Mineralium Deposita (v.51, #2)

Volcanogenic massive sulphide (VMS) deposits are commonly enriched in Cu, Zn and Pb and can also be variably enriched in Au, As, Sb, Se and Te. The behaviour of these elements during hydrothermal alteration of the oceanic crust is not well known. Ocean Drilling Program (ODP) Hole 1256D penetrates a complete in situ section of the upper oceanic crust, providing a unique sample suite to investigate the behaviour of metals during hydrothermal alteration. A representative suite of samples was analysed for Au, As, Sb, Se and Te using low detection limit methods, and a mass balance of metal mobility has been carried out through comparison with a fresh Mid-Oceanic Ridge Basalt (MORB) glass database. The mass balance shows that Au, As, Se, Sb, S, Cu, Zn and Pb are depleted in the sheeted dyke and plutonic complexes by −46 ± 12, −27 ± 5, −2.5 ± 0.5, −27 ± 6, −8.4 ± 0.7, −9.6 ± 1.6, −7.9 ± 0.5 and −44 ± 6 %, respectively. Arsenic and Sb are enriched in the volcanic section due to seawater-derived fluid circulation. Calculations suggest that large quantities of metal are mobilised from the oceanic crust but only a small proportion is eventually trapped as VMS mineralisation. The quantity of Au mobilised and the ratio of Au to base metals are similar to those of mafic VMS, and ten times enrichment of Au would be needed to form a Au-rich VMS. The Cu-rich affinity of mafic VMS deposits could be explained by base metal fractionation both in the upper sheeted dykes and during VMS deposit formation.
Keywords: Volcanic massive sulphide; Au-rich VMS; ODP Hole 1256D; Hydrothermal alteration; Oceanic crust

We present Mo isotopic ratios of molybdenite from five porphyry molybdenum deposits (Chagele, Sharang, Jiru, Qulong, and Zhuonuo) and one quartz-molybdenite vein-type deposit (Jigongcun) along the Gangdese metallogenic belt in the Tibetan Plateau. These deposits represent a sequence of consecutive events of the India-Asia collision at different periods. Additional molybdenite samples from the Henderson Mo deposit (USA), the oceanic subduction-related El Teniente (Chile), and Bingham (USA) porphyry Cu-(Mo) deposits were analyzed for better understanding the controls on the Mo isotope systematics of molybdenite. The results show that molybdenite from Sharang, Jiru, Qulong, and Zhuonuo deposits have similar δ97Mo (∼0 ‰), in agreement with the values of the Henderson Mo deposit (−0.10 ‰). In contrast, samples from the Changle and Jigongcun deposit have δ97Mo of 0.85 ‰ to 0.88 ‰ and −0.48 %, respectively. Molybdenite from the El Teniente and Bingham deposits yields intermediate δ97Mo of 0.27 and 0.46 ‰, respectively. The Mo isotopes, combined with Nd isotope data of the ore-bearing porphyries, indicate that source of the ore-related magmas has fundamental effects on the Mo isotopic compositions of molybdenite. Our study indicates that molybdenite related to crustal-, and mantle-derived magmas has positive or negative δ97Mo values, respectively, whereas molybdenite from porphyries formed by crust-mantle mixing has δ97Mo close to 0 ‰. It is concluded that the Mo isotope composition in the porphyry system is a huge source signature, without relation to the tectonic setting under which the porphyry deposits formed.
Keywords: Molybdenite; Molybdenum isotope; Gangdese; Tibetan Plateau

Sorption behavior of the Pt(II) complex anion on manganese dioxide (δ-MnO2): a model reaction to elucidate the mechanism by which Pt is concentrated into a marine ferromanganese crust by Mamiko Yamashita Maeno; Hironori Ohashi; Kotaro Yonezu; Akane Miyazaki; Yoshihiro Okaue; Koichiro Watanabe; Tamao Ishida; Makoto Tokunaga; Takushi Yokoyama (211-218).
It is difficult to directly investigate the chemical state of Pt in marine ferromanganese crusts (a mixture of hydrous iron(III) oxide and manganese dioxide (δ-MnO2)) because it is present at extremely low concentration levels. This paper attempts to elucidate the mechanism by which Pt is concentrated into marine ferromanganese crust from the Earth’s continental crust through ocean water. In this investigation, the sorption behavior of the Pt(II) complex ions on the surface of the δ-MnO2 that is a host of Pt was examined as a model reaction. The δ-MnO2 sorbing Pt was characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) to determine the chemical state of the Pt. Hydrolytic Pt(II) complex ions were specifically sorbed above pH 6 by the formation of a Mn-O-Pt bond. XPS spectra and XANES spectra for δ-MnO2 sorbing Pt showed that the sorbed Pt(II) was oxidized to Pt(IV) on δ-MnO2. The extended X-ray absorption fine structure (EXAFS) analysis showed that the coordination structure of Pt sorbed on δ-MnO2 is almost the same as that of the [Pt(OH)6]2− complex ion used as a standard. Therefore, the mechanism for the concentration of Pt in marine ferromanganese crust may be an oxidative substitution (penetration of Pt(IV) into structure of δ-MnO2) by a reduction-oxidation reaction between Pt(II) in [PtCl4-n(OH)n]2− and Mn(IV) in δ-MnO2 through a Mn-O-Pt bond.
Keywords: Sorption of Pt; δ-MnO2 ; XPS; XAFS; Ferromanganese crust

The Kiggavik-Andrew Lake structural trend consists of four mineralized zones, partially outcropping, lying 2 km south of the erosional contact with the unmetamorphosed sandstone and basal conglomerates of the Paleoproterozoic Thelon Formation. The mineralization is controlled by a major E-W fault system associated with illite and sudoite alteration halos developed in the Archean metagraywackes of the Woodburn Lake Group. Aluminum phosphate sulfate (APS) minerals from the alunite group crystallized in association with the clay minerals in the basement alteration halo as well as in the overlying sandstones, which underwent mostly diagenesis. APS minerals are Sr- and S-rich (svanbergite end-member) in the sedimentary cover overlying the unconformity, whereas they are light rare earth elements (LREE)-rich (florencite end-member) in the altered basement rocks below the unconformity. The geochemical signature of each group of APS minerals together with the petrography indicates three distinct generations of APS minerals related to the following: (1) paleoweathering of continental surfaces prior to the basin occurrence, (2) diagenetic processes during the burial history of the lower unit of the Thelon sandstones, and (3) hydrothermal alteration processes which accompanied the uranium deposition in the basement rocks and partially overlap the sedimentary-diagenetic mineral parageneses. In addition, the association of a first generation of APS minerals with both detrital cerium oxide and aluminum oxy-hydroxide highlights the fact that a part of the detrital material of the basal Thelon Formation originated from eroded paleolaterite (allochthonous regolith). The primary rare earth element (REE)-bearing minerals (e.g., monazite, REE carbonates, and allanite) of the host rocks were characterized to identify the potential sources of REE. The REE chemical composition highlights a local re-incorporation of the REE released from the alteration processes in the APS minerals of hydrothermal origin. The distinctive geochemical signatures between diagenetic (or sedimentary) and hydrothermal APS minerals suggest a different source material in the Thelon basin than in the Athabasca basin.
Keywords: APS minerals; Thelon; Hydrothermal alteration; Paleo-laterite

Numerous polymetallic volcanogenic massive sulfide (VMS), vein, and replacement deposits are distributed along the Changning–Menglian suture zone in Sanjiang Tethyan metallogenic province, SW China. Laochang is the largest Pb–Zn–Ag vein and replacement deposit in this area, with a proven reserve of 0.51 Mt Pb, 0.34 Mt Zn, and 1,737 t Ag. Its age and relationship to magmatic events and VMS deposits in the region, however, have long been debated. In this paper, we present pyrite Re–Os and titanite U–Pb ages aiming to provide significant insights into the timing and genesis of the Pb–Zn–Ag mineralization. Pyrite grains in textural equilibrium with galena, sphalerite, and chalcopyrite from stratabound Pb–Zn–Ag and Cu-bearing Pb–Zn–Ag orebodies have a Re–Os isochron age of 45.7 ± 3.1 Ma (2σ, mean square weighted deviation (MSWD) = 0.45), whereas titanite grains intergrown with sulfide minerals yield a weighted mean 206Pb/238U age of 43.4 ± 1.2 Ma (2σ, n = 8). A Mo-mineralized granitic porphyry intersected by recent drilling below the Laochang Pb–Zn–Ag ores yields a zircon U–Pb age of 44.4 ± 0.4 Ma (2σ, n = 12). Within analytical uncertainties, the ages of the Pb–Zn–Ag deposit and the concealed Mo-mineralized porphyry are indistinguishable, indicating that they are products of a single magmatic hydrothermal system. The results show that Laochang Pb–Zn–Ag deposit is significantly younger than the host mafic volcanic rock (zircon U–Pb age of 320.8 ± 2.7 Ma; 2σ, n = 12) and Silurian VMS deposits along the Changning–Menglian suture zone, arguing against its origin as a Carboniferous VMS deposit as many researchers claimed. The initial 187Os/188Os ratio (0.540 ± 0.012) obtained from the pyrite Re–Os isochron suggests that metals were likely derived from the granitic porphyry that formed from a hybrid magma due to mixing of crustal- and mantle-derived melts, rather than from the mafic volcanic host rocks as previously thought. Our results favor that the Laochang Pb–Zn–Ag deposit is the shallow product of a porphyry Mo system. Thus, there is potential for discovery of porphyry Mo or Cu–Mo deposits below Laochang and similar Pb–Zn–Ag deposits in the Changning–Menglian suture zone.
Keywords: Geochronology; Stratabound Pb–Zn–Ag mineralization; Porphyry Mo deposits; Changning–Menglian suture

Metal-rich fluid inclusions provide new insights into unconformity-related U deposits (Athabasca Basin and Basement, Canada) by Antonin Richard; Michel Cathelineau; Marie-Christine Boiron; Julien Mercadier; David A. Banks; Michel Cuney (249-270).
The Paleoproterozoic Athabasca Basin (Canada) hosts numerous giant unconformity-related uranium deposits. The scope of this study is to establish the pressure, temperature, and composition (P-T-X conditions) of the brines that circulated at the base of the Athabasca Basin and in its crystalline basement before, during and after UO2 deposition. These brines are commonly sampled as fluid inclusions in quartz- and dolomite-cementing veins and breccias associated with alteration and U mineralization. Microthermometry and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data from five deposits (Rabbit Lake, P-Patch, Eagle Point, Millennium, and Shea Creek) complement previously published data for the McArthur River deposit. In all of the deposits investigated, fluid inclusion salinity is between 25 and 40 wt.% NaCl equiv., with compositions displaying a continuum between a “NaCl-rich brine” end-member (Cl > Na > Ca > Mg > K) and a “CaCl2-rich brine” end-member (Cl > Ca ≈ Mg > Na > K). The CaCl2-rich brine has the highest salinity and shows evidence for halite saturation at the time of trapping. The continuum of compositions between the NaCl-rich brine and the CaCl2-rich brine end-members combined with P-T reconstructions suggest anisothermal mixing of the two brines (NaCl-rich brine, 180 ± 30 °C and 800 ± 400 bars; CaCl2-rich brine, 120 ± 30 °C and 600 ± 300 bars) that occurred under fluctuating pressure conditions (hydrostatic to supra-hydrostatic). However, because the two brines were U bearing and therefore oxidized, brine mixing was probably not the driving force for UO2 deposition. Several scenarios are put forward to account for the Cl-Na-Ca-Mg-K composition of the brines, involving combinations of seawater evaporation, halite dissolution, mixing with a halite-dissolution brine, Mg/Ca exchange by dolomitization, Na/Ca exchange by albitization of plagioclase, Na/K exchange by albitization of K-feldspar, and Mg loss by Mg-rich alteration. Finally, the metal concentrations in the NaCl-rich and CaCl2-rich brines are among the highest recorded compared to present-day sedimentary formation waters and fluid inclusions from basin-hosted base metal deposits (up to 600 ppm U, 3000 ppm Mn, 4000 ppm Zn, 6000 ppm Cu, 8000 ppm Pb, and 10,000 ppm Fe). The CaCl2-rich brine carries up to one order of magnitude more metal than the NaCl-rich brine. Though the exact origin of major cations and metals of the two brines remains uncertain, their contrasting compositions indicate that the two brines had distinct flow paths and fluid-rock interactions. Large-scale circulation of the brines in the Athabasca Basin and Basement was therefore a key parameter for metal mobility (including U) and formation of unconformity-related U deposits.
Keywords: Brines; Metals; Fluid inclusions; Unconformity; Uranium; Athabasca

Nickel dispersion and enrichment at the bottom of the regolith: formation of pimelite target-like ores in rock block joints (Koniambo Ni deposit, New Caledonia) by Michel Cathelineau; Benoît Quesnel; Pierre Gautier; Philippe Boulvais; Clément Couteau; Maxime Drouillet (271-282).
In New Caledonian Ni deposits, the richest Ni silicate ores occur in fractures within the bedrock and saprolite, generally several tens of meters to hundred meters below the present-day surface. Fracture-related Ni silicate ore accounts for high Ni grades, at least a few weight percent above the average exploited grade (2.5 %). These Ni-rich veins are affected by active dissolution-precipitation processes at the level of the water table. Ni in solution is precipitated as silicates in thin layer cementing joints. This mineralization is characterized by chemical and mineralogical concentric zoning with an outer green rim around an inner white zone composed, from the edge to the centre of the block, (i) a highly oxidized and altered zone, (ii) a green pure Ni-rich pimelite zone, (iii) a zone (limited to a few centimetres) with a mixture of Ni-poor kerolite and Ni-rich pimelite and intermediate colours and (iv) a large white Mg-kerolite mineralization zone. This study proposes that the concentric zonation results from evapo-precipitation process related to alternate periods of hydration and drying, induced by water table movements. This extensive dispersion of Ni in concentrically zoned ores can partly explain the rather monotonous Ni grade of the bulk exploitation at the base of the regolith with values between 2 and 3 wt%.
Keywords: Kerolite-pimelite; Garnierite; Ni-laterite; New Caledonia; Dissolution-precipitation

Genesis of the vein-type tungsten mineralization at Nyakabingo (Rwanda) in the Karagwe–Ankole belt, Central Africa by S. Dewaele; F. De Clercq; N. Hulsbosch; K. Piessens; A. Boyce; R. Burgess; Ph. Muchez (283-307).
The vein-type tungsten deposit at Nyakabingo in the central Tungsten belt of Rwanda is located in the eastern flank of the complex Bumbogo anticlinal structure. The host rock is composed of alternating sequences of sandstones, quartzites, and black pyritiferous metapelitic rocks. Two types of W-mineralized quartz veins have been observed: bedding-parallel and quartz veins that are at high angle to the bedding, which are termed crosscutting veins. Both vein types have been interpreted to have been formed in a late stage of a compressional deformation event. Both vein types are associated with small alteration zones, comprising silicification, tourmalinization, and muscovitization. Dating of muscovite crystals at the border of the veins resulted in a maximum age of 992.4 ± 1.5 Ma. This age is within error similar to the ages obtained for the specialized G4 granites (i.e., 986 ± 10 Ma). The W-bearing minerals formed during two different phases. The first phase is characterized by scheelite and massive wolframite, while the second phase is formed by ferberite pseudomorphs after scheelite. These minerals occur late in the evolution of the massive quartz veins, sometimes even in fractures that crosscut the veins. The ore minerals precipitated from a H2O–CO2–CH4–N2–NaCl–(KCl) fluid with low to moderate salinity (0.6–13.8 eq. wt% NaCl), and minimal trapping temperatures between 247 and 344 °C. The quartz veins have been crosscut by sulfide-rich veins. Based on the similar setting, mineralogy, stable isotope, and fluid composition, it is considered that both types of W-mineralized quartz veins formed during the same mineralizing event. Given the overlap in age between the G4 granites and the mineralized quartz veins, and the typical association of the W deposits in Rwanda, but also worldwide, with granite intrusions, W originated from the geochemically specialized G4 granites. Intense water–rock interaction and mixing with metamorphic fluids largely overprinted the original magmatic-hydrothermal signature.
Keywords: Fluid flow; Karagwe–Ankole belt; Neoproterozoic; Rwanda; Tungsten mineralization