The composition of magmatic Ni–Cu–(PGE) sulfide deposits in the Tati and Selebi-Phikwe belts of eastern Botswana

We studied a number of magmatic Ni–Cu–(PGE) sulfide deposits in two distinct belts in eastern Botswana. The Tati belt contains several relatively small deposits (up to 4.5 Mt of ore at 2.05% Ni and 0.85% Cu) at Phoenix, Selkirk and Tekwane. The deposits are hosted by ca 2.7 Ga, low- to medium-grade metamorphosed gabbroic–troctolitic intrusions situated within or at the periphery of a greenstone belt. The deposits of the Selebi-Phikwe belt are larger in size (up to 31 Mt of ore grade). They are hosted by high-grade metamorphosed gabbronorites, pyroxenites and peridotites believed to be older than ca 2.0 Ga that intruded gneisses of the Central Zone of the Limpopo metamorphic belt. The composition of the sulfide mineralisation in the two belts shows systematic variation. Most of the mineralisation in the Tati belt contains 2–9% Ni and 0.05–4% Cu (Cu/Cu + Ni = 0.4–0.7), whereas most of the mineralisation in the Selebi-Phikwe belt contains 1–3% Ni and 0.1–4% Cu (Cu/Cu + Ni = 0.4–0.9). The Cu–Ni tenors of the ores in both belts are consistent with crystallization from a basaltic magma. The Tati ores contain mostly >3 ppm Pt + Pd (Pt/Pd 0.1–1), with Pd/Ir = 100–1,000, indicative of a differentiated basaltic magma that remained S-undersaturated before emplacement. Most of the Selebi-Phikwe ores have <0.5 ppm Pt + Pd (Pt/Pd < 0.1–1), with Pd/Ir = 10–500. This suggests a relatively less differentiated magma that reached S saturation before emplacement. The Tati rocks show flat mantle-normalised incompatible trace element patterns (average Th/Yb_N = 1.57), except for strong enrichments in large ion lithophile elements (Cs, Rb, Ba, U, K). Such patterns are characteristic of relatively uncontaminated oceanic arc magmas and suggest that the Tati intrusions were emplaced in a destructive plate margin setting. Most of the Selebi-Phikwe rocks (notably Dikoloti) have more fractionated trace element signatures (average Th/Yb_N = 4.22), possibly indicating digestion of upper crustal material during magma emplacement. However, as there are also samples that have oceanic arc-like signatures, an alternative possibility is that the composition of most Selebi-Phikwe rocks reflects tectonic mingling of the intrusive rocks with the country rocks. The implication is that orogenic belts may have a higher prospectivity for magmatic Ni–Cu ores than presently recognised. The trigger mechanism for sulfide saturation and segregation in all intrusions remains unclear. Whereas the host rocks to the intrusions appear to be relatively sulfur poor, addition of crustal S to the magmas is suggested by low Se/S ratios in some of the ores (notably at Selebi-Phikwe). External S sources may thus remain unidentified due to poor exposure and/or S mobility in response to metamorphism.     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Atacamite formation by deep saline waters in copper deposits from the Atacama Desert,Chile: evidence from fluid inclusions,groundwater geochemistry,TEM, and <Superscript>36</Superscript>Cl data

The presence of large amounts of atacamite in oxide zones from ore deposits in the Atacama Desert of northern Chile requires saline solutions for its formation and hyperarid climate conditions for its preservation. We investigated the nature and origin of atacamite-forming solutions by means of coupling groundwater geochemical analyses with fluid inclusion data, high-resolution mineralogical observations, and chlorine-36 (³⁶Cl) data in atacamite from the Mantos Blancos and Spence Cu deposits. In both deposits, the salinities of fluid inclusions in atacamite are comparable to those measured in saline groundwaters sampled from drill holes. The average salinity of fluid inclusions in atacamite for the Mantos Blancos and Spence deposits (~7–9 and 2–3 wt.% NaCl_eq, respectively) are strongly correlated to the salinities at which gypsum supersaturates from groundwaters in both deposits (total dissolved solids ~5–9 and 1–3 wt.% NaCl_eq, respectively). This correlation is confirmed by transmission electron microscopy observations of atacamite-bearing samples, revealing an intimate association between atacamite and gypsum that can be traced down to the nanometer scale. ³⁶Cl data in atacamite provide new lines of evidence concerning the origin and age of the saline waters that formed atacamite in various stratabound and porphyry Cu deposits from the Atacama Desert. All atacamite samples show very low ³⁶Cl-to-Cl ratios (11 × 10⁻¹⁵ to 28 × 10⁻¹⁵ at at⁻¹), comparable to previously reported ³⁶Cl-to-Cl ratios of deep formation waters and old groundwaters. In addition, ³⁶Cl-to-Cl ratios in atacamite correlate with U and Th concentration in the host rocks but are independent from distance to the ocean. This trend supports an interpretation of the low ³⁶Cl-to-Cl ratios in atacamite as representing subsurface production of fissiogenic ³⁶Cl in secular equilibrium with the solutions involved in atacamite formation. Therefore, ³⁶Cl in atacamite strongly suggest that the chlorine in saline waters related to atacamite formation is old (>1.5 Ma) but that atacamite formation occurred more recently (<1.5 Ma) than suggested in previous interpretations. Our data provide new constraints on the origin of atacamite in Cu deposits from the Atacama Desert and support the recent notion that the formation of atacamite in hyperarid climates such as the Atacama Desert is an ongoing process that has occurred intermittently since the onset of hyperaridity.     

Zircon U–Pb and phlogopite <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar age of the Chengchao and Jinshandian skarn Fe deposits,southeast Hubei Province,Middle–Lower Yangtze River Valley metallogenic belt,China

The Chengchao and Jinshandian deposits in the southeast Hubei Province are the two largest skarn Fe deposits in the Middle–Lower Yangtze River Valley metallogenic belt (MLYRVMB), China. They are characterized by NW-striking orebodies that are developed along the contacts between the Late Mesozoic granitoid and Triassic carbonate and clastic rocks. New sensitive high-resolution ion microprobe and laser ablation inductively coupled plasma mass spectrometry zircon U–Pb dating of the mineralization-related quartz diorite and granite at Chengchao yield ages of 129 ± 2 and 127 ± 2 Ma, respectively, and those at Jinshandian of 127 ± 2 and 133 ± 1 Ma, respectively. These results are interpreted as the crystallization age of these intrusions. Hydrothermal phlogopite samples from the skarn ores at Chengchao and Jinshandian have the plateau ⁴⁰Ar–³⁹Ar ages of 132.6 ± 1.4 and 131.6 ± 1.2 Ma, respectively. These results confirm that both intrusions and associated skarn Fe mineralization were formed contemporaneously in the middle Early Cretaceous time. New zircon U–Pb and phlogopite ⁴⁰Ar–³⁹Ar ages in this study, when combined with available precise geochronological data, demonstrate that there were two discontinuous igneous events, corresponding to two episodes of skarn Fe-bearing mineralization in the southeast Hubei Province: (1) 140–136 Ma diorites and quartz diorites and 141–137 Ma skarn Cu–Fe or Fe–Cu deposits and (2) 133–127 Ma quartz diorites and granites and 133–132 Ma skarn Fe deposits. This scenario is similar to that proposed for the entire MLYRVMB. The intrusions related to skarn Fe deposits show obviously petrological and geochemical differences from those related to skarn Cu–Fe or Fe–Cu deposits. The former are quartz diorite and diorite in petrology and have similar adakitic geochemical signatures and in equilibrium with a garnet-rich residue, whereas the latter are petrologically granite and quartz diorite that are distinguishable from adakitic rocks and in equilibrium with a plagioclase residue. These features indicated that two episodes of magmatism and the formation of skarn Fe-bearing deposits in the southeast Hubei Province, MLYRVMB, might be associated lithosphere thinning induced by asthenosphere upwelling during the Late Mesozoic.     

Stable isotope characteristics and origin of ore-forming fluids in copper-gold-polymetallic deposits within strike-slip pull-apart basin of Weishan-Yongping continental collision orogenic belt, Yunnan Province, China

More than 140 middle-small sized deposits or minerals are present in the Weishan-Yongping ore concentration area which is located in the southern part of a typical Lanping strike-slip and pull-apart basin. It has plenty of mineral resources derived from the collision between the Indian and Asian plates. The ore-forming fluid system in the Weishan-Yongping ore concentration area can be divided into two subsystems, namely, the Zijinshan subsystem and Gonglang arc subsystem. The ore-forming fluids of Cu, Co deposits in the Gonglang arc fluid subsystem have δD values between −83.8‰ and −69‰, δ¹⁸O values between 4.17‰ and 10.45‰, and δ¹³C values between −13.6‰ and 3.7‰, suggesting that the ore-forming fluids of Cu, Co deposits were derived mainly from magmatic water and partly from formation water. The ore-forming fluids of Au, Pb, Zn, Fe deposits in the Zijinshan subsystem have δD values between −117.4‰ and −76‰, δ¹⁸O values between 5.32‰ and 9.56‰, and Δ¹³C values between −10.07‰ and −1.5‰. The ore-forming fluids of Sb deposits have δD values between −95‰ and −78‰, δ¹⁸O values between 4.5‰ and 32.3‰, and Δ¹³C values between −26.4‰ and −1.9‰. Hence, the ore-forming fluids of the Zijinshan subsystem must have been derived mainly from formation water and partly from magmatic water. Affected by the collision between the Indian and Asian plates, ore-forming fluids in Weishan-Yongping basin migrated considerably from southwest to northeast. At first, the Gonglang arc subsystem with high temperature and high salinity was formed. With the development of the ore-forming fluids, the Zijinshan subsystem with lower temperature and lower salinity was subsequently formed. Translated from Mineral Deposits, 2006, 25(1): 60–70 [译自: 矿床地质]     

Sulfur isotopic zonation in the Cadia district,southeastern Australia: exploration significance and implications for the genesis of alkalic porphyry gold–copper deposits

The alkalic porphyry gold–copper deposits of the Cadia district occur in the eastern Lachlan Fold Belt of New South Wales, Australia. The district comprises four porphyry deposits (Ridgeway, Cadia Quarry, Cadia Hill, and Cadia East) and two iron–copper–gold skarn deposits (Big Cadia and Little Cadia). Almost 1,000 tonnes of contained gold and more than four million tonnes of copper have been discovered in these systems, making Cadia the world’s largest known alkalic porphyry district, in terms of contained gold. Porphyry gold–copper ore at Cadia is associated with quartz monzonite intrusive complexes, and is hosted by central stockwork and sheeted quartz–sulfide–(carbonate) vein systems. The Cadia porphyry deposits are characterized by cores of potassic and/or calc–potassic alteration assemblages, and peripheral halos of propylitic alteration, with late-stage phyllic alteration mostly restricted to fault zones. Hematite dusting is an important component of the propylitic alteration assemblage, and has produced a distinctive reddening of feldspar minerals in the volcanic wall rocks around the mineralized centers. Sulfide mineralization is strongly zoned at Ridgeway and Cadia East, with bornite-rich cores surrounded by chalcopyrite-rich halos and peripheral zones of pyrite mineralization. The Cadia Hill and Cadia Quarry deposits have chalcopyrite-rich cores and pyrite-rich halos, and Cadia Hill contains a high-level bornite-rich zone. Distinctive sulfur isotopic zonation patterns have been identified at Ridgeway, Cadia Hill, and Cadia East. The deposit cores are characterized by low δ³⁴S_sulfide values (−10 to −4‰), consistent with sulfide precipitation from an oxidized (sulfate-predominant) magmatic fluid at 450 to 400°C. Pyrite grains that occur in the propylitic alteration halos typically have δ³⁴S_sulfide values near 0‰. There is a gradual increase in δ³⁴S_sulfide values outwards from the deposit cores through the propylitic halos. Water–rock interaction during propylitic alteration caused magmatic sulfate reduction and concomitant oxidation of ferrous iron-bearing minerals, resulting in enrichment of ³⁴S in pyrite and also producing the distinctive reddened, hematite-rich alteration halos to the Cadia deposits. These results show that sulfur isotope analyses have potential applications in the exploration of alkalic porphyry-style deposits, with zones of depleted δ³⁴S_sulfide values most prospective for high-grade mineralization.     

The Sarylakh and Sentachan gold-antimony deposits,Sakha-Yakutia: A case of combined mesothermal gold-quartz and epithermal stibnite ores

New mineralogical, thermobarometric, isotopic, and geochemical data provide evidence for long and complex formation history of the Sarylakh and Sentachan Au-Sb deposits conditioned by regional geodynamics and various types of ore mineralization, differing in age and source of ore matter combined in the same ore-localizing structural units. The deposits are situated in the Taryn metallogenic zone of the East Yakutian metallogenic belt in the central Verkhoyansk-Kolyma Fold Region. They are controlled by the regional Adycha-Taryn Fault Zone that separates the Kular-Nera Terrane and the western part of the Verkhoyansk Fold-Thrust Belt. The fault extends along the strike of the northwest-trending linear folds and is deep-rooted and repeatedly reactivated. The orebodies are mineralized crush zones accompanied by sulfidated (up to 100 m wide) quartz-sericite metasomatic rocks and replacing dickite-pyrophyllite alteration near stibnite veinlets. Two stages of low-sulfide gold-quartz and stibnite mineralization are distinguished. The formation conditions of the early milk white quartz in orebodies with stibnite mineralization at the Sarylakh and Sentachan deposits are similar: temperature interval 340–280°C, salt concentration in fluids 6.8–1.6 wt % NaCl equiv, fluid pressure 3430–1050 bar, and sodic bicarbonate fluid composition. The ranges of fluid salinity overlapped at both deposits. In the late regenerated quartz that attends stibnite mineralization, fluid inclusions contain an aqueous solution with salinity of 3.2 wt % NaCl equiv and are homogenized into liquid at 304–189°C. Syngenetic gas inclusions contain nitrogen 0.19 g/cm³ in density. The pressure of 300 bar is estimated at 189°C. The composition of the captured fluid is characterized as K-Ca bicarbonatesulfate. The sulfur isotopic composition has been analyzed in pyrite and arsenopyrite from ore and metasomatic zones, as well as in coarse-, medium-, and fine-grained stibnite varieties subjected to dynamometamorphism. The following δ³⁴S values, ‰ have been established at the Sarylakh deposit: −2.0 to −0.9 in arsenopyrite, −5.5 to −1.1 in pyrite, and −5.5 to −3.6 in stibnite. At the Sentachan deposit: −0.8 to +1.0 in arsenopyrite, +0.5 to +2.6 in pyrite, and −3.9 to +0.6 in stibnite. Sulfides from the Sentachan deposit is somewhat enriched in ³⁴S. The ¹⁸O of milk white quartz at the Sarylakh deposit varies from +14.8 to 17.0‰ and from +16.4 to + 19.3‰ at the Sentachan. The δ¹⁸O of regenerated quartz is +16.5‰ at the Sarylakh and +17.6 to +19.8‰ at the Sentachan. The δ¹⁸O of carbonates varies from +15.0 to 16.3% at the Sarylakh and from +16.7 to +18.2‰ at the Sentachan. The δ¹³C of carbonates ranges from −9.5 to −12.1‰ and −7.8 to −8.5‰, respectively. The calculated $ \delta ^{18} O_{H_2 O} $ \delta ^{18} O_{H_2 O} of the early fluid in equilibrium with quartz and dolomite at 300δC are +7.9 to +10.1‰ for the Sarylakh deposit and +9.5 to +12.4‰ for the Sentachan deposit (+4.9 and 6.0‰ at 200°C for the late fluid, respectively). Most estimates fall into the interval characteristic of magmatic water (°¹⁸O = +5.5 to +9.5‰).     

Arsenic, antimony and other toxic elements in the drinking water of Eastern Thessaly in Greece and its possible effects on human health

Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l⁻¹, As 1–125 μg l⁻¹, Br 6–60 μg l⁻¹, Cl 500–25,000 μg l⁻¹, Cr 1–6 μg l⁻¹, Cu 1–15 μg l⁻¹, Fe 10–352 μg l⁻¹, Mg 2,940–40,100 μg l⁻¹, Mn 0–8 μg l⁻¹, Na 3,650–13,740 μg l⁻¹, P 20–48 μg l⁻¹, Pb 0–7 μg l⁻¹, Sb 0–21 μg l⁻¹, Si 3,310–13,240 μg l⁻¹ and Zn 7–994 μg l⁻¹. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.     

Cl/Br ratios and stable chlorine isotope analysis of magmatic–hydrothermal fluid inclusions from Butte,Montana and Bingham Canyon,Utah

A bulk geochemical study has been carried out on fluid inclusion leachates extracted from quartz veins from porphyry Cu deposits in Butte, Montana, USA and Bingham Canyon, Utah, USA. The leachates mostly represent low-salinity magmatic–hydrothermal fluid inclusions. Their halogen ratios (Br/Cl) of fluid inclusion leachates were determined by ion chromatography, and δ³⁷Cl values of the leachates were measured by continuous-flow isotope ratio mass spectrometry. Br/Cl ratios from early pre-Main stage and later Main stage veins at Butte range from 0.60 to 1.88 × 10⁻³ M. Ratios are similar in pre-Main stage veins with sericite bearing selvages and Main stage samples ranging from 0.81 to 1.08 × 10⁻³ and from 0.92 to 1.88 × 10⁻³ M, respectively, clustering below seawater (1.54 × 10⁻³ M) and overlapping mantle values (~1–2 × 10⁻³ M). Two samples associated with early pre-Main stage potassic alteration yield distinctly lower Br/Cl ratios of 0.60 and 0.64 × 10⁻³ M. Butte δ³⁷Cl values range from −0.8‰ to −2.3‰ with no significant difference between pre-Main stage and Main stage samples. Br/Cl ratios for quartz veins from Bingham Canyon range from 0.18 to 3.68 × 10⁻³ M. Br/Cl ratios from Bingham range above and below previously reported for porphyry copper deposits. In contrast to Butte, δ³⁷Cl values for Bingham are lower, ranging from −0.9‰ to −4.1‰. In the absence of any processes which can significantly fractionate chlorine isotopes at high temperatures, we suggest that the porphyry system at Bingham, and to a lesser extent at Butte, have inherited negative chlorine isotopic signatures from the subducting slab generated at low temperatures.     

The role of bitumen in strata-bound copper deposit formation in the Copiapo area, Northern Chile

In northern Chile, between 27 and 33°S, there are numerous deposits where residual petroleum is associated with Cu-(Ag) mineralisation (the most famous being El Soldado). All of these deposits are hosted by Lower Cretaceous volcanic or volcanoclastic facies along the axis of a former backarc basin. This close relationship suggests that the generation, migration and emplacement of hydrocarbons in the Cretaceous volcanic units is a regional process, associated with the evolution of the Cretaceous backarc basin and points to the importance of pyrobitumen as an exploration tool for similar Cu–(Ag) deposits. The present work analyses four small strata-bound copper deposits located along a north–south belt approximately 10 km east of Copiapó in northern Chile. These deposits are typically hosted by pyrobitumen-rich andesitic volcanic to volcanoclastic rocks intercalated with the marine carbonate Pabellón Formation, the youngest formation within the Chañarcillo Group. The strong genetic and spatial relationships between the pyrobitumen-rich lavas and the mineral deposits allow us to define this volcanic belt as the Ocoita-Pabellón Metallotect. Two hydrothermal events can be distinguished based on the mineralogical, textural, fluid inclusion and isotope data of ore and gangue and on the optical properties of residual petroleum. During the early event, petroleum was mobilised from the source rocks into the primary and secondary porosity of the lavas by Fe-rich hydrothermal fluids, which precipitated pyrite as an early sulphide phase. The second event is characterised by Cu-rich hydrothermal fluids, which induced three successive sub-stages of Cu-sulphide precipitation. The hydrothermal fluids chemically and thermally altered the first-stage bitumen, transforming it into pyrobitumen. The present work documents similarities between the Ocoita-Pabellón Metallotect and the El Soldado ore deposit and emphasises important differences. In the El Soldado host rocks, a petroleum reservoir existed prior to the arrival of the mineralising hydrothermal fluids, the framboidal pyrite was formed by assistance of bacteria, the S of the Cu sulphides was inherited from the pyrite, and the fluid source was basin connate-metamorphic brine. In the Ocoita-Pabellón Metallotect, the hydrocarbons were mobilised into the host rocks by hydrothermal fluids; the pyrite is epigenetic, the δ³⁴S values of pyrite and copper sulphides are very different, with distinctive light δ³⁴S signature of Cu sulphides (δ³⁴S between −44.7 and −17.9‰), and the calculated δ¹⁸O of hydrothermal fluids indicates the participation of meteoric water in the late phases of the hydrothermal system.

Fluid Inclusion Studies of Gold Deposits in the Gezhen Shear Zone,Hainan Province,China

The Tuwaishan, Baoban, Erjia, Bumo and other gold deposits in western Hainan occur in Precambrian metamorphic clastic rocks and are structurally controlled by the Gezhen shear zone. Fluid inclusion studies have been carried out of the gold deposits mentioned above. The homogenization temperatures of the whole fluid inclusion population range from 140°C to 370°C, indicating that gold was precipitated mainly at 240–250°C. The salinities are within the range of 2.0–9.2 wt% NaCl equiv. and the pressure of formation of the deposits was estimated at about 270×10⁵−500×10⁵Pa, corresponding to a depth of about 1.1–2.0 km under lithostatic confinement. Chemical studies show that the ore fluid is of the Na⁺(K⁺)-Ca²⁺-Cl⁻(F⁻) type. Theδ ¹⁸O andδD values of the fluid vary from −2.7‰- +4.4‰ and −50‰–−87‰ Evidence developed from fluid inclusions and geological setting indicates that the ore fluid was a mixture of magmatic and meteoric-hydrothermal waters. Changes in chemical composition andδ ¹⁸O andδD of fluid inclusions from one ore field to another seem to be related with regional tectonism, metamorphism and magmatism.     

Archaean Au−Ag mineralisation at Racetrack,near Kalgoorlie,Western Australia: a high crustal-level expression of the Archaean composite lode-gold system

The Racetrack Au−Ag deposit, in the Archaean Yilgarn Block, Western Australia, is hosted by a porphyritic basalt in a low greenschist facies setting and is associated with a brittle strike-slip fault system. Three distinct and successive stages of hydrothermal activity and late quartz-carbonate veining resulted in multiple veining and/or brecciation: Stages I and II are Au-bearing, whereas Stage III and late veins are barren. The ore shows features of both classic epithermal and mesothermal deposits. Alteration assemblages, typified by sericitization, carbonization, silicification and chloritization, are similar to those of mesothermal gold deposits, wheras the quartz vein-textures including comb, rosette, plumose and banded, ore mineralogyof arsenopyrite, pyrite, chalcopyrite, sphalerite, galena, freibergite, tetrahedrite, tennantite, fahlore, electrum and gold, and metal associations (Cu, As, Ag, Sn, Sb, W, Au and Pb) are more characteristics of epithermal deposits. Fluid inclusions related to Stage II are two phase and aqueous with 1–8 (average 4) wt. % NaCl equiv. and CO₂ content of <0.85 molal. Pressure-corrected homogenisation temperatures range from 190°C to 260°C. Mineral assemblages indicate that ore fluid pH ranged between 4.2 and 5.3, f_{O 2} between 10^−38.8 and 10^−39.6 bars, and m_Σs between 10^−3.2 and 10^−3.6. Calculated chemical and stable isotope compositions require a component of surface water in the ore fluid depositing the mineralisation, but evidence for deep crustal Pb indicates that deeply sourced fluids were also involved. The deposit is interpreted to have formed in a shallow environment via mixing of deeply sourced fluids, from at least as deep as the base of the greenstone belt, with surface waters. It therefore represents the upper crustal end-member of the crustal depth spectrum of Archaean lode-gold mineralisation.     

Gold mineralization in the Mazowe area, Harare-Bindura-Shamva greenstone belt, Zimbabwe: II. Genetic relationships deduced from mineralogical, fluid inclusion and stable isotope studies, and the Sm-Nd isotopic composition of scheelites

In the Mazowe area some 40 km NW of Harare in Zimbabwe, gold mineralization is hosted in a variety of lithologies of the Archean Harare-Bindura-Shamva greenstone belt, in structures related to the late Archean regional D2/3 event. Conspicuous mineralzogical differences exist between the mines; the mainly granodiorite-hosted workings at Mazowe mine are on pyrite-rich reefs, mines of the Bernheim group have metabasalt host rocks and are characterized by arsenopyrite-rich ores, and Stori's Golden Shaft and Alice mine, both in metabasalts, work sulfide-poor quartz veins. In contrast to the mineralogical diversity, near-identical fluid inventories were found at the different mines. Both H₂O-CO₂-CH₄ fluids of low salinity, and highly saline fluids are present and are regarded to indicate fluid mixing during the formation of the deposits. Notably, these fluid compositions in the Mazowe gold field markedly contrast to ore fluids “typical” of Archean mesothermal gold deposits on other cratons. Stable isotope compositions of quartz from the various deposits (δ¹⁸O=10.8 to 13.2‰ SMOW), calcite (δ¹⁸O=9.5 to 11.9‰ SMOW and δ¹³C=−3.2 to −8.0‰ PDB), inclusion water (δD=−28 to −40‰ SMOW) and sulfides (δ³⁴S=1.3 to 3.2‰ CDT) are uniform within the range typical for Archean lode gold deposits worldwide. The fluid and stable isotope compositions support the statement that the mineralization in the Mazowe gold field formed from relatively reduced fluids with a “metamorphic” signature during a single event of gold mineralization. Microthermometric data further indicate that the deposits formed in the PT range of 1.65–2.3 kbar and 250–380 °C. Ages obtained by using the Sm/Nd and Rb/Sr isotope systems on scheelites are 2604 ± 84 Ma for the mineralization at Stori's Golden Shaft mine, and 2.40 ± 0.20 Ga for Mazowe mine. The Archean age at Stori's is regarded as close to the true age of gold mineralization in the area, whereas the Proterozoic age at Mazowe mine probably reflects later resetting. Received: 30 September 1998 / Accepted: 17 August 1999     

Assessment of heavy-metal contamination of floodplain soils due to mining and mineral processing in the Harz Mountains, Germany

2 study area was assessed with respect to its heavy-metal load on the basis of the current guideline values. The heavy-metal loads of the soils in the study area have ranges of <0.2–200 mg kg⁻¹ for Cd, <10–30,000 mg kg⁻¹ for Pb, 7–10,000 mg kg⁻¹ for Cu and 50–55,000 mg kg⁻¹ for Zn. Mobility of the heavy metals was determined by extraction at different pH values. The acid neutralisation capacity (ANC_x) at these pH values was also determined to estimate the probability that the pH can drop to pH=x. The ANC values in the study area ranged from 6 to 3000 mmol H⁺ kg⁻¹, from −33 to 800 mmol H⁺ kg⁻¹ and from −74 to 160 mmol H⁺ kg⁻¹ for ANC_3.5, ANC_5.0 and ANC_6.2, respectively. Together with pedological data, the extraction experiments permit differentiation between soil units that have been placed in the same environmental hazard class on the basis of total heavy-metal loads. Received: 10 August 1998 · Accepted: 14 August 1999     

Petrology,geochemistry and U–Pb geochronology of magmatic rocks from the high-sulfidation epithermal Au–Cu Chelopech deposit,Srednogorie zone,Bulgaria

The Chelopech deposit is one of the largest European gold deposits and is located 60 km east of Sofia, within the northern part of the Panagyurishte mineral district. It lies within the Banat–Srednegorie metallogenic belt, which extends from Romania through Serbia to Bulgaria. The magmatic rocks define a typical calc-alkaline suite. The magmatic rocks surrounding the Chelopech deposit have been affected by propylitic, quartz–sericite, and advanced argillic alteration, but the igneous textures have been preserved. Alteration processes have resulted in leaching of Na₂O, CaO, P₂O₅, and Sr and enrichment in K₂O and Rb. Trace element variation diagrams are typical of subduction-related volcanism, with negative anomalies in high field strength elements (HFSE) and light element, lithophile elements. HFSE and rare earth elements were relatively immobile during the hydrothermal alteration related to ore formation. Based on immobile element classification diagrams, the magmatic rocks are andesitic to dacitic in compositions. Single zircon grains, from three different magmatic rocks spanning the time of the Chelopech magmatism, were dated by high-precision U–Pb geochronology. Zircons of an altered andesitic body, which has been thrust over the deposit, yield a concordant ²⁰⁶Pb/²³⁸U age of 92.21 ± 0.21 Ma. This age is interpreted as the crystallization age and the maximum age for magmatism at Chelopech. Zircon analyses of a dacitic dome-like body, which crops out to the north of the Chelopech deposit, give a mean ²⁰⁶Pb/²³⁸U age of 91.95 ± 0.28 Ma. Zircons of the andesitic hypabyssal body hosting the high-sulfidation mineralization and overprinted by hydrothermal alteration give a concordant ²⁰⁶Pb/²³⁸U age of 91.45 ± 0.15 Ma. This age is interpreted as the intrusion age of the andesite and as the maximum age of the Chelopech epithermal high-sulfidation deposit. ¹⁷⁶Hf/¹⁷⁷Hf isotope ratios of zircons from the Chelopech magmatic rocks, together with published data on the Chelopech area and the about 92-Ma-old Elatsite porphyry–Cu deposit, suggest two different magma sources in the Chelopech–Elatsite magmatic area. Magmatic rocks associated with the Elatsite porphyry–Cu deposit and the dacitic dome-like body north of Chelopech are characterized by zircons with ɛHf_T90 values of ∼5, which suggest an important input of mantle-derived magma. Some zircons display lower ɛHf_T90 values, as low as −6, and correlate with increasing ²⁰⁶Pb/²³⁸U ages up to about 350 Ma, suggesting assimilation of basement rocks during magmatism. In contrast, zircon grains in andesitic rocks from Chelopech are characterized by homogeneous ¹⁷⁶Hf/¹⁷⁷Hf isotope ratios with ɛHf_T90 values of ∼1 and suggest a homogeneous mixed crust–mantle magma source. We conclude that the Elatsite porphyry–Cu and the Chelopech high-sulfidation epithermal deposits were formed within a very short time span and could be partly contemporaneous. However, they are related to two distinct upper crustal magmatic reservoirs, and they cannot be considered as a genetically paired porphyry–Cu and high-sulfidation epithermal related to a single magmatic–hydrothermal system centered on the same intrusion.     

Himalayan magmatism and porphyry copper–molybdenum mineralization in the Yulong ore belt, East Tibet

Summary ?The NW–SE-trending Yulong porphyry Cu–Mo ore belt, situated in the Sanjiang0 area of eastern Tibet, is approximately 400 km long and 35 to 70 km wide. Complex tectonic and magmatic processes during the Himalayan epoch have given rise to favorable conditions for porphyry-type Cu–Mo mineralization. Porphyry masses of the Himalayan epoch in the Yulong ore belt are distributed in groups along regional NW–SE striking tectonic lineaments. They were emplaced mainly into Triassic and Lower Permian sedimentary-volcanic rocks. K–Ar und U–Pb isotopic datings give an intrusion age range of 57–26 Ma. The porphyries are mainly of biotite monzogranitic and biotite syenogranitic compositions. Geological and geochemical data indicate that the various porphyritic intrusions in the belt had a common or similar magma source, are metaluminous to peraluminous, Nb–Y–Ba-depleted, I-type granitoids, and belong to the high-K calc-alkaline series. Within the Yulong subvolcanic belt a number of porphyry stocks bear typical porphyry type Cu–Mo alteration and mineralization. The most prominent porphyry Co–Mo deposits include Yulong, Malasongduo, Duoxiasongduo, Mangzong and Zhanaga, of which Yulong is one of the largest porphyry Cu (Mo) deposits in China with approximately 8 × 10⁶ tons of contained Cu metal. Hydrothermal alteration at Yulong developed around a biotite–monzogranitic porphyry stock that was emplaced within Upper Triassic limestone, siltstone and mudstone. The earliest alteration was due to the effects of contact metamorphism of the country rocks and alkali metasomatism (potassic alteration) within and around the porphyry body. The alteration of this stage was accompanied by a small amount of disseminated and veinlet Cu–Mo sulfide mineralization. Later alteration–mineralization zones form more or less concentric shells around the potassic zone, around which are distributed a phyllic or quartz–sericite–pyrite zone, a silicification and argillic zone, and a propylitic zone. Fluid inclusion data indicate that three types of fluids were involved in the alteration–mineralization processes: (1) early high temperature (660–420 °C) and high salinity (30–51 wt% NaCl equiv) fluids responsible for the potassic alteration and the earliest disseminated and/or veinlet Cu–Mo sulfide mineralization; (2) intermediate unmixed fluids corresponding to phyllic alteration and most Cu–Mo sulfide mineralization, with salinities of 30–50 wt% NaCl equiv and homogenization temperatures of 460–280 °C; and (3) late low to moderate temperature (300–160 °C) and low salinity (6–13 wt% NaCl equiv) fluids responsible for argillic and propylitic alteration. Hydrogen and oxygen isotopic studies show that the early hydrothermal fluids are of magmatic origin and were succeeded by increasing amounts of meteoric-derived convective waters. Sulfur isotopes also indicate a magmatic source for the sulfur in the early sulfide mineralization, with the increasing addition of sedimentary sulfur outward from the porphyry stock. Received August 29, 2001; revised version accepted May 1, 2002 Published online: November 29, 2002     

Trace Metals (Cd,Cu, Hg,and Pb) Accumulation Recorded in the Intertidal Mudflat Sediments of Three Coastal Lagoons in the Gulf of California,Mexico

²¹⁰Pb geochronologies of Cd, Cu, Hg, and Pb fluxes were obtained from the intertidal mudflat sediments of the coastal lagoons Chiricahueto, Estero de Urías, and Ohuira in the Mexican Pacific. The Cu and Hg sediment concentrations at the three lagoons fell within the ranges of 6–76 μg g⁻¹ and 0.1 to 592 ng g⁻¹, respectively; Chiricahueto and Estero de Urías sediments had comparable Cd and Pb concentrations within the ranges of 0.2–2.1 μg g⁻¹ and 10–67 μg g⁻¹, respectively; whereas in Ohuira lagoon, Cd concentrations were lower (0.1–0.5 μg g⁻¹) and Pb concentrations were higher (115–180 μg g⁻¹) than in the other lagoons. The metal fluxes (μg cm⁻² y⁻¹) for the three lagoons fell within the ranges of 0.02–0.15 for Cd, 0.7–6.0 for Cu, 0.001–0.045 for Hg, and 0.7–20 for Pb. The Hg pollution in Estero de Urías was attributed to the exhausts of the thermoelectric plant of Mazatlan and the metal enrichment in Chiricahueto and Ohuira was related to the agrochemical wastes from the croplands surrounding these lagoons.     

Distribution and enrichment of trace metals in marine sediments of Bay of Bengal,off Ennore,south-east coast of India

In order to avoid the pollution of trace metals in marine environment, it is necessary to establish the data and understand the mechanisms influencing the distribution of trace metals in marine environment. The concentration of heavy metals (Fe, Mn, Cr, Cu, Ni, Pb, Zn, Co and Cd) were studied in sediments of Ennore shelf, to understand the metal contamination due to heavily industrialized area of Ennore, south-east coast of India. Concentration of metals shows significant variability and range from 1.7 to 3.7% for Fe, 284–460 μg g⁻¹ for Mn, 148.6–243.2 μg g⁻¹ for Cr, 385–657 μg g⁻¹ for Cu, 19.8–53.4 μg g⁻¹ for Ni, 5.8–11.8 μg g⁻¹ for Co, 24.9–40 μg g⁻¹ for Pb, 71.3–201 μg g⁻¹ for Zn and 4.6–7.5 μg g⁻¹ for Cd. For various metals the contamination factor (CF) and geoaccumulation index (I _geo) has been calculated to assess the degree of pollution in sediments. The geoaccumulation index shows that Cd, Cr and Cu moderately to extremely pollute the sediments. This study shows that the major sources of metal contamination in the Ennore shelf are land-based anthropogenic ones, such as discharge of industrial wastewater, municipal sewage and run-off through the Ennore estuary. The intermetallic relationship revealed the identical behavior of metals during its transport in the marine environment.     

Origin of the Tongshankou porphyry–skarn Cu–Mo deposit,eastern Yangtze craton,Eastern China: geochronological,geochemical, and Sr–Nd–Hf isotopic constraints

The Tongshankou Cu–Mo deposit, located in the westernmost Daye district of the Late Mesozoic Metallogenic Belt along the Middle-Lower reaches of the Yangtze River, eastern China, consists mainly of porphyry and skarn ores hosted in the Tongshankou granodiorite and along the contact with the Lower Triassic marine carbonates, respectively. Sensitive high-resolution ion microprobe zircon U–Pb dating constrains the crystallization of the granodiorite at 140.6 ± 2.4 Ma (1σ). Six molybdenite samples from the porphyry ores yield Re–Os isochron age of 143.8 ± 2.6 Ma (2σ), while a phlogopite sample from the skarn ores yields an ⁴⁰Ar/³⁹Ar plateau age of 143.0 ± 0.3 Ma and an isochron age of 143.8 ± 0.8 Ma (2σ), indicating an earliest Cretaceous mineralization event. The Tongshankou granodiorite has geochemical features resembling slab-derived adakites, such as high Sr (740–1,300 ppm) and enrichment in light rare earth elements (REE), low Sc (<10 ppm), Y (<13.3 ppm), and depletion in heavy REE (<1.2 ppm Yb), and resultant high Sr/Y (60–92) and La/Yb (26–75) ratios. However, they differ from typical subduction-related adakites by high K, low MgO and Mg#, and radiogenic Sr–Nd–Hf isotopic compositions, with (⁸⁷Sr/⁸⁶Sr) _t  = 0.7062–0.7067, ɛ _Nd(t) = −4.37 to −4.63, (¹⁷⁶Hf/¹⁷⁷Hf) _t  = 0.282469–0.282590, and ɛ _Hf(t) = −3.3 to −7.6. The geochemical and isotopic data, coupled with geological analysis, indicate that the Tongshankou granodiorite was most likely generated by partial melting of enriched lithospheric mantle that was previously metasomitized by slab melts related to an ancient subduction system. Magmas derived from such a source could have acquired a high oxidation state, as indicated by the assemblage of quartz–magnetite–titanite–amphibole–Mg-rich biotite in the Tongshankou granodiorite and the compositions of magmatic biotite that fall in the field between the NiNiO and magnetite–hematite buffers in the Fe³⁺–Fe²⁺–Mg diagram. Sulfur would have been present as sulfates in such highly oxidized magmas, so that chalcophile elements Cu and Mo were retained as incompatible elements in the melt, contributing to subsequent mineralization. A compilation of existing data reveals that porphyry and porphyry-related Cu–Fe–Au–Mo mineralization from Daye and other districts of the Metallogenic Belt along the Middle-Lower reaches of the Yangtze River took place coevally in the Early Cretaceous and was related to an intracontinental extensional environment, distinctly different from the arc-compressive setting of the Cenozoic age that has been responsible for the emplacement of most porphyry Cu deposits of the Pacific Rim.     

Crustal sulfur is required to form magmatic Ni–Cu sulfide deposits: evidence from chalcophile element signatures of Siberian and Deccan Trap basalts

Process models for ore formation in magmatic Ni–Cu–platinum group element (PGE) sulfide systems require that S saturation is achieved in a mafic–ultramafic magma. Traditional models explain the achievement of S saturation or sulfide saturation either by the addition of crustal S, by the felsification of the magma by crustal contamination, or by mixing between primitive and evolved magmas. Which process matters most is important to industry-oriented exploration models where crustal S sources are believed to be encouraging features of a metallotect. Studies of the Siberian Trap flood basalts at Noril’sk have demonstrated that chalcophile element depletion is linked to assimilation of silica-rich crust, but it is less clear whether this contaminant contained an appreciable amount of S. At Noril’sk, the Ni–Cu–PGE sulfide deposits are associated with subvolcanic intrusions that were emplaced into Permian and Carboniferous sedimentary sequences rich in shales, marlstones, and evaporites. Similar to the Siberian Trap basalts, the Deccan Trap contains a volumetrically important suite of crustally contaminated tholeiitic basalts. We present new PGE data for samples from a stratigraphic sequence of basalts from the southern Deccan province. Two of the formations in this sequence (the Bushe and Poladpur Formations) have geochemical signatures indicative of a wide degree of crustal contamination of a magma type that gave rise to the stratigraphically higher Ambenali Formation (a product of transitional midocean ridge basalt magmatism). There are no known deposits or occurrences of Ni–Cu–PGE sulfides associated with subvolcanic intrusions in the Deccan province. Despite the fact that the Bushe Formation exhibits a stronger crustal contamination signature than the most contaminated Siberian Trap basalt formations, and the Poladpur lavas are also strongly crustally contaminated, the Bushe and Poladpur basalts are undepleted in Ni, Cu, or PGE. This indicates that the contaminated Deccan Trap lavas did not achieve S saturation. This, in turn, places constraints on the potential of the Deccan Trap in southern India to host significant magmatic sulfide deposits. Conversely, this observation also indicates that an S-rich crustal contaminant is required for the genesis of magmatic Ni–Cu–PGE sulfide deposits.