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
Juvenile
(mantle) ?
MINERAL RESOURCES AND GEOFLUIDS Bodnar (kluweronline)
Department of Earth Sciences
50
• Sources of constituents 100 200 300 400 500 600 800 900
• Fluid transport Temperature (°C)
• Constituents: transport and precipitation mechanisms
(metals)
Fluids in the
porphyry system Magma c fluid: phase separa on
Temperature (°C)
Stable isotopes may help to discriminate fluid sources Basinal brines:
marine vs evaporite dissolu on
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.
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
Note that sulfides and sulfates can form from the same fluid
Fry (2005)
• Sources of constituents
• Fluid transport
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
Duration of hydrothermal
systems Transport and precipita on: parameters
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-
Precipita on
Precipita on
0.5 kbars
1 kbar
2 kbars
2 kbars
2 kbars
Precipita on 2 kbars
Mo
Orogenic gold...
Mo
Cu
Au
Mo Cu
Au
Precipita on
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
In orogenic gold
deposits ....
BIF formation (Holland & U. Petersen 1995)
(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-
■ Anhydrite
In saline solutions precipitation favored by decreasing T
Madan, Bulgaria