Mineralium Deposita (v.49, #6)

Two drill cores of the UG2 chromitite from the eastern and western Bushveld Complex were studied by whole-rock analysis, ore microscopy, SEM/Mineral Liberation Analysis (MLA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. The top and base of the UG2 main seam have the highest bulk-rock Pd and Pt concentrations. Sulfides mostly occur as aggregates of pentlandite, chalcopyrite, and rare pyrrhotite and pyrite or as individual grains associated mostly with chromite grains. In situ LA-ICP-MS analyses reveal that pentlandite carries distinctly elevated platinum-group element (PGE) contents. In contrast, pyrrhotite and chalcopyrite contain very low PGE concentrations. Pentlandite shows average maximum values of 350–1,000 ppm Pd, 200 ppm Rh, 130–175 ppm Ru, 20 ppm Os, and 150 ppm Ir, and is the principal host of Pd and Rh in the studied ores of the UG2. Mass balance calculations were conducted for samples representing the UG2 main seam of the drill core DT46, eastern Bushveld. Pentlandite consistently hosts elevated contents of the whole-rock Pd (up to 55 %) and Rh (up to 46 %), and erratic contents of Os (up to 50 %), Ir (2 to 17 %), and Ru (1–39 %). Platinum-group mineral (PGM) investigations support these mass balance results; most of the PGM are Pt-dominant such as braggite/cooperite and Pt-Fe alloys or laurite (carrying elevated concentrations of Os and Ir). Palladium and Rh-bearing PGM are rare. Both PGE concentrations and their distribution in base-metal sulfides (BMS) in the UG2 largely resemble that of the Merensky Reef, as most of the Pd and Rh are incorporated in pentlandite, whereas pyrrhotite, chalcopyrite, and pyrite are almost devoid of PGE.
Keywords: Platinum-group elements (PGE); UG2; Bushveld Complex; South Africa; LA-ICP-MS; MLA

The Grasvally Norite–Pyroxenite–Anorthosite (GNPA) member within the northern limb of the Bushveld Complex is a mineralized, layered package of mafic cumulates developed to the south of the town of Mokopane, at a similar stratigraphic position to the Platreef. The concentration of platinum-group elements (PGE) in base metal sulfides (BMS) has been determined by laser ablation inductively coupled plasma–mass spectrometry. These data, coupled with whole-rock PGE concentrations and a detailed account of the platinum-group mineralogy (PGM), provide an insight into the distribution of PGE and chalcophile elements within the GNPA member, during both primary magmatic and secondary hydrothermal alteration processes. Within the most unaltered sulfides (containing pyrrhotite, pentlandite, and chalcopyrite only), the majority of IPGE, Rh, and some Pd occur in solid solution within pyrrhotite and pentlandite, with an associated Pt–As and Pd–Bi–Te dominated PGM assemblage. These observations in conjunction with the presence of good correlations between all bulk PGE and base metals throughout the GNPA member indicate the presence and subsequent fractionation of a single PGE-rich sulfide liquid, which has not been significantly altered. In places, the primary sulfides have been replaced to varying degrees by a low-temperature assemblage of pyrite, millerite, and chalcopyrite. These sulfides are associated with a PGM assemblage characterized by the presence of Pd antimonides and Pd arsenides, which are indicative of hydrothermal assemblages. The presence of appreciable quantities of IPGE, Pd and Rh within pyrite, and, to a lesser, extent millerite suggests these phases directly inherited PGE contents from the pyrrhotite and pentlandite that they replaced. The replacement of both the sulfides and PGM occurred in situ, thus preserving the originally strong spatial association between PGM and BMS, but altering the mineralogy. Precious metal geochemistry indicates that fluid redistribution of PGE is minimal with only Pd, Au, and Cu being partially remobilized and decoupled from BMS. This is also indicated by the lower concentrations of Pd evident in both pyrite and millerite compared with the pentlandite being replaced. The observations that the GNPA member was mineralized prior to intrusion of the Main Zone and that there was no local footwall control over the development of sulfide mineralization are inconsistent with genetic models involving the in situ development of a sulfide liquid through either depletion of an overlying magma column or in situ contamination of crustal S. We therefore believe that our observations are more compatible with a multistage emplacement model, where preformed PGE-rich sulfides were emplaced into the GNPA member. Such a model explains the development and distribution of a single sulfide liquid throughout the entire 400–800 m thick succession. It is therefore envisaged that the GNPA member formed in a similar manner to its nearest analogue the Platreef. Notable differences however in PGE tenors indicate that the ore-forming process may have differed slightly within the staging chambers that supplied the Platreef and GNPA member.
Keywords: Bushveld Complex; Northern limb; Platinum-group elements; Platinum-group minerals; Sulfides; Laser-ablation ICP-MS

Fluid–rock interaction related to the circulation of hydrothermal fluids can strongly modify the physicochemical properties of wall rocks in porphyry Cu deposits. These processes can also produce compositional and textural changes in ferromagnetic minerals, which can be quantified using magnetic methods. In the Escondida porphyry Cu deposit of northern Chile, each hydrothermally altered lithology is characterized by a discrete assemblage of Fe–Ti oxide minerals. These minerals have distinctive bulk magnetic susceptibility (K bulk), temperature-dependent magnetic susceptibility, and magnetic hysteresis parameters. Selectively altered rocks (i.e., potassic and chloritic alteration types) exhibit the highest K bulk values (>3.93 × 10−3 SI units), and their hysteresis parameters indicate multidomain magnetic mineral behavior. This suggests that these rocks are composed of the coarsest magnetic grain sizes within the deposit. Optical analyses and susceptibility–temperature curves confirm that the magnetic signals in selectively altered rocks are mainly carried by secondary magnetite. In contrast, pervasively altered rocks (i.e., quartz-sericite and argillic alteration types) exhibit low K bulk values (<1.93 × 10−4 SI units) and contain smaller pseudo-single domain magnetic grain assemblages. This is consistent with the destruction and/or reduction in size of magnetite under acidic conditions. The results therefore demonstrate a genetic relationship between the hydrothermal alteration processes, Fe–Ti oxide minerals, and magnetic properties of the wall rock in the Escondida deposit. These magnetic methods can be considered a sensitive and efficient petrophysical tool for the identification and semi-quantification of alteration assemblages, and facilitating the recognition and mapping of discrete hydrothermal zones during exploration and operation of porphyry Cu deposits.
Keywords: Escondida deposit; Fe–Ti oxide minerals; Hydrothermal alteration; Magnetic properties; Porphyry Cu

Tuwu is the largest porphyry copper deposit discovered in the Eastern Tianshan Mountains, Xinjiang, China. A newly recognized volcanic complex in the Early Carboniferous Qi’eshan Group at Tuwu consists of basalt, andesite, and diorite porphyry. The plagiogranite porphyry was emplaced into this complex at 332.8±2.5 Ma (U–Pb zircon SIMS determination). Whole-rock element geochemistry shows that the volcanic complex and plagiogranite porphyry formed in the same island arc, although the complex was derived by partial melting of the mantle wedge and the plagiogranite porphyry by partial melting of a subducting slab. The diorite and the plagiogranite porphyries have both been subjected to intense hydrothermal alteration and associated mineralization, but the productive porphyry is the plagiogranite porphyry. Three alteration and mineralization stages, including pre-, syn- and post-ore stages, have been recognized. The pre-ore stage formed a barren propylitic alteration which is widespread in the volcanic complex. The syn-ore stage is divided into three sub-stages: Stage 1 is characterized by potassic alteration with chalcopyrite + bornite + chalcocite; Stage 2 is marked by chlorite–sericite–albite alteration with chalcopyrite ± pyrite ± bornite; Stage 3 is represented by phyllic alteration with chalcopyrite + pyrite ± molybdenite. The post-ore stage produced a barren argillic alteration limited to the diorite porphyry. A specific feature of the Tuwu deposit is that the productive porphyry was emplaced into a very mafic package, and reaction of the resulting fluids with the ferrous iron-rich hostrocks was a likely reason that Tuwu is the largest porphyry in the district.
Keywords: Volcanic complex; Porphyry; Mafic hostrock; Hydrothermal alteration; Tuwu; Xinjiang

Geological and isotopic evidence for magmatic-hydrothermal origin of the Ag–Pb–Zn deposits in the Lengshuikeng District, east-central China by Changming Wang; Da Zhang; Ganguo Wu; M. Santosh; Jing Zhang; Yigan Xu; Yaoyao Zhang (733-749).
The Lengshuikeng ore district in east-central China has an ore reserve of ∼43 Mt with an average grade of 204.53 g/t Ag and 4.63 % Pb + Zn. Based on contrasting geological characteristics, the mineralization in the Lengshuikeng ore district can be divided into porphyry-hosted and stratabound types. The porphyry-hosted mineralization is distributed in and around the Lengshuikeng granite porphyry and shows a distinct alteration zoning including minor chloritization and sericitization in the proximal zone; sericitization, silicification, and carbonatization in the peripheral zone; and sericitization and carbonatization in the distal zone. The stratabound mineralization occurs in volcano-sedimentary rocks at ∼100–400 m depth without obvious zoning of alterations and ore minerals. Porphyry-hosted and stratabound mineralization are both characterized by early-stage pyrite–chalcopyrite–sphalerite, middle-stage acanthite–native silver–galena–sphalerite, and late-stage pyrite–quartz–calcite. The δ34S values of pyrite, sphalerite, and galena in the ores range from −3.8 to +6.9‰ with an average of +2.0‰. The C–O isotope values of siderite, calcite, and dolomite range from −7.2 to −1.5‰ with an average of −4.4‰ (V-PDB) and from +10.9 to +19.5‰ with an average of +14.8‰ (V-SMOW), respectively. Hydrogen, oxygen, and carbon isotopes indicate that the hydrothermal fluids were derived mainly from meteoric water, with addition of minor amounts of magmatic water. Geochronology employing LA–ICP–MS analyses of zircons from a quartz syenite porphyry yielded a weighted mean 206Pb/238U age of 136.3 ± 0.8 Ma considered as the emplacement age of the porphyry. Rb–Sr dating of sphalerite from the main ore stage yielded an age of 126.9 ± 7.1 Ma, marking the time of mineralization. The Lengshuikeng mineralization classifies as an epithermal Ag–Pb–Zn deposit.
Keywords: Stable isotope; Geochemistry; Porphyry; Stratabound; Ag–Pb–Zn; Lengshuikeng

Large rounded pyrite grains (>1 mm), commonly referred to as “buckshot” pyrite grains, are a characteristic feature of the auriferous conglomerates (reefs) in the Witwatersrand and Ventersdorp supergroups, Kaapvaal Craton, South Africa. Detailed petrographic analyses of the reefs indicated that the vast majority of the buckshot pyrite grains are of reworked sedimentary origin, i.e., that the pyrite grains originally formed in the sedimentary environment during sedimentation and diagenesis. Forty-one of these reworked sedimentary pyrite grains from the Main, Vaal, Basal, Kalkoenkrans, Beatrix, and Ventersdorp Contact reefs were analyzed for their multiple sulfur isotope compositions (δ34S, Δ33S, and Δ36S) to determine the source of the pyrite sulfur. In addition, five epigenetic pyrite samples (pyrite formed after sedimentation and lithification) from the Middelvlei and the Ventersdorp Contact reefs were measured for comparison. The δ34S, Δ33S, and Δ36S values of all 41 reworked sedimentary pyrite grains indicate clear signatures of mass-dependent and mass-independent fractionation and range from −6.8 to +13.8 ‰, −1.7 to +1.7 ‰, and −3.9 to +0.9 ‰, respectively. In contrast, the five epigenetic pyrite samples display a very limited range of δ34S, Δ33S, and Δ36S values (+0.7 to +4.0 ‰, −0.3 to +0.0 ‰. and −0.3 to +0.1 ‰, respectively). Despite the clear signatures of mass-independent sulfur isotope fractionation, very few data points plot along the primary Archean photochemical array suggesting a weak photolytic control over the data set. Instead, other factors command a greater degree of influence such as pyrite paragenesis, the prevailing depositional environment, and non-photolytic sulfur sources. In relation to pyrite paragenesis, reworked syngenetic sedimentary pyrite grains (pyrite originally precipitated along the sediment-water interface) are characterized by negative δ34S and Δ33S values, suggesting open system conditions with respect to sulfate supply and the presence of microbial sulfate reducers. On the contrary, most reworked diagenetic sedimentary pyrite grains (pyrite originally precipitated below the sediment-water interface) show positive δ34S and negative Δ33S values, suggesting closed system conditions. Negligible Δ33S anomalies from epigenetic pyrite suggest that the sulfur was sourced from a mass-dependent or isotopically homogenous metamorphic/hydrothermal fluid. Contrasting sulfur isotope compositions were also observed from different depositional environments, namely fluvial conglomerates and marine-modified fluvial conglomerates. The bulk of the pyrite grains from fluvial conglomerates are characterized by a wide range of δ34S values (−6.2 to +4.8 ‰) and small Δ33S values (±0.3 ‰). This signature likely represents a crustal sulfate reservoir derived from either volcanic degassing or from weathering of sulfide minerals in the hinterland. Reworked sedimentary pyrite grains from marine-modified fluvial conglomerates share similar isotope compositions, but also produce a positive Δ33S/δ34S array that overlaps with the composition of Archean barite, suggesting the introduction of marine sulfur. These results demonstrate the presence of multiple sources of sulfur, which include atmospheric, crustal, and marine reservoirs. The prevalence of the mass-dependent crustal sulfur isotope signature in fluvial conglomerates suggests that sulfate concentrations were probably much higher in terrestrial settings in comparison to marine environments, which were sulfate-deficient. However, the optimum conditions for forming terrestrial sedimentary pyrite were probably not during fluvial progradation but rather during the early phases of flooding of low angle unconformities, i.e., during retrogradational fluvial deposition, coupled in some cases with marine transgressions, immediately following inflection points of maximum rate of relative sea level fall.

Between 1957 and 1990, the Peñarroya Mining and Metallurgical Company (SMMPE) disposed about 60 million tonnes of tailings materials directly to the Mediterranean Sea. A substantial part of it (12.5 Mt) was dragged back by the sea currents progressively infilling the Portman Bay (Murcia, SE Spain), thus making the shoreline advance between 500 and 600 m seaward. The Roberto froth flotation plant processed mineral from manto-type deposits belonging to the Sierra de Cartagena-La Unión lead-zinc district. One of the mineral assemblages present in these deposits comprises greenalite, magnetite, sulfides, carbonates, and silica. Despite that magnetite recovery was undertaken by SMMPE between 1959 and 1967, we estimate that magnetite contained in the tailings hosts a substantial resource that could be as large as 2.3 Mt of iron ore. The ore contains magnetite ± hematite ± siderite. Tidal waves and sea currents led to gravimetric classification of the tailings material, with concentration of the dense iron oxides in the sandy fractions, eventually forming a coastal placer iron deposit. A major problem for magnetic separation is the intimate intergrowth between magnetite, hematite, and siderite. Besides, the sands contain large concentrations of Pb (0.27 %), Zn (0.72 %), and As (559 ppm).
Keywords: Iron ore; Beach placer deposit; Magnetite; Portman Bay; La Unión; Spain