Unique W-rich alloy of Os and Ir and associated Fe-rich alloy of Os, Ru, and Ir from California

A shell-like polycrystalline grain (ca. 1 mm) of W-(Mo)-bearing Os-Ir alloy (11.4-18.6 wt% W; up to 1.5% Mo) is present in a very old collection (probably the 1890s) of tiny nuggets from Trinity Co., California. An extensive compositional series [(Os0.43-0.80Ir0.28-0.05) W0.12-018], and inverse Ir-Os correlation, are observed; the mean composition [Os0.676W0.153Ir0.124Fe0.021Mo0.015Ru0 011; Sigma atoms = 1], based on results of 50 electron-microprobe analyses, displays a ratio (Os + Ir):W of 5:1. The observed variations and element correlations suggest that (W + Mo) contents are controlled by Ir, and incorporated via the following substitution scheme: [(W + Mo) + Ir] <-> Os. The X-ray diffraction data indicate that the W-rich alloy has a hexagonal close-packed structure, related to that of osmium and allargentum, with a = 2.7297(4) angstrom, c = 4.3377(6) angstrom, and V = 27.99(l) angstrom(3); the c:a ratio is 1.59. The probable space-group is P6(3)/mmc, and Z = 2; the calculated density is 21.86(l) g/cm(3). The W-rich alloy is associated with an Os-Ru-Ir alloy rich in Fe (7.0-9.7 wt%), which exhibits atomic Fe <-> [Os + Ru] and Ir <-> [Os + Ru] mechanisms of substitution. We suggest that these W-(Mo)- and Fe-rich alloys formed by metasomatic alteration of a primary Os-Ir-Ru alloy, associated with mineralized ultramafic-mafic rocks of ophiolite affinity. A fluid phase may well have remobilized and transported W, Mo, and Fe. The W-rich alloy likely crystallized from a reducing fluid under conditions of low fugacities Of O-2 and S-2, thus promoting the observed siderophile behavior of W and Mo. These unusual W-(Mo)- and Fe-rich alloy grains were likely derived, as a placer material, from the Trinity ophiolite complex of northern California.