.