fluid inclusions is also possible (Guillong et al. 2008).
An
A extensive literature now exists on the composition of
B metal crustal abundances. Second-order processes, such as
Effects of magmatic sulfide saturation on trapping or
Figure 2
providing metals in magmatichydrothermal systems.
(A) Aqueous fluid saturation occurs before sulfide saturation in the
magma. Metal content in residual melt increases because metals are
not significantly sequestered by the crystallizing silicate oxide
minerals (a1 a3) and metals are optimally transferred to the
magmatic fluid when saturation occurs. (B) Sulfide saturation
occurs before aqueous fluid saturation in the magma. Metal
concentrations initially increase until sulfide saturation occurs
(b1b2) then sharply decrease (b3). Transfer of metals to fluid is
not optimal because significant proportions of metals have been
sequestered by sulfides. (b4) Magmatic sulfides may be destabilized
by aqueous fluids exsolved from the same magma in which sulfide
saturation previously occurred. (b5) Magmatic sulfides may be
destabilized by aqueous fluids exsolved from an underplated mafic
magma. (b6) A sulfide-undersaturated mafic magma may recycle
the sulfides and release the metals contained therein once the mafic
magma becomes saturated in an aqueous fluid.
Richards 2009). Alternatively, subsequent oxidation of
magmatic sulfides can also supply metals to aqueous fluids
(Fig. 2).
SULFUR AND METAL CONTENT
OFHYDROTHERMAL FLUIDS
In contrast to bulk salinity (NaCl+KCl+CaCl2), which is
reliably determined by microthermometry of fluid inclu-
sions, the concentrations of metals and sulfur in hydro-
thermal fluids became measurable when in situ methods
such as LAICPMS and PIXE were developed in the late
1990s. These methods can accurately analyse individual
fluid inclusions trapped in minerals during growth or during
post-growth deformation, providing quantitative determi-
nations of the metal content to the ppm level (e.g. Heinrich
et al. 2003). In combination with near-infrared microscopy,
in situ methods have been extended to the analysis of fluid
inclusions in opaque sulfide minerals (Kouzmanov et al.
2010). Quantification of sulfur concentrations in individual
E lements
ore-forming fluids from magmatichydrothermal systems,
including porphyry, skarn and epithermal polymetallic
deposits worldwide (see Kouzmanov and Pokrovski 2012).
Metal contents of pristine magmatic fluids show patterns
that are controlled by the metal abundances in the source
magmas and by elevated fluidmelt partition coefficients.
As a result, metal concentrations in pristine magmatic fluids
typically range between 10s and 1,000sppm, one to three
orders of magnitude higher than the corresponding average
separation of aqueous liquid and vapour phases, result in
additional enrichment, with the brine phase containing up
to several wt% Fe, Cu, Zn, Pb and Mn; thus these metals
become major fluid constituents, along with Na and K.
Concentrations of other metals of economic interest, such
as Mo, As, Sb and Ag, vary between 10s and 100s ppm.
Some of these metals, especially those transported as
sulfide complexes (e.g. Au), may also be enriched in the
vapour phase (Heinrich et al. 2003; Pokrovski et al. 2013).
The sulfur content of magmatichydrothermal ore-forming
fluids varies substantially, reaching wt% concentrations,
and so indicating that the major ingredients for sulfide
precipitation are available from the hydrothermal fluid
itself and do not require an external source.
For VHMS, iron oxidecoppergold (IOCG), sediment-
hosted, and orogenic gold deposits, data pertaining to
the mineralizing fluid compositions are still fragmentary.
Nevertheless, existing datasets on some sediment-hosted
deposits indicate that, despite the two orders of magni-
tude lower metal contents (10s to 100s ppm Zn and Pb)
in basinal brines compared to magma-derived fluids, the
reported measured concentrations are much higher than
those predicted in the past (e.g. Wilkinson et al. 2009).
These new findings sharply changed the understanding
of transport mechanisms, of metal deposition efficiency,
and of the time span of hydrothermal sulfide ore-forming
processes.
SULFUR SOURCES AND MAIN REACTIONS
Geological and isotope evidence indicates that sulfur in
hydrothermal sulfides can have four sources: (i) segregated
from a magma together with water; (ii) leached from sulfides
disseminated in rocks (since most magmatic, sedimen-
tary, and metamorphic rocks contain small quantities of
sulfides, mainly pyrite and pyrrhotite); (iii) derived from
sulfate minerals in evaporites; (iv) derived from seawater
sulfate and basinal brines.
Sulfide precipitation can be described by the following
schematic reaction (where aq = aqueous, Me = metal, s=
solid)
Me2+ (aq) + H2 S (aq) = MeS (s) + 2H + (aq) (1)
At least three of the four sulfur sources listed above contain
sulfur in oxidized form. But, as shown by reaction (1),
sulfur must be in its reduced state (S2) to allow precipita-
tion of sulfides. In addition to biogenic sulfate reduction
(Rickard et al. 2017 this issue), there are two other sulfate
reduction mechanisms that are key for the precipitation
of hydrothermal sulfides.
Magmatichydrothermal fluids, depending on their oxida-
tion state, contain different proportions of sulfur species,
including H2S, HS , SO2, SO42, HSO4, and S3. Hydrothermal
fluids originating from calc-alkaline magmas are enriched
in oxidized sulfur species, to a large extent made up of SO2.
In the following disproportionation reaction, which occurs
upon fluid cooling, S 4+ undergoes both oxidation and
99 A pr il 2017