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Titanium oxide minerals along the P2 fault in the eastern Athabasca Basin are characterized to constrain their origin and the geological history of the area. Two types of rutile are recognized in the basement rocks. Early rutile is disseminated in graphitic metapelite and quartzite, and it formed during regional metamorphism and post-metamorphic hydrothermal activity. Late rutile occurs as a needle-like alteration product of mica and likely formed during retrogression of the basement. In graphitic metapelite, early rutile commonly occurs with an assemblage of oxy-dravite, quartz, graphite, zircon, pyrite, biotite, and muscovite. In quartzite, rutile occurs with quartz, sillimanite, muscovite, and zircon. Metamorphic rutile is characterized by high Nb/Ta ratios (up to 47) with high concentrations of U (up to 126 ppm) and V4+ (up to 1.44 wt%; V valance calculated from EPMA data). Hydrothermal rutile contains distinctly low Nb/Ta (as low as 4.80) with high Ta (≤3050 ppm), and relatively low V (as V 3+; as low as 0.02 wt%) and U (as low as 9.06 ppm), reflecting fluids in reduced oxidation conditions. Anatase forms small anhedral (rarely coarse and euhedral) grains in the basal sandstones and altered basement rocks. In sandstones, anatase occurs with the late diagenetic mineral assemblage, whereas in basement rocks it commonly occurs with the clay-sized minerals related to uranium mineralization. In both rocks, anatase likely formed through the dissolution of rutile and/or other Ti-bearing minerals. Anatase is characterized by variably high Fe (up to 0.99 wt%; possibly contributed by hematite micro-or nanoinclusions) and U (up to 180 ppm). The mineral assemblages and composition of anatase suggest its protracted crystallization from relatively low temperature, oxidizing, acidic, uraniferous fluids of the sandstones during late diagenesis and hydrothermal activity. Therefore, the occurrence of anatase records the incursion of basin fluids into the basement, and the interaction of basement rocks with fluids responsible for the formation of the McArthur River uranium deposit. The results of this study confirm that Ti-oxides are useful in unraveling the geological history of an area that underwent prolonged hydrothermal activity.

Evidence of secondary gold enrichment due to the addition of new gold into an earlier orogenic quartz-carbonate vein deposit by magmatic-hydrothermal fluids is strongly suggested for the Madrid Deposit, hosted in the Hope Bay Greenstone Belt in Nunavut, Canada. The conclusion is based on an extensive in situ microanalytical protocol (SEM, confocal Raman microspectroscopy, microthermometry, decrepitate mound analysis, LA-ICP-MS, cathodoluminescence, SIMS) not previously applied to gold systems. This approach was used to characterize the mineralogy and fluid inclusion systematics associated with the upgrading event. Mineralization comprised of only Ag-bearing gold (“electrum”; 89.8 at. % Au avg.; n = 8) is present throughout all investigated laminated and brecciated orogenic quartz veins. However, in high-grade vein intersections where gold grades are locally elevated (up to 122 g/t), assemblages containing tennantite-tetrahedrite + chalcopyrite + electrum (80.7 at. % Au avg.; n = 15) ± Ag Pb Au tellurides occur that are texturally late-stage relative to electrum-only mineralization. Subdomains of quartz coeval with this later assemblage are optically- and texturally-distinct from earlier orogenic quartz. This late mineral assemblage is absent in all low-grade vein intersections (∼1 g/t Au avg.) examined where only electrum is identified. Quartz-hosted fluid inclusions (H2O NaCl ± CO2) of intermediate salinity (16.7 ± 1.2 wt.% NaCl equiv.; n = 93) were identified only in the high-grade vein samples and are present along healed planes associated with tennantite-tetrahedrite + chalcopyrite + electrum ± Ag Pb Au telluride assemblages. In situ SIMS δ18O analyses of quartz, combined with temperature constraints from mineral equilibria, show that early orogenic vein quartz and late quartz subdomains associated with gold upgrading precipitated from fluids with similar δ18OH2O values of 4.5–12.4‰ (n = 10) and −5.5 to 11.8‰ (n = 13), respectively. Isotopic data suggests that meteoric water was a negligible component in fluids responsible for gold precipitation. Microthermometry and Raman spectroscopy show that upgrading fluids were distinct in composition compared to the earlier metamorphic fluids (H2O NaCl CO2 ± CH4 ± N2; 4.6 ± 1.6 wt.% NaCl equiv., n = 33) and later Canadian Shield basement brines (H2O NaCl; 22.4 ± 1.2 wt.% NaCl equiv., n = 12) which have also been identified in the fluid inclusion record at Madrid. Laser ablation ICP-MS analyses indicate the gold upgrading fluids are enriched in As Sb Zn Pb and LILE (Cs Ba Rb Sr); these data are consistent with late fluids derived from an evolved magmatic-hydrothermal system. Trace element mapping of pyrite, coupled with principle component analysis of the data, confirms a strong correlation between Au and Ag Te Sb Bi W( As) in upgraded veins, whereas only Au and As strongly correlate in low-grade veins. The study suggests that gold upgrading, either involving newly introduced gold or remobilization of existing gold, can be linked to the incursion of a late magmatic-hydrothermal fluid that post-dated formation of the main orogenic-type auriferous quartz vein system. The geological setting and mineral-chemical features suggest an intrusion-related (i.e., porphyry), or intermediate-sulfidation epithermal mineralization style for the later event. This work provides another example of the importance of compositionally distinct cumulative hydrothermal events in the development of high-grade gold deposits in orogenic settings.

The reaction of Pt(tfd)(2) [tfd = S(2)C(2)(CF(3))(2)] with excess 2,3-dimethyl-1,3-butadiene initially yields the expected 1:1 adduct, in which the diene has added across two sulfur atoms on separate tfd ligands. However, within 1 day at 50 degrees C, this kinetic product quantitatively converts into a thermodynamic product where two dienes have added to one tfd ligand via unprecedented addition across the dithiolene CS bonds. The new reaction is highly selective for the C(2)-symmetric diastereomer. A new chiral bisthioether chelate ligand has formed in the product, which has been characterized crystallographically.

A bis-double-decker complex has been assembled from the nickel bisdithiolene complex [Ni(S 2C 2Me 2) 2] (1-/2-) and two [Cp*Fe] (+) units (Cp* = C 5Me 5). The complex, [(eta (5)-Cp*-Fe-mu-eta (5),eta (5)-((S 2C 2Me 2) 2Ni)Fe-eta (5)-Cp*] ( n ) ( 1 ( n )), was isolated in two charge states ( n = 0, 1). The structure of 1 (+) was confirmed by X-ray crystallography for 1 (+)PF 6 (-) and 1 (+)BF 4 (-), and it shows the nickel bisdithiolene units pi-donating to iron centers. Both salts crystallize in a centrosymmetric space group (center of inversion at nickel). Computational (density functional theory) data indicate a highly delocalized spin density for 1 (+). The reaction of 1 with 1 or 2 equiv of HBF 4 leads to oxidation to form 1 (+) or 1 (2+), respectively. On an electrochemical time scale, reversibility is observed for the redox series 1/ 1 (+)/ 1 (2+), with an additional slower step for oxidation of 1 (2+).