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Topics

Hydrothermal fluids:
•  Sources and types of hydrothermal fluids
an introduc@on
(types, composi@on, transport, and precipita@on) •  Sources of constituant

•  Fluid transport

•  Constituants: transport and precipitation


mechanisms

MINERAL RESOURCES AND GEOFLUIDS


Department of Earth Sciences

!  Reminder: three types of ore-bearing fluids


! 
! 
Magmas
Hydrothermal fluids Water in the crust
!  Magmas
Meteoric Seawater

CONSTITUANTS
FLUID (S, LIGANDS, TRANSPORT PRECIPITATION
METALS)

FOC
US
Connate ?

Magma?c Metamorphic
This chapter:

•  Sources and types of hydrothermal fluids


Juvenile
• 
• 
Sources of constituents
Fluid transport (mantle) ?
•  Constituents: transport and precipitation mechanisms Bodnar (kluweronline)

L. Fontboté, Friday, April 22, 2016 1


Types of hydrothermal fluids: Salinity vs T
60

50
Salinity(wt % NaCl equivalent

"Secondary" (metals)
40 magma?c fluid


ng
30 Basinal ixi
m
brines ric
teo
e
c -m
20 a?
m
ag
M "Primary"
Metamorphic fluids magma?c
10
fluid
Secondary magma?c fluid

100 200 300 400 500 600 800 900


Temperature (°C) (Hedenquist)

Fluids in the
porphyry system

Sillitoe, modified by Kouzmanov and Sillitoe, modified by Kouzmanov and


Prokovski, 2012 Prokovski, 2012

Temperature (°C) Temperature (°C)


Kouzmanov and Pokrovski, 2012

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Stable isotopes may help to discriminate fluid sources
Magma@c fluid: phase separa@on

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

Stable isotopes may help to discriminate fluid sources

Hedenquist &
Richards, 1998

Yardley and Bodanr, 2014

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Basinal brines: Acidity and oxidation
marine vs evaporite dissolu@on
state
!  When hydrothermal fluids of magmatic origin arrive at the upper
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.

Grandia et al. Econ


Geol.

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.

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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.

Bodnar (kluweronline)

Topics

•  Sources and types of hydrothermal fluids

•  Sources of constituents

•  Fluid transport

•  Constituents: transport and precipitation


mechanisms

L. Fontboté, Friday, April 22, 2016 5


S source SO4= or S= ?
■ Magmatic S. •  in a fluid there is SO4= and S= *
–  Already empiric evidences: the magmatic •  in order to form sulfates, SO4= must be
rocks contain small amounts of pyrrhotite, dominant (=> oxidizing conditions)
at low T, pyrite.
•  in order to form sulfides, S= must be
dominant (=> reducing conditions)
■ S of host rocks (e.g., evaporites, pyrite
•  SO4= reduction
shales, dissminated magmatic sulfides in
–  bacterial reduction (low T, up to ~ 80°C)
eruptive and intrusive rocks) –  by hydrocarbons (TSR)
–  other reductants (Fe2+, C4+)
■ Sea water sulfate * and other S species like HSO4-, HS-, ...

Sulfur species Availability of reduced S – A frequent limi@ng


factor for ore deposit forma@on!

■  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, Compiled by I. Marton based on Ohmoto and Rye (1979) and Cline et al (2005)
but sulphate fluids are also important in some situations e.g. high sulfidation ore
deposits (Yardley and Bodnar, 2014)

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Topics
Metal sources
•  "Partioned" from a magma into a hydrothermal
fluid •  Sources and types of hydrothermal fluids
•  Leached from host rocks
•  Sources of constituents

•  Fluid transport

•  Constituents: transport and precipitation


mechanisms
•  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.

Fluid transport -1
A.  Thermal anomalies of magmatic origin : 80% of crustal fluid flow Fluid transport -2
B.  Thermal anomalies caused by crustal thinning
C.  Gravitational movement ■ Most transport takes place above the brittle/
D.  Others: "buoyancy"= ascension by density differences ductile transition (because of permeability). This
(controlled by salinity or temperature), sediment
compression
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!

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Duration of hydrothermal Topics
systems
Three evidence lines: •  Sources and types of hydrothermal fluids

-  fluid mass balance •  Constituant sources


-  cooling
•  Fluid transport
-  age determina@ons
•  Constituants: transport and precipitation
-  => Certain ore deposits formed by magma@c- mechanisms
hydrothermal fluids very rich in metals may form in
n x 1000 years, not in millions of years!
-  Other deposit types need much more @me

Transport and precipita@on: factors Metal transport in the fluid: Complexes


At high T, metal solubilities are high.
•  "ligands" (complexes, mainly with Cl-) At T < 400°C metal solubility is in most cases controlled by
following complexes:
•  T
Chloride complexes
•  pH Only effective complexes for virtually all base metals! in part also for gold!
MeCl2(aq) + H2S(aq) = MeS(s) + 2H+ + 2Cl-
•  oxida@on state: Among others, it controls the S Pb, Zn, Cu
species (H2S, HS-, SO4=,...) examples: ZnCl2(aq) + H2S(aq) = ZnS(s) + 2H++ 2Cl-
AuCl2-(aq) + 1/2H2O = Au(s) + 2Cl- + H+ + 1/4O2
•  P Sulfide complexes Au
(+ presence of enough S and metals) 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-

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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


Zn-Pb Zn-Pb Cu

Mo

Au
Cu Au
Mo

Zn-Pb
Ag
Zn-Pb

Mo
Au
Cu
Au
Mo Cu

Fontboté, Kouzmanov. Chiaradia, Pokrovski, 2017, Elements Kouzmanov and Pokrovski, 2012

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Solubily: Influence of pression
Solubility: The case of Au
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!) According to the environment different mechanisms to
(Pressure controls also phase separation, "boiling". Extremely important
for metal solubility!) precipitate Au.

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

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


1 kbar
2 kbars
2 kbars
Orogenic gold...

2 kbars
2 kbars

Hemley et al. (1992)

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Solubility: The case of Au
Solubility: The case of Au

Mixing with
low pH fluids

Corbett & Leach 1997

Au transported as chloride favors precipitation


T decrease or pH increase
Au transported as bi-sulfide increases solubility
Corbett and Leach, 1997

In orogenic gold Fe-C-O-H Fe-Si-O-H


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 Brookings (1988)

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Solubility: Some gangue minerals Quartz solubility
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

Yardley and Bodnar, 2014

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


Solubility: Some gangue minerals oken subsequent to boiling

Calcite: precipitation largely controlled by increasing T,


also by decreasing P (=> increasing pH!)

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

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Geopetal ("snow on the roof") carbonate precipita@on on
Bladed calcite, typical product of precipita@on by boiling
quartz : typical for abrupt CO2 degassing
and PCO drop (pH increase) 2

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


© L. Fontboté (2003)

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)

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