Water

in the crust
Hydrothermal fluids: Meteoric Seawater

an introduc on
(types, composi on, transport, and precipita on)
Connate ?
Lluís Fontboté
Dept. Earth Sciences, Univ. Geneva, Switzerland

Honorary Lecturer Society of Economic Geologists (SEG) Magma c Metamorphic

Juvenile
(mantle) ?
MINERAL RESOURCES AND GEOFLUIDS Bodnar (kluweronline)
Department of Earth Sciences

  Reminder: three types of ore-forming fluids

 
 
Magmas
Hydrothermal fluids
Types of hydrothermal fluids: Salinity vs T
60
  Surficial fluids (marine, meteoric)

50

Salinity(wt % NaCl equivalent

CONSTITUANTS "Secondary"
FLUID (S, LIGANDS, TRANSPORT PRECIPITATION magma c fluid
40
METALS)
S
FOCU 30 Basinal ixi
ng
m
brines ric
eo
et
c -m
20 m
a
ag
M
"Primary"
This chapter: Metamorphic fluids magma c
10
fluid
•  Sources and types of hydrothermal fluids Secondary magma c fluid

•  Sources of constituents 100 200 300 400 500 600 800 900
•  Fluid transport Temperature (°C)
•  Constituents: transport and precipitation mechanisms
 (metals)

Sillitoe, modified by Kouzmanov and

Prokovski, 2012

(Hedenquist) Temperature (°C)

Kouzmanov and Pokrovski, 2012

Fluids in the
porphyry system Magma c fluid: phase separa on

Sillitoe, modified by Kouzmanov and

Prokovski, 2012

Temperature (°C)
Stable isotopes may help to discriminate fluid sources Basinal brines:
marine vs evaporite dissolu on

Grandia et al. Econ

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

Hedenquist &
Richards, 1998
 Fluid inclusions
Red beds, one of the few oxidizing lithologies
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.

Be aware: Frequently red (oxidized) at surface but

grey (reduced) below….even at Mars 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.

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

Topics
SO4= or S= ?
•  in a fluid there is SO4= and S= *
•  Sources and types of hydrothermal fluids •  in order to form sulfates, SO4= must be dominant (=>
oxidizing conditions)
•  Sources of constituents •  in order to form sulfides S= is needed. The availability of S=
is often the key factor for ore deposit formation
•  Fluid transport •  S= by SO4= reduction:
–  bacterial reduction (low T, up to ~ 80°C)

• 
–  in prsence of hydrocarbons (TSR ~ > 80°C)
Constituents: transport and precipitation –  other reductants (Fe2+, C4+)
mechanisms •  Disproportionation reaction
•  Isotopic ratios give information on:
–  reduction mode, sources
–  temperature
* and other S species like HSO4-, HS -, ...
Bacterial Sulphate Reduc on (BSR) "Disproportionation" reaction
Typical for cooling of magmatic-hydrothermal fluids

4SO2 + 4H2O = H2S + 3H2SO4

Note that sulfides and sulfates can form from the same fluid

Fry (2005)

BSR yields typically large ∂34S spreads with negative values

"Thermochemical sulfate Sulfur species

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

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

■  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)
 Topics
Sulfur species in typical ore fluids

•  Sources and types of hydrothermal fluids

•  Sources of constituents

•  Fluid transport

•  Constituents: transport and precipitation

mechanisms

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017 Elements

Fluid transport -1
Metal sources A.  Thermal anomalies of magmatic origin : 80% of crustal fluid flow
•  "Partioned" from a magma into a hydrothermal B.  Thermal anomalies caused by crustal thinning
fluid C.  Gravitational movement
D.  Others: "buoyancy" by salinity differences, sediment
•  Leached from rocks compression, gas expulsion

•  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.
 Topics
Fluid transport -2
■ Most transport takes place above the brittle/
•  Sources and types of hydrothermal fluids
ductile transition (because of permeability). This
explains that most ore deposits have formed ant •  Constituant sources
depths less then 8-10 km.
•  Fluid transport
■ Primary permeability
•  Constituants: transport and precipitation
■ Secondary permeability (fractures, dissolution) mechanisms
■ Hydraulic breccias (when Pf >Pl)
■ The paramount importance of focusing fluids:
most deposits occur along fractures!

Duration of hydrothermal
systems Transport and precipita on: parameters

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

Three evidence lines:
•  T
-  fluid mass balance •  pH
-  cooling •  oxida on state: it controls mainly the S species
-  age determina ons (H2S, HS-, SO4=,...)
•  P
-  => Certain ore deposits formed by magma c-
hydrothermal fluids very rich in metals may form by (+ presence of enough S and metals)
short pulses (~<1000 years)
-  Other deposit types need much more me
 Metal transport in the fluid: Complexes Zn-Pb Zn-Pb Cu
At high T, metal solubilities are high. Mo

At T < 400°C metal solubility is in most cases controlled by Au

following complexes: Cu
Mo
Au

Chloride complexes
Only effective complexes for virtually all base metals! in part also for gold!
MeCl 2(aq) + H2S(aq) = MeS(s) + 2H+ + 2Cl-
Zn-Pb
examples: ZnCl2(aq) + H2S(aq) = ZnS(s) + 2H+ + 2Cl- Ag Zn-Pb
AuCl 2-(aq) + 1/2H2O = Au(s) + 2Cl- + H+ + 1/4O2
Sulfide complexes Au
Mo
Cu
Only effective Au transport below 250°C! No base metals
Mo Cu
Au
Me(HS)2 -(aq)
+ 1/2 H2 = MeS(s) + 2H2S(aq)
example: Au(HS)2-(aq) + 1/2 H2 = Au(s) + H2S + HS-

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017 Elements

Solubility: Salinity and T influence

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
 Zoning example: The porphyry system
Reminder: Zn2+Cl-2 + H2S = ZnS + H+ + Cl-, therefore Zn and S can be transported together under low pH or under
oxidizing condi ons (with S as SO42= )

Precipita on

Precipita on

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

Kouzmanov and Pokrovski, 2012

Solubily: Influence of pression

Reminder: Zn2+Cl-2 + H2S = ZnS + H+ + Cl-, therefore Zn and S can be transported together under low pH or under
oxidizing condi ons (with S as SO42= )
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!)
Precipita on (Pressure controls also phase separation, "boiling". Extremely important
for metal solubility!)

0.5 kbars

1 kbar
2 kbars
2 kbars

2 kbars
Precipita on 2 kbars

Hemley et al. (1992)

G. Anderson
 Solubility: The case of Au Zn-Pb Zn-Pb Cu

Mo

According to the environment different mechanisms to Au

precipitate Au.
Cu Au
Mo

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

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

Zn-Pb
Ag Zn-Pb

Orogenic gold...
Mo
Cu
Au
Mo Cu
Au

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017 Elements

Solubility: The case of Au

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

Precipita on

Precipita on Pokrovski et al., 2014

Au transported as chloride favors precipitation

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

G. Anderson
 •  At low T, Fe can be transported in solu on ONLY in the ferrous state
(Fe2+); under oxidizing condi ons ferriciron (Fe3+) precipitates.
Solubility: The case of Au

Mixing with
low pH fluids

Corbett and Leach, 1997

Brookings (1988)

In orogenic gold
deposits ....
BIF formation (Holland & U. Petersen 1995)

.. one of the possibilities is to

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

Oxidation of Fe (II) by cyanobacterial O 2

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

 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

(Brookings, 1988)

Pyrolusite (MnO2)
Quartz solubility

■  :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
Yardley and Bodnar, 2014
http://www.mindat.org/picshow.php?id=12969
 Solubility: Some gangue minerals
Quartz solubility 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!),

More on ligands: HCO3- o en subsequent to boiling

•  H2O + CO2 <-> H+ + HCO3- <-> 2H+ + CO32-

•  boiling and pressure decrease:
•  CO2 amount decreases, reaction to the left, pH
increases!

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

 Bladed calcite, typical product of precipita on by boiling Solubility: Some gangue minerals
and PCO drop (pH increase)
2

■  Anhydrite
In saline solutions precipitation favored by decreasing T

A Upwelling porphyry copper fluids in potassic alteration zones

B Descending acid sulfate fluids

Madjarovo, vein nr. 2, Bulgaria

(Redrawn from Blount and Dickson, 1969)
(Redrawn from Blount 1977, in Corbett & Leach 1997)
© L. Fontboté (2003)

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

quartz : typical for abrupt CO2 degassing

Madan, Bulgaria