Invisible gold in natural and synthetic arsenian pyrite and marcasite correlates with anomalous As content and Fe deficiency, and high contents of invisible gold in most natural and all synthetic arsenopyrite correlate with excess As and Fe deficiency. As-rich, Fe-deficient arsenopyrite synthesized hydrothermally contains up to 3.0 wt% Au uniformly distributed in growth zones of light backscattered electron contrast. At the Deep Star gold deposit, Carlin Trend, Nevada, the sulfide compositions apparently span the full range of metastability from FeSz to near FeAsS (40 at% S); arsenian pyrite contains up to 0.37 wt% Au, but arsenopyrite has excess S and is relatively Au poor. Observed minimum Fe contents are 29.1 at% in arsenian pyrite and marcasite from the Deep Star deposit and 31.3 at% in synthetic arsenopyrite. We suggest that invisible gold in arsenian pyrite and marcasite and arsenopyrite from sediment-hosted gold deposits represents Au removed from ore fluids by chemisorption at As-rich, Fe-deficient surface sites and incorporated into the solids in metastable solid solution. However, the oxidation state of invisible gold (Aua, AU1+) remains uncertain because the chemisorption process is intrinsically nonsystematic in terms of crystal-chemical parameters and does not result in definitive atomic substitution trends.

Apatite-group phosphates are nearly ubiquitous in carbonatites, but our understanding of these minerals is inadequate, particularly in the areas of element partitioning and petrogenetic interpretation of their compositional variation among spatially associated rocks and within individual crystals. In the present work, the mode of occurrence, and major-and trace-element chemistry of apatite (sensu lato) from calcite and dolomite carbonatites, their associated cumulate rocks (including phoscorites) and hydrothermal parageneses were studied using a set of 80 samples from 50 localities worldwide. The majority of this set represents material for which no analytical data are available in the literature. Electron-microprobe and laser-ablation mass-spectrometry data (~600 and 400 analyses, respectively), accompanied by back-scattered-electron and cathodoluminescence images and Raman spectra, were used to identify the key compositional characteristics and zoning patterns of carbonatitic apatite. These data are placed in the context of phosphorus geochemistry in carbonatitic systems and carbonatite evolution, and compared to the models proposed by previous workers. The documented variations in apatite morphology and zoning represent a detailed record of a wide range of evolutionary processes, both magmatic and fluid-driven. The majority of igneous apatite from the examined rocks is Cl-poor fluorapatite or F-rich hydroxylapatite ( 0.3 apfu F) with 0.2-2.7 wt.% SrO, 0-4.5 wt.% LREE 2 O 3 , 0-0.8 wt.% Na 2 O, and low levels of other cations accommodated in the Ca site (up to 1000 ppm Mn, 2300 ppm Fe, 200 ppm Ba, 150 ppm Pb, 700 ppm Th and 150 ppm U), none of which show meaningful correlation with the host-rock type. Silicate, (SO 4) 2and (VO 4) 3anions, substituting for (PO 4) 3-, tend to occur in greater abundance in crystals from calcite carbonatites (up to 4.2 wt.% SiO 2 , 1.5 wt.% SO 3 and 660 ppm V). Although (CO 3) 2groups are very likely present in some samples, Raman micro-spectroscopy proved inconclusive for apatites with small P-site deficiencies and other substituent elements in this site. Indicator REE ratios sensitive to redox conditions (Ce, Eu) and hydrothermal overprint (Y) form a fairly tight cluster of values (0.8-1.3, 0.8-1.1 and 0.6-0.9, respectively) and may be used in combination with trace-element abundances for the development of geochemical exploration tools. Hydrothermal apatite forms in carbonatites as the product of replacement of primary apatite, or is deposited in fractures and interstices as euhedral crystals and aggregates associated with typical late-stage minerals (e.g., quartz and chlorite). Hydrothermal apatite is typically depleted in Sr, REE, Mn and Th, but enriched in F (up to 4.8 wt.%) relative to its igneous precursor, and also differs from the latter in at least some of key REE ratios [e.g., shows (La/Yb) cn  25, or a negative Ce anomaly]. The only significant exception is Sr(REE,Na)-rich replacement zones and overgrowths on igneous apatite from some dolomite(-bearing) carbonati...

The Bogosu-Prestea mining district of southwestern Ghana is a 33 km section of the Early Proterozoic Ashanti Gold Belt. Greenschist facies carbonaceous and carbonate-bearing turbidites and greywackes, and mafic dikes host numerous economic mesothermal gold deposits. Structurally higher ores in the Bogosu concession have brittle deformation and consist of disseminated-sulphide lodes in tectonically-disrupted sedimentary rocks and carbonate-altered mafic dikes. Most gold occurs as micrometre-size particles in arsenian pyrite, and as "invisible" gold in arsenian pyrite and arsenopyrite. The structurally deeper ores of the adjoining Prestea concession are associated with brittle-ductile deformation and consist of extensive crack-seal quartz-veins and graphitic shear zones. Only minor amounts of "invisible" gold were detected; in these deeper lodes, gold occurs dominantly as abundant microscopic and larger particles in sulphide/arsenide minerals and in gangue. The gold distribution patterns revealed by SIMS microprobe analysis and ion maps, EMP and colour staining suggest that most of the primary gold in the Bogosu-Prestea system precipitated in solidsolution with sulphide/arsenide minerals. However, postdepositional concentration and redistribution occurred, in increasing degree with: 1) increase in metamorphic/hydrothermal gradients in the gold system (depth), 2) decrease in the refractory properties of the host mineral, and 3) increase in the amount of post-depositional, host-mineral recrystallization and deformation. Gold evolved from primary solid-solution within sulphide/arsenide minerals, to colloidal and micrometre-size particles concentrated in voids, fractures and internal grain boundaries, and finally to microscopic and larger particles at sulphide/arsenide grain margins and in the gangue assemblage. The general conclusions presented here are applicable to As-rich gold deposits of all ages, worldwide. The presence of gold in late fractures is insufficient evidence for late-stage introduction of gold in mesothermal gold systems.

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