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Hydrothermal Geochemistry 17 February 2005

Fe-As-S system Ternary phase

Not important metallurgically, not common minerals, so less
well-studied. Some debate over
whether apy has
Slow reaction rates for apy make it attractive geologically,
variable Fe:S+As
but difficult experimentally; retains initial conditions.
Data of Sharp et al.
Can use XRD to determine As content of apy:
suggest there is minimal
variability and
%As = 866.67d 131 - 1381.12 arsenopyrite lies directly
on the binary between
pyrrhotite and loellingite

If apy is non-stoichiometric, then it If apy lies on binary join, then

Pseudobinary requires an additional phase to buffer composition is fixed with only a single
relations the composition (i.e., py + po) coexisting species (either py or lo)

Fairly simple system but

some variation in apy
Not stable with py above
491EC @ 1bar; shifts to
higher T as function of P
Note immiscibility between
py + apy even though
they have the same

Scott, 1983 Sharp et al., 1985

Sulfidation reactions Effects of pressure

in the Fe-As-S system
The composition of apy is a Apy stability field shifts
function of both T and aS2 to higher T, fS2 with
increasing P
Note py-po buffer, As
liquid-solid, T of reactions This is a function of
changes in partial molar
For slopes of apy volume of sulfidation
composition to change in py reactions
or lo fields, extreme non-
ideal behavior is required

Fe-As-S systems 1
Hydrothermal Geochemistry 17 February 2005

P dependence as a function of molar volume Application to natural

Results in minor differences
Seems to work for most
in T determinations, but
intermediate T assemblages
significant differences in fS2
determinations (up to a log Highly metamorphosed
unit) assemblages yield T lower
than metamorphism,
Isopleths must be vertical
indicating reequilibration
outside the po field because
during retrograde stages (?)
of the lack of variability in
Fe:S+As Low-T assemblages may be
too LT to completely reach
equilibrium, and therefore
may yield inaccurate data

Arsenian pyrite deposition Arsenian pyrite deposition

Arsenian pyrite is clearly a non-equilibrium phase based on As commonly transported as arsenate ion (AsO33-), so
phase relations already described (unclear whether asmc is deposition in pyrite with Au may take place in reactions
stable either, probably not) such as:
Probably formed during rapid and/or high-T deposition where H3 AsO3( aq ) + Au( HS ) 2− + 3H2 S ↔ 2( AuAs) S2 + 2 H2 + HS − + 3H2 O
structure can be less selective about incorporating
impurities H2 + H3 AsO3( aq ) + Au( HS ) 2− ↔ AuAsS + HS − + 3H2 O

Gold deposition as native metal described by: Or for thioarsenide species:

Au( HS ) 2 + H2 ( aq ) ↔ Au 0 + H2 S( aq ) + HS − 3H2 + 3 Au( HS ) 2− + H3 As3S6( aq ) ↔ AuAsS + 6 H2 S + 3HS −
Last two more likely, given arrangement of As and Au in

Fe-As-S systems 2