POTENTIAL APPLICATIONS OF LAM-ICP-MS TECHNOLOGY IN ECONOMIC GEOLOGY: A PRELIMINARY STUDY OF MOLYBDENITE AND PYRITE.
Phillip Blevin1 and Simon Jackson2
1 GEMOC ANU
2 GEMOC Macquarie
The laser ablation microprobe (LAM)-ICP-MS offers enormous potential
in advancing trace element studies of minerals and materials through
significantly improved detection limits for in situ analysis,
and the ability to generate profiles through minerals by progressive
ablation. Molybdenite (MoS2) and pyrite from several ore deposits
were examined to ascertain trace element occurrences and abundances,
evaluate problems relating to inclusions and zoning, characterise
the suitability of MoS2 samples for Re-Os dating, as well as exploring
more general applications in ore deposit studies. The results
of the MoS2 analytical campaign are reported on here.
The sulfides were analyzed in 100 micrometer thick sections using
a UV laser ablation microprobe (LAM)-ICP-MS at Macquarie University.
In the absence of a suitable sulfide reference material, standardisation
was performed using a silicate reference material, NIST SRM 610,
with a nominal concentration of 500 ppm of most elements. Differences
in ablation yield between analyses were corrected by internal
standardization using Mo (MoS2) and Fe (pyrite) concentrations,
which were calculated from stoichiometry or had previously been
determined by electron microprobe microanalysis. This protocol
is expected to give semi-quantitative results. Indeed, averaged
Re contents determined by this method agreed well with those obtained
by previous workers using MoS2 separates from the same deposits.
Data were collected using a time-resolved data acquisition protocol,
allowing signals to be examined for assessment of zoning and to
be selectively integrated to minimize contributions to the signal
from inclusions and host minerals. The elements analysed were
Si, Ti, Cr, Fe, Ni, Cu, Zn, As, Se, Zr, Nb, Mo, Pd, Ag, Sn, Sb,
Te, W, Re, Au, Pb and Bi. Samples were sourced from numerous East
Australian occurrences as well as from overseas porphyry Mo and
porphyry Cu systems.
Trace element behaviour
Re, W, Se, Te, Bi and possibly Sn were found to comprise important
lattice substitutions in MoS2. This is evidenced by the high degree
of correlation of these elements with Mo. Zonation, particularly
of Bi, was present in some instances. More commonly, Bi correlates
with either Pb, or with Se and Te. This is consistent with the
occurrence of discrete inclusions of galenobismutite and cosalite
(Bi-Pb), ikunolite (Bi-Se), joseite and tetradymite (Bi-Te), bismuthinite
and native bismuth. Transient correlations of Sb and Cu with Bi
suggests the presence of bismuthinite-stibnite and bismuthinite-aikinite
solid solutions. Ablation of MoS2 crystals oriented both parallel
and perpendicular to the c axis suggest that most inclusions occur
along cleavages, but an exsolution origin for some of the inclusions
cannot be ruled out. Au is present as isolated Au_ inclusions
and in Bi-bearing inclusions. Pd also reports in some samples.
High Sn registrations at the commencement of ablation runs represent
surface contamination during polishing.
Deposit and Metallogenic Studies
MoS2 from chalcophile dominated (porphyry Cu-Au) deposits have
higher Re, and lower Bi, W and Sn contents and Se/Te ratios than
MoS2 from lithophile (Mo, W, Sn) dominated deposits. Re and W
contents are sensitive indicators of the degree of compositional
evolution of the related igneous rocks, and thus provide a useful
genetic fingerprint. The systematic variation of Re contents in
MoS2 from different deposit types has implications for understanding
the occurrence of Mo and Au in otherwise lithophile dominated
ore deposits (and related granitoids) that are also highly depleted
in other siderophile and chalcophile elements. In particular,
the results imply that Re becomes uncoupled from Mo during magmatic
differentiation. Significant Au deposits are known to be related
to these igneous rocks.
Assessment of Molybdenites for Re-Os dating
A suggested test for assessing MoS2 samples for Re-Os dating involves
comparing their Re contents with their structural polytype. "3R"
MoS2 has been assumed to grow via a screw dislocation mechanism
triggered by incorporation of Re. By inference, low Re "3R"
MoS2 crystals are inferred to have lost Re subsequent to crystallisation,
and therefore potentially may yield unreliable Re-Os dates. Results
of this study suggest that W and Bi may also occur as lattice
components within MoS2. The degree of structural mismatch of Bi,
W and Sn within the MoS2 lattice are on par or higher than that
for Re, thus the presence of these elements during crystallisation
should trigger 3R polytype formation. Under these circumstances
there should be no (a priori) reason to doubt the veracity
of dates obtained from low Re, "3R" MoS2 samples obtained
from lithophile dominated deposits.
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