Hydrothermal

fluids:
an introduc?on
(types, composi?on, transport, and precipita?on)

Lluís Fontboté
Dept. Earth Sciences, Univ. Geneva, Switzerland

Honorary Lecturer Society of Economic Geologists (SEG)

MINERAL RESOURCES AND GEOFLUIDS

Department of Earth Sciences

!  Reminder: three types of ore-forming fluids

!  Magmas
!  Hydrothermal fluids
!  Surficial fluids (marine, meteoric)

CONSTITUANTS
FLUID (S, LIGANDS, TRANSPORT PRECIPITATION
METALS)

US
FOC

This chapter:

•  Sources and types of hydrothermal fluids

•  Sources of constituents
•  Fluid transport
•  Constituents: transport and precipitation mechanisms

L. Fontboté, 20 May 2019 1

 Water in the crust
Meteoric Seawater

Connate ?

MagmaIc Metamorphic

Juvenile
(mantle) ?
Bodnar (kluweronline)

Types of hydrothermal fluids: Salinity vs T

60

50
Salinity(wt % NaCl equivalent

"Secondary"
40 magmaIc fluid

ng
30 Basinal ixi
m
brines ric
eo
et
c -m
20 aI
m
ag
M "Primary"
Metamorphic fluids magmaIc
10
fluid
Secondary magmaIc fluid

100 200 300 400 500 600 800 900

Temperature (°C)

L. Fontboté, 20 May 2019 2

 (metals)

(Hedenquist)

Fluids in the
porphyry system

Sillitoe, modified by Kouzmanov and

Prokovski, 2012

Temperature (°C)

L. Fontboté, 20 May 2019 3

 Sillitoe, modified by Kouzmanov and
Prokovski, 2012

Temperature (°C)
Kouzmanov and Pokrovski, 2012

Magma?c fluid: phase separa?on

L. Fontboté, 20 May 2019 4

Stable isotopes may help to discriminate fluid sources

unr.edu/homepage/arehart/Courses/471-671/ Lecture_09._Isotopes_handout.pdf

Hedenquist &
Richards, 1998

L. Fontboté, 20 May 2019 5

Basinal brines:
marine vs evaporite dissolu?on

Grandia et al. Econ

Geol.

Acidity and oxidation

state
!  Most hydrothermal fluids of magmatic origin arrive at the upper part
of the crust, they tend to be acidic and oxidizing.

!  However, by water-rock interaction the fluids will tend

!  to neutralize (reaction with carbonates, feldpars….), and
!  to reduce (reaction with Fe2+ abundant in most rocks, organic C)

!  On the other hand, basinal brines or other saline fluids that

originally were not acidic, by interaction with rocks during their
migration path, may become acidic. For example, Na+ can be fixed
by plagioclases and plagioclase Cl- may form ClH.

L. Fontboté, 20 May 2019 6

 Red beds, one of the few oxidizing lithologies

Be aware: Frequently red (oxidized) at surface but

grey (reduced) below….even at Mars

h[p://spaceref.com/mars/nasa-curiosity-rover-drills-hole-into-mar?an-surface.html

L. Fontboté, 20 May 2019 7

 Fluid inclusions

When minerals crystallize from a melt or fluid phase, small

amounts of these phases may be preserved in melt or fluid
inclusions. These inclusions are very important informa?on
sources concerning:
- Forma?on temperature and salinity (microscope with
hea?ng and cooling stage)
- Composi?on (LA-ICP-MS)

Figures. Ulrich, T., Günther, D, Heinrich, C.A. (1999) Nature, v. 399, p. 676-679.

Metal content in ore fluids

•  In porphyry type systems, up to n x 10000

ppm

•  In deposits formed by basinal brines, like for

example MVT and SHMS deposits, only in
the n x 100 ppm range.

L. Fontboté, 20 May 2019 8

 Topics

•  Sources and types of hydrothermal fluids

•  Sources of constituents

•  Fluid transport

•  Constituents: transport and precipitation

mechanisms

L. Fontboté, 20 May 2019 9

 S source
•  Magmatic S
Already empiric evidences: the magmatic rocks
contain small amounts of pyrrhotite, at low T,
pyrite.
•  S of host rocks (e.g., evaporites, pyrite
shales, disseminated magmatic sulfides in
eruptive and intrusive rocks)
•  Seawater sulfate and of basinal fluids

SO4= or S= ?
•  in a fluid there is SO4= and S= *
•  in order to form sulfates, SO4= must be dominant (=>
oxidizing conditions)
•  in order to form sulfides S= is needed. The availability of S=
is often the key factor for ore deposit formation
•  S= by SO4= reduction:
–  bacterial reduction (low T, up to ~ 80°C)
–  in prsence of hydrocarbons (TSR ~ > 80°C)
–  other reductants (Fe2+, C4+)
•  Disproportionation reaction
•  Isotopic ratios give information on:
–  reduction mode, sources
–  temperature
* and other S species like HSO4-, HS-, ...

L. Fontboté, 20 May 2019 10

Bacterial Sulphate Reduc?on (BSR)

Fry (2005)

BSR yields typically large ∂34S spreads with negative values

"Thermochemical sulfate
reduction" (TSR)
"Thermochemical sulfate reduction" (TSR)
important in presence of hydrocarbons

SO42= + CH4 + 2H+ = H2S + CO2 + H2O

L. Fontboté, 20 May 2019 11

 "Disproportionation" reaction
Typical for cooling of magmatic-hydrothermal fluids

4SO2 + 4H2O = H2S + 3H2SO4

Note that sulfides and sulfates can form from the same fluid

Sulfur species

■  Schematic log fO2 – pH diagram to illustrate the relative distribution of the

predominance fields of the major S-species and the hematite-magnetite buffer.
Under relatively acid conditions, reduced species often predominate, especially
since many crustal assemblages are more reducing than hematite-magnetite,
but sulphate fluids are also important in some situations e.g. high sulfidation ore
deposits (Yardley and Bodnar, 2014)

L. Fontboté, 20 May 2019 12

 Sulfur species in typical ore fluids

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017 Elements

Metal sources
•  "Partioned" from a magma into a hydrothermal
fluid
•  Leached from rocks

•  Pb, Nd and Sr isotope ratios (among others) may indicate

•  H, O, S, and C isotope ratios may indicate fluid sources and
indirectly the metal sources.

L. Fontboté, 20 May 2019 13

 Topics

•  Sources and types of hydrothermal fluids

•  Sources of constituents

•  Fluid transport

•  Constituents: transport and precipitation

mechanisms

Fluid transport -1
A.  Thermal anomalies of magmatic origin : 80% of crustal fluid flow
B.  Thermal anomalies caused by crustal thinning
C.  Gravitational movement
D.  Others: "buoyancy" by salinity differences, sediment
compression, gas expulsion

L. Fontboté, 20 May 2019 14

 Fluid transport -2
■ Most transport takes place above the brittle/
ductile transition (because of permeability). This
explains that most ore deposits have formed ant
depths less then 8-10 km.

■ Primary permeability
■ Secondary permeability (fractures, dissolution)
■ Hydraulic breccias (when Pf >Pl)
■ The paramount importance of focusing fluids:
most deposits occur along fractures!

Duration of hydrothermal
systems
Three evidence lines:

-  fluid mass balance

-  cooling
-  age determina?ons

-  => Certain ore deposits formed by magma?c-

hydrothermal fluids very rich in metals may form by
short pulses (~<1000 years)
-  Other deposit types need much more ?me

L. Fontboté, 20 May 2019 15

 Topics

•  Sources and types of hydrothermal fluids

•  Constituant sources

•  Fluid transport

•  Constituants: transport and precipitation

mechanisms

Transport and precipita?on: parameters

•  "ligands" (complexes, mainly with Cl-)

•  T
•  pH
•  oxida?on state: it controls mainly the S species
(H2S, HS-, SO4=,...)
•  P
(+ presence of enough S and metals)

L. Fontboté, 20 May 2019 16

 Metal transport in the fluid: Complexes
At high T, metal solubilities are high.
At T < 400°C metal solubility is in most cases controlled by
following complexes:

Chloride complexes
Only effective complexes for virtually all base metals! in part also for gold!
MeCl2(aq) + H2S(aq) = MeS(s) + 2H+ + 2Cl-
Pb, Zn, Cu
examples: ZnCl2(aq) + H2S(aq) = ZnS(s) + 2H+ + 2Cl-
AuCl2-(aq) + 1/2H2O = Au(s) + 2Cl- + H+ + 1/4O2
Sulfide complexes Au
Only effective Au transport below 250°C! No base metals

Me(HS)2-(aq) + 1/2 H2 = MeS(s) + 2H2S(aq)

example: Au(HS)2-(aq) + 1/2 H2 = Au(s) + H2S + HS-

To remember (metal transport below 400°C):

•  Saline fluids may transport Pb, Zn, Cu, Ag, and

Au*.
•  At T < 250°C Au is best (~only) transported by
sulfide complexes
•  In general, non saline fluids can transport Au,
(some Ag), U, REE, but CANNNOT transport
base metals.
•  U can be transported by carbonate complexes
and W by OH- complexes.
* Below 250°C, Au transport as chloride complex is ineffective

L. Fontboté, 20 May 2019 17

 Zn-Pb Zn-Pb Cu

Mo

Au
Cu Au
Mo

Zn-Pb
Ag Zn-Pb

Mo
Cu
Au
Mo Cu
Au

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017 Elements

Solubility: Salinity and T influence

L. Fontboté, 20 May 2019 18

 Zoning example: The porphyry system

Kouzmanov and Pokrovski, 2012

Reminder: Zn2+Cl-2 + H2S = ZnS + H+ + Cl-, therefore Zn and S can be transported together under low pH or under
oxidizing condiIons (with S as SO42= )

PrecipitaIon

PrecipitaIon

G. Anderson

L. Fontboté, 20 May 2019 19

 Reminder: Zn2+Cl-2 + H2S = ZnS + H+ + Cl-, therefore Zn and S can be transported together under low pH or under
oxidizing condiIons (with S as SO42= )

PrecipitaIon

PrecipitaIon

Simplified diagram, not to scale! Only for illustra?on of main processes

Solubily: Influence of pression

For metals, direct effect of pressure is less dramatic than pH, Eh and T.
In general, solubility increases if P decreases. (Opposite to intuitive
expectation!)
(Pressure controls also phase separation, "boiling". Extremely important
for metal solubility!)

0.5 kbars

1 kbar
2 kbars
2 kbars

2 kbars
2 kbars

Hemley et al. (1992)

L. Fontboté, 20 May 2019 20

 Solubility: The case of Au
According to the environment different mechanisms to
precipitate Au.

High sulfidation (acidic and oxidizing conditions).....

Low sulfidation (close to neutrality, reducing conditions)...

Orogenic gold...

Reminder: Zn2+Cl-2 + H2S = ZnS + H+ + Cl-, therefore Zn and S can be transported together under low pH or under
oxidizing condiIons (with S as SO42= )

PrecipitaIon

PrecipitaIon

G. Anderson

L. Fontboté, 20 May 2019 21

 Zn-Pb Zn-Pb Cu

Mo

Au
Cu Au
Mo

Zn-Pb
Ag Zn-Pb

Mo
Cu
Au
Mo Cu
Au

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017 Elements

Solubility: The case of Au

Pokrovski et al., 2014

Au transported as chloride favors precipitation

T decrease or pH increase
Au transported as bi-sulfide increases solubility

L. Fontboté, 20 May 2019 22

 Solubility: The case of Au

Mixing with
low pH fluids

Corbett and Leach, 1997

In orogenic gold
deposits ....

.. one of the possibilities is to

destabilize the bi-sulfide
complex (e.g., Au(HS)2-(aq) )
by forming sulfides in the host
rock

Haeberlin, et al. (2004) La Lima vein, Pataz, Peru

L. Fontboté, 20 May 2019 23

•  At low T, Fe can be transported in soluIon ONLY in the ferrous state
(Fe2+); under oxidizing condiIons ferriciron (Fe3+) precipitates.

Brookings (1988)

BIF formation (Holland & U. Petersen 1995)

Oxidation of Fe (II) by cyanobacterial O2

L. Fontboté, 20 May 2019 24

 (Brookings, 1988)

Pyrolusite (MnO2)

■  :Km-3 Mine, Lavrion Mines, Lavrion (Laurion; Laurium), Lavrion District, Attikí (Attica;
Attika) Prefecture, Greece Area 8mm. Dendrites of black pyrolusite on light yelow-brown
goethite after siderite
http://www.mindat.org/picshow.php?id=12969

L. Fontboté, 20 May 2019 25

 Solubility: Some gangue minerals
Silica: Below 350°C - precipitation largely controlled by decreasing T
Above 350°C- strongly influenced by (A) and
pressure (C, e.g. porphyry stockwork veins!)
Important: Retrograde solubility

Quartz solubility

Yardley and Bodnar, 2014

L. Fontboté, 20 May 2019 26

 Quartz solubility

More on ligands: HCO3-

•  H2O + CO2 <-> H+ + HCO3- <-> 2H+ + CO32-
•  boiling and pressure decrease:
•  CO2 amount decreases, reaction to the left, pH
increases!

L. Fontboté, 20 May 2019 27

 Solubility: Some gangue minerals
Calcite: precipitation largely controlled by increasing T,
also by decreasing P (=> increasing pH!)
H2O + CO2 <-> H+ + HCO3- <-> 2H+ + CO32-

Bladed calcite, typical for CO2 degassing (pH increase!),

open subsequent to boiling

Madjarovo, vein nr. 2, Bulgaria © L. Fontboté (2003)

L. Fontboté, 20 May 2019 28

 Bladed calcite, typical product of precipita?on by boiling
and PCO drop (pH increase)
2

Madjarovo, vein nr. 2, Bulgaria © L. Fontboté (2003)

Geopetal ("snow on the roof") carbonate precipita?on on

quartz : typical for abrupt CO2 degassing

Madan, Bulgaria
© L. Fontboté (2003)

L. Fontboté, 20 May 2019 29

 Solubility: Some gangue minerals
■  Anhydrite
In saline solutions precipitation favored by decreasing T

A Upwelling porphyry copper fluids in potassic alteration zones

B Descending acid sulfate fluids

(Redrawn from Blount and Dickson, 1969)

(Redrawn from Blount 1977, in Corbett & Leach 1997)

L. Fontboté, 20 May 2019 30