Isotope geochemistry of ore fluids for the Dongsheng sandstone-type uranium deposit, China

The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution²³⁰Th_excess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (²³⁰Th), 0.43–1.40 ppm (²³²Th), 0.09–0.49 ppb (²³⁴U) and 1.66–8.24 ppm (²³⁸U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the²³⁰Th_excess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant²³⁰Th_excess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.     

Geo-chemical Behavior of Uranium in the Sambhar Salt Lake, Rajasthan (India): Implications to "Source" of Salt and Uranium "Sink"

Among several salt lakes in the Thar Desert of western India, the Sambhar is the largest lake producing about 2 × 10⁵ tons of salt (NaCl) annually. The “lake system” (lake waters, inflowing river waters, and sub-surface brines) provides a unique setting to study the geo-chemical behavior of uranium isotopes (²³⁸U, ²³⁴U) in conjunction with the evolution of brines over the annual wetting and evaporation cycles. The concentration of ²³⁸U and the total dissolved solids (TDS) in lake water increase from ~8 μg L⁻¹ and ~8 g L⁻¹ in monsoon to ~1,400 μg L⁻¹ and 370 g L⁻¹, respectively, during summer time. The U/TDS ratio (~1 μg g⁻¹ salt) and the ²³⁴U/²³⁸U activity ratio (1.65 ± 0.05), however, remain almost unchanged throughout the year, except when U/TDS ratio approaches to 3.8 at/or beyond halite crystallization. These observations suggest that uranium behaves conservatively in the lake waters during the annual cycle of evaporation. Also, uranium and salt content (TDS) are intimately coupled, which has been used to infer the origin and source of salt in the lake basin. Furthermore, near uniform ratios in evaporating lake waters, when compared to the ratio in seawater (~0.1 μg g⁻¹ salt and 1.14 ± 0.02, respectively), imply that aeolian transport of marine salts is unlikely to be significant source of salt to the lake in the present-day hydrologic conditions. This inference is further consistent with the chemical composition of wet-precipitation occurring in and around the Sambhar lake. The seasonal streams feeding the lake and groundwaters (within the lake’s periphery) have distinctly different ratios of U/TDS (2–69 μg g⁻¹ salt) and ²³⁴U/²³⁸U (1.15–2.26) compared to those in the lake. The average U/TDS ratio of ~1 μg g⁻¹ salt in lake waters and ~19 μg g⁻¹ salt in river waters suggest dilution of the uranium content by the recycled salt and/or removal processes presently operating in the lake during the extraction of salt for commercial use. Based on mass-balance calculations, a conservative estimate of "uranium sink" (in the form of bittern crust) accounts for ~5 tons year⁻¹ from the lake basin, an estimate similar to its input flux from rivers, i.e., 4.4 tons year⁻¹.     

Study of shallow groundwater quality evolution under saline intrusion with environmental isotopes and geochemistry

Evolution of the shallow groundwater quality under saline intrusion in porous aquifer system has been studied with environmental isotopes and geochemistry in the Laizhou Bay area, China. Two campaigns of water sampling from various sources were carried out in spring and winter for environmental isotopic and chemical analyses. The origin of groundwater salinity from intrusion of both modern seawater and deep brine water was identified by analysing the correlations between ¹⁸O, D, T, Cl⁻, SO₄²⁻ and electrical conductivity. The results indicate that the brine is originated from evaporating and concentrating of intruded seawater and its δD and δ¹⁸O are different from modern seawater but similar to those of mixture of seawater with fresh groundwater. It is hard to distinguish the salinity origin in this area by the δD–δ¹⁸O relationship alone. The relations between δ¹⁸O and conductivity, Cl⁻ and SO₄²⁻ have been used to identify the salinity origin due to the distinct difference in salinity between the brine and seawater, conjunctively with use of T. A threshold of T = 12 TU was adopted to identify the origin of saline groundwater.     

Hydrogeochemical study of the Terme and Karakurt thermal and mineralized waters from Kirşehir Area,central Turkey

The Terme and Karakurt thermal resorts are located in the center of Kirşehir city in central Anatolia. Thermal waters with temperatures of 44–60°C are used for central heating and balneologic purposes. Paleozoic rocks of the Kirşehir Massif are the oldest units in the study area. The basement of the Massif comprises Paleozoic metamorphic schist and marbles which partly contain white quartzite layers of a few tens of cm thickness. The metamorphic schists which are cut by granites of Paleocene age are overlain by horizontally bedded conglomerate, sandstone, claystone, and limestone of upper Paleocene-Eocene age. Among the thermal and cold waters collected from the areas of Terme and Karakurt, those from thermal waters are enriched with Ca–HCO₃ and cold waters are of Ca–Mg–HCO₃ type waters. The pH values of samples are 6.31–7.04 for the thermal well waters, 6.41 for thermal spring, 7.25 and 7.29 for the cold waters, and 7.52 for the Hirla lake water. EC values are 917–2,295 μS/cm for the thermal well waters, 2,078 μS/cm for thermal spring, and 471 and 820 μS/cm for the cold springs. The lowest TDS content is from water of T10 thermal well in the Terme area (740.6 mg/l). The hot and cold waters of Terme show very similar ion contents while the Karakurt hot waters at western most parts are characterized by distinct chemical compositions. There is ion exchange in thermal waters from the T5 (5), T6 (6), T12 (7), and T1 (8) wells in the Terme area. The thermal waters show low concentrations of Fe, Mn, Ni, Al, As, Pb, Zn and Cu. Waters in the study area are of meteoric origin, and rainwater percolated downwards through faults and fractures, and are heated by the geothermal gradient, later rising to the surface along permeable zones. δ¹³C_VPDB values measured on dissolved inorganic carbon in samples range from −1.65 to +5.61‰ for thermal waters and from −11.81 to −10.15‰ for cold waters. Carbon in thermal waters is derived from marine carbonates or CO₂ of metamorphic origin while carbon in cold waters originates from freshwater carbonates.     

Geochemical evolution of uraniferous soda lakes in Eastern Mongolia

Extremely high concentrations of uranium (U) were discovered in shallow, groundwater-fed hyperalkaline soda lakes in Eastern Mongolia. A representative groundwater sample in this area is dilute and alkaline, pH = 7.9, with 10 mM TIC and 5 mM Cl⁻. In contrast, a representative lake water sample is pH ~ 10 with TIC and Cl⁻ each more than 1,000 mM. Groundwater concentrations of U range from 0.03 to 0.43 μM L⁻¹. Lake water U ranges from 0.24 to >62.5 μM, possibly the highest naturally occurring U concentrations ever reported in surface water. Strontium isotopes ⁸⁷Sr/⁸⁶Sr varied in groundwaters from 0.706192 to 0.709776 and in lakes ⁸⁷Sr/⁸⁶Sr varied from 0.708702 to 0.709432. High concentrations of U, Na, Cl⁻, and K correlate to radiogenic Sr in lake waters suggesting that U is sourced from local Cretaceous alkaline rhyolites. Uranium-rich groundwaters are concentrated by evaporation and U(VI) is chelated by CO₃⁻² to form the highly soluble UO₂(CO₃)₃⁻⁴. Modeled evaporation of lakes suggests that a U-mineral phase is likely to precipitate during evaporation.     

Effects of pH and Ca competition on complexation of cadmium by fulvic acids and by natural organic ligands from a river and a lake

The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca²⁺ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd²⁺] ranged from 10⁻¹³ to 10⁻¹² mol/l, and the conditional stability constant with natural ligands was log K _CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10⁻⁶ mol/g C. In the softwater River Wyre, dissolved [Cd²⁺] ranged from 4 × 10⁻¹² to 1 × 10⁻¹¹ mol/l, and the ligands were weaker (log K _CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10⁻⁶ mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.     

The source of fluoride toxicity in Muteh area,Isfahan, Iran

Endemic dental fluorosis has been observed in most inhabitants of three villages of Muteh area, located in northwest of Isfahan province, with mottled enamel related to high levels of fluoride in drinking water (1.8–2.2 ppm). Forty-seven groundwater samples from six villages were collected and fluoride concentrations along with physico-chemical parameters were analyzed. Fluoride concentration in this area varies from 0.2 to 9.2 mg/l with highest fluoride level at Muteh gold mine (Chahkhatun mine). Fluoride concentration positively correlates with pH and HCO₃ ⁻ indicating that alkaline pH provides a suitable condition for leaching of fluoride from surrounding rocks. The district is mainly covered by three lithological units, namely, metamorphic and granite rocks, alluvial sediments, and carbonate rocks. Factor analysis shows that parameters can be classified into four components: electrical conductivity (EC), total dissolved solids (TDS), Cl⁻, Na⁺ and K⁺, pH and F⁻, SO₄ ²⁻and Mg²⁺, HCO₃ ⁻ and Ca₂ ⁺. The groundwaters from the three geological units were compared using Mann–Whitney U test. The order of median fluoride concentration is: metamorphic and granite rocks > alluvial sediments > carbonate rocks. Hence, the fluoride content is most probably related to fluoride-bearing minerals such as amphibole and mica group minerals in metamorphic and granitic rocks. The concentration of fluoride in drinking water wells located near the metamorphic complex in Muteh area is above 2 ppm.     

Upwellings in Lake Baikal

Based on shipboard and satellite observations, the characteristics of upwelling in Lake Baikal in the period of direct temperature stratification have been determined for the first time. Coastal upwellings appear annually under the effect of run-down and alongshore winds and are traced along the coast to a distance of up to 60–100 km and up to 250 km in North Baikal. Analogous to the way it occurs in seas, water rises from the depths of 100–200 m (350 m as a maximum) at the velocity of 0.1 × 10⁻²−6.5 × 10⁻² cm/s. Divergence in the field of intràbasin cyclonic macrovortices produces upwelling in the Baikal pelagic zone and downwelling in the vicinity of shores; this lasts from 7 to 88 days and covers the depth interval of 80–300 m in August and up to 400–800 m in early-mid November. The area of upwellings occupies up to 20–60% of the separate basins of the lake. Vertical circulation of water in the field of pelagic upwellings leads to intensification of coastal currents and to formation of the thermobar with a heat inert zone in the central part of the lake in November, and this thermobar is not observed in other lakes, at that.     

The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa. II: fluid inclusion, fluid chemistry and stable isotope constraints

The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ³⁴S) and carbonate gangue (δ¹³C and δ¹⁸O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H₂O–NaCl–CaCl₂ (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH₄–CO₂–HS⁻ fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H₂O–CaCl₂–NaCl ±(CH₄–CO₂–HS⁻), 2 to 25 wt% NaCl+CaCl₂). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO₄. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to ³⁴S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ³⁴S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ³⁴S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ¹⁸O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ¹³C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO₂ during the early and main stages of mineralisation. On the other hand, δ¹³C and δ¹⁸O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH₄ and CO₂ during waning stages of hydrothermal fluid flow.     

Geochemistry of granites and metasediments of the urban area of Vila Real (northern Portugal) and correlative radon risk

Radon concentration was evaluated in dwellings of the urban area of Vila Real (Northern Portugal). The area is mainly composed of Hercynian granites and Cambrian metasediments, and CR-39 passive detectors (n = 112) were used for the purpose. The results obtained in winter conditions suggest that the most productive geological unit is the Hercynian granite G1 (geometric mean of 364 Bq/m³), while Cambrian metasediments of the Douro Group show the lowest average indoor radon concentration (236 Bq/m³). The geological, geochemical and radiological data obtained suggest that the most effective control on the radon concentrations of the area is related with the uranium content of the rocks; indeed, the highest contents were observed in granite G1 (21 ppm) and the lowest in the metasediments (3 ppm). This is also confirmed by the results obtained for groundwater, where granites present the highest concentrations of dissolved radon (up to 938 Bq/l), uranium (5–18 ppb) and gross α activities (0.47–0.92 Bq/l). No important radiometric anomalies were found in relation with geological structures such as faults, veins and contacts, but a moderate increase of the uranium content can occur locally in such structures. Petrographic observations and SEM studies show that uranium is mainly contained within the rock in heavy accessory minerals (apatite, zircon, monazite, xenotime), which reduces radon emanation. Notwithstanding, due to the high U contents granites show a significant potential to induce indoor radon concentrations in dwellings in excess of the recommended value of 400 Bq/m³. Overall, we can conclude that the region of Vila Real presents a moderate to high radon risk in dwellings and groundwater.     

Nitrate contamination of groundwater in an agroecosystem in Zhangye Oasis,Northwest China

In order to assess the extent of groundwater contamination by nitrate (NO₃ ⁻–N) and to provide information about the deterioration of the groundwater quality in Zhangye Oasis, Northwest China, a study was conducted in this area. The mean value of NO₃ ⁻–N concentrations in groundwater samples was 10.66 ± 0.19 mg l⁻¹. NO₃ ⁻–N concentrations exceeding 10 mg l⁻¹ (the threshold for drinking water set by the World Health Organization) were found in 32.4% of 71 wells, and were 13, 33.3, 52.4 and 50.0% in the groundwater samples from drinking wells, irrigation wells, hand-pumping wells and groundwater table observation wells, respectively. The result showed that the groundwater samples that had NO₃ ⁻–N concentrations exceeding the threshold for drinking water were mostly collected from a depth of less than 20 m. Groundwater NO₃ ⁻–N concentrations in areas used for the cultivation of vegetables, seed maize and intercropped maize were significantly higher than those in urban or paddy areas. NO₃ ⁻–N contamination of groundwater in areas with sandy soil was more severe than in those with loam soil.     

Groundwater quality,nitrate pollution and irrigation environmental management in the Neogene sediments of an agricultural region in central Thessaly (Greece)

The degradation of groundwater quality, which has been noted in the recent years, is closely connected to the intensification of agriculture, the unreasonable use of chemical fertilizers and the excess consumption of large volumes of irrigation water. In the hilly region of central Thessaly in Greece, which suffers the consequences of intense agricultural use, a hydrogeological study is carried out, taking groundwater samples from springs and boreholes in the Neogene aquifers. The aim of this study is the investigation of irrigation management, water quality and suitability for various uses (water supply, irrigation), the degradation degree and the spatial distribution of pollutants using GIS. The following hydrochemical types prevail in the groundwater of the study area: Ca–Mg–HCO₃, Mg–Ca–Na–HCO₃ and Na–HCO₃. In the above shallow aquifers, especially high values of NO₃ ⁻ (31.7–299.0), NH₄ ⁺ (0.12–1.11), NO₂ ⁻ (0.018–0.109), PO₄ ³⁻ (0.07–0.55), SO₄ ²⁻ (47.5–146.5) and Cl⁻ (24.8–146.5) are found, particularly near inhabited areas (values are in mg L⁻¹). The water of shallow aquifers is considered unsuitable for human use due to their high polluting load, while the water of the deeper aquifers is suitable for human consumption. Regarding water suitability for irrigation, the evaluation of SAR (0.153–7.397) and EC (481–1,680 μS cm⁻¹) resulted in classification category ‘C3S1’, indicating high salinity and low sodium water which can be used for irrigation in most soils and crops with little to medium danger of development of exchangeable sodium and salinity. The statistical data analysis, the factor analysis and the GIS application have brought out the vulnerable-problematic zones in chemical compounds of nitrogen and phosphates. The groundwater quality degradation is localized and related exclusively to human activities. Based on 2005 and 2008 estimates, the annual safe yield of the region’s aquifers were nearly 41.95 MCM. However, the existing situation is that 6.37 MCM of water is over extracted from these aquifers.     

Chalcophile element geochemistry and petrogenesis of high-Ti and low-Ti magmas in the Permian Emeishan large igneous province,SW China

Sulfide-poor mafic layered intrusions, sills/dykes and lava flows in the Funing region, SW China, are part of the ~260 Ma Emeishan large igneous province. They belong to either a high-Ti group (TiO₂ = 1.6–4.4 wt%) with elevated Ti/Y ratios (351–1,018), or a low-Ti group (TiO₂ < 1.2 wt%) with low Ti/Y ratios (133–223). This study investigates the role of fractionation of olivine, chromite and sulfide on the distributions of chalcophile elements, Ni, Cu and PGE, of the high-Ti and low-Ti group rocks at Funing. The high-Ti group rocks contain 1.6–5.3 ppb Pt + Pd, 0.06–0.43 ppb Ir and 0.01–0.13 ppb Ru, and show relative constant (Cu/Pd)_PM ratios (4.0–9.7) and a negative correlation between Ni/Pd and Cu/Ir ratios. Fractionated IPGE/PPGE patterns and very negative Ru anomalies of the high-Ti group rocks, together with low Fo values (59–62 mol%) of olivine, indicate that the high-Ti magmas may have experienced fractionation of olivine and chromite under S-undersaturated condition. Based on the PGE concentrations, the low-Ti group rocks can be further divided into two subgroups; a high-PGE low-Ti subgroup and a low-PGE low-Ti subgroup. The high-PGE low-Ti group rocks are rich in MgO (10–20 wt%), but Fo values of olivine from the rocks are low (74–76 mol%). The rocks contain highly variable PGE (Pt + Pd = 1.7–88 ppb, Ir = 0.05–1.3 ppb), Ni (179 –1,380 ppm) and Cu (59–568 ppm). They have Cu/Zr ratios >1, low (Y/Pd)_PM ratios (0.2–7.1) and nearly constant (Cu/Pd)_PM ratios (1.5–3.8). The even and parallel chalcophile element patterns of the high-PGE low-Ti subgroup rocks are likely a result of olivine-dominated fractionation under S-undersaturated condition. The low-PGE low-Ti group rocks have low MgO (4.5–8.9 wt%) and very poor PGE (Pt + Pd 0.5–1.6 ppb, Ir 0.004–0.02 ppb) with low Cu/Zr ratios (0.1–0.5), high (Y/Pd)_PM (26–70) and variable (Cu/Pd)_PM ratios (2.8–14). The trough-like chalcophile element patterns of the low-PGE low-Ti subgroup rocks indicate that the magmas were sulfide saturation and sulfide melts were extracted from the magmas. The extracted sulfide melts might be potential Ni–Cu sulfide ores at depth in the Funing region.     

Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits

The author’s database, which presently includes data from more than 18500 publications on fluid and melt inclusions in minerals and is continuing to be appended, was used to generalize results on physicochemical parameters of the formation of hydrothermal deposits and occurrences of tin and tungsten. The database includes data on 320 tin and tin-tungsten deposits and occurrences and 253 tungsten and tungstentin deposits around the world. For most typical minerals of these deposits (quartz, cassiterite, tungsten, scheelite, topaz, beryl, tourmaline, fluorite, and calcite), histograms of homogenization temperatures of fluid inclusions were plotted. Most of 463 determinations made for cassiterite are in the range of 300–500°C with maximum at 300–400°C, while those for wolframite and scheelite (453 determinations) fall in the range of 200–400°C with maximum at 200–300°C. Representative material on pressures of hydrothermal fluids included 330 determinations for tin and 430 determinations for tungsten objects. It was found that premineral, ore, and postmineral stages spanned a wide pressure range from 70–110 bar to 6000–6400 bar. High pressures of the premineral stages at these deposits are caused by their genetic relation with felsic magmatism. Around 50% of pressure determinations lie in the range of 500–1500 bar. The wide variations in total salinity and temperatures (from 0.1 to 80 wt % NaCl equiv and 20–800°C) were obtained for mineral-forming fluids at the tin (1800 determinations) and tungsten (2070 determinations) objects. Most of all determinations define a salinity less than 10 wt % NaCl equiv. (∼60%) and temperature range of 200–400°C (∼70%). The average composition of volatile components of fluids determined by different methods is reported. Data on gas composition of the fluids determined by Raman spectroscopy are examined. Based on 180 determinations, the fluids from tin objects have the following composition (in mol %): 41.2 CO₂, 39.5 CH₄, 19.15 N₂, and 0.15 H₂S. The volatile components of tungsten deposits (190 determinations) are represented by 56.1 CO₂, 30.7 CH₄, 13.2 N₂, and 0.01 H₂S. Thus, the inclusions of tungsten deposits are characterized by higher CO₂ content and lower (but sufficiently high) contents of CH₄ and N₂. The concentrations of tin and tungsten in magmatic melts and mineral-forming fluids were estimated from analysis of individual inclusions. The geometric mean Sn contents are 87 ppm (+ 610 ppm/−76 ppm) in the melts (569 determinations) and 132 ppm (+ 630 ppm/−109 ppm) in the fluids (253 determinations). The geometric mean W values are 6.8 ppm (+ 81/−6.2 ppm) in the magmatic melts (430 determinations) and 30 ppm (+ 144 ppm/−25 ppm) in the mineral-forming fluids (391 determinations).     

H,O,S and Pb isotope studies of uranium ore deposits in granitoid rocks of South China

Most altered clay minerals in uranium ore deposits in granites in the selected provinces of South China haveδ ¹⁸O _m values ranging from 6.22 to 7.24,δD_m from −60 to −70,δ ¹⁸O from +3.05 to −3.07, and from −20.2 to −37.5‰. Relative enrichment of³²S in the uranium ore deposits and greater variations in Pb isotopic composition of galenas from them show that uranium ores in the granites were formed in such a way that uranium in shallow-source granites had been mobilized by heated meteoric waters and then migrated to local favourable locations along great faults to form uranium ore deposits. Zhang Shaoli, Yang Wenjin, Tang Chunjing and Xu Wenxin did part of this work.     

Platinum-group elements in ores from the Kalmakyr porphyry Cu–Au–Mo deposit, Uzbekistan: bulk geochemical and laser ablation ICP-MS data

We studied primary ore samples from Kalmakyr, a giant Cu–Au–Mo porphyry deposit in eastern Uzbekistan. Disseminated and stockwork-type high-grade Cu–Au–Mo mineralization showed average concentrations of 55 ppb Pd, 5.5 ppb Pt, 0.95 ppb Rh, 0.49 ppb Ir, and 4.1 ppm Au (n = 8). This type of mineralization is characterized by the presence of pyrite, chalcopyrite, molybdenite, and gold. A peak Pd content of 292 ppb was determined in a base-metal-rich quartz vein in granodiorite porphyry, which contains galena, sphalerite, chalcopyrite, tetrahedrite, and gold. Palladium correlates with Cu, Ag, Se, and S. Mineralogical and laser ablation ICP-MS study confirmed that Pd is homogeneously distributed in chalcopyrite, which contains up to 110 ppm Pd, and tetrahedrite, containing up to 20 ppm Pd. An assessment of the Pd and Pt budget at Kalmakyr showed the potential of approximately 17 t of Pd and 1.7 t of Pt.     

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ³⁴S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.     

Concentration levels of some inorganic contaminants in streams and sediments in areas of pyrometallurgical and hydrometallurgical activities at the Obuasi gold mine,Ghana

This study assessed the levels of selected inorganic contaminants in streams and stream sediments in the effluent areas relating to the pyrometallurgical and hydrometallurgical treatment of gold ores in the Obuasi gold mine, Ghana. Water and stream sediment samples were taken from specific locations during the consecutive rainy and dry seasons, and concentrations of phosphate (PO₄ ³⁻), nitrate (NO₃ ⁻), chloride (Cl⁻), sulphate (SO₄ ²⁻), sodium (Na⁺), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), arsenic (As), copper (Cu), iron (Fe), zinc (Zn) and lead (Pb), were determined. Alkalinity, pH, temperature and specific electrical conductivity were also measured. In the water samples, the average pH range for both the seasons is 6.9–7.4, most anions and metals have relatively higher concentrations in the wet season than in the dry season at both the metallurgical sites. Trace metals concentrations were comparatively low (<0.01–5.00 mg/l), higher in the dry season at the pyrometallurgical sites. Irrespective of seasons, SO₄ ²⁻ (0.80–949.50 mg/l) and PO₄ ³⁻ (<0.01–6.30 mg/l) were pronounced at the pyrometallurgical sites, while NO₃ ⁻ (0.01–98.45 mg/l) and Cl⁻ (1.88-49.05 mg/l) were higher at the hydrometallurgical sites. In water samples, Ca²⁺ and SO₄ ²⁺ were the dominant cation and anion, respectively. In the stream sediments, except pH, NO₃ ⁻, Cl⁻, Na⁺ and Mg²⁺, all other parameter values were relatively higher at the hydrometallurgical areas. The average concentrations of Ca²⁺, Mg²⁺, As and Fe are remarkably high at both metallurgical sites (3,217–46,026 mg/kg). Overall, the level of parameters in the water samples are pronounced at pyrometallurgical sites, whereas the levels in sediments are higher at the hydrometallurgical sites.     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.