Sulphur isotope distribution in the Pb-Zn-deposit Bleiberg (Carinthia,Austria)

The sulphur isotope composition of 233 sulphides and 40 sulphates has been investigated and evaluated in combination with 29 earlier published data. The total variation of δ³⁴S values for the sulphides and the sulphates ranges from ?40 up to ?1 ‰ and from +7 up to +20 ‰, respectively. For the mineral species the variations are (with number of samples in brackets): galena (96) ?32 up to ?2 ‰, sphalerite (141) ?30 up to ?4 ‰, marcasite (16) ?27 up to ?1 ‰, pyrite (10) ?26 up to ?13 ‰, molybedenite (3) ?40 up to ?29 ‰, anhydrite and gypsum (8) +15 up to +20 ‰, coelestine (1) +19 ‰, and barite (33) +7 up to +18 ‰. The frequency distribution of the δ³⁴S values corresponds with the complexity of the ore forming processes which resulted in six strata-bound ore mineralizations. The sulphate values clearly show that the sulphate sulphur originates from sea water sulphate. The sulphides are formed by bacteriogeneric processes from seawater sulphate, and their sulphur isotope composition depends on the lithofacies of the sediments as well as on the following diagenetic processes.     

Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes

Fluid inclusion studies in combination with hydrogen, oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst-bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul, Brazil. Monophase liquid inclusions in colourless quartz, amethyst, calcite, barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice-melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I, celadonite, chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low δ³⁴S_V-CDT values of pyrite (?25 to ?32?‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst, goethite and anhydrite), III (early subhedral calcite) and IV (barite, late subhedral calcite and gypsum), the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3, 3.4 and 0.3 wt% NaCl-equivalent characterise the mineralisation stages II, III and IV, respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in δ¹⁸O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80–90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C, while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst-precipitating fluid in combination with δD values of amethyst-hosted fluid inclusions (?59 to ?51?‰) show a significant ¹⁸O-shift from the meteoric water line. This ¹⁸O-shift, high salinities of the fluid inclusions with chloride-sulphate composition, and high δ³⁴S values of anhydrite and barite (7.5 to 9.9?‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

Sulphate Sources in the Sava and Ljubljanica Rivers, Slovenia, Inferred from Sulphur and Oxygen Isotope Compositions

Measurements were made of sulphur and oxygen isotope ratios of sulphate in some Slovenian rivers, lakes and tap waters. δ³⁴S ranged from −0.2 to + 13.3‰, δ¹⁸O ranged from +4.9 to + 13.6‰, and the sulphate content varied from 0.8 to 41.4 mg/L. Rivers flowing from the Julian Alps contain a very low amount of sulphate that is leached from a thin horizon of soil by rain. As confirmed by their low δ¹⁸O values, these sulphates do not enter the rivers directly in rain, but arise from biochemical cycling in the soil. The low δ³⁴S of this sulphate indicates that it originates from the oxidation of sedimentary sulphides. The evolution of sulphates along the river course was investigated for the Sava and Ljubljanica rivers. The variations observed in sulphate from the waters studied result from variations in the contribution of sulphates of different origin. Downstream the Sava River sulphate is depleted in the heavy isotopes of both sulphur and oxygen, with δ-values gradually tending toward the δ-values of groundwater sulphates in the watershed. In contrast, the δ-values of sulphate in the Ljubljanica River are almost constant and similar to those of sulphate in local groundwater. Introduction of water from Italian and Slovenian mines was recorded in the Soča River, where the lowest δ³⁴S value of sulphate sulphur (−0.2‰) was observed. In addition, the influence of sulphate from the oxidation of sedimentary sulphides was recorded in the Sotla River. No evidence was found for introduction of sulphate from factories.     

Hydrogeochemistry and possible sulfate sources in karst groundwater in Chongqing, China

Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are affected by both natural environment and people. Therefore, the study of karst groundwater hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. This paper focused on the major ion chemistry and sulfate isotope of karst groundwater in Chongqing for tracing the sulfate sources and related hydrochemical processes. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO₃ type or Ca(Mg)-HCO₃ type. However, some hydrochemical types were the K + Na + Ca-SO₄ type (G25 site) or Ca-HCO₃ + SO₄ type (G26 and G14 sites), indicating that the hydrochemistry of these sites may be strongly influenced by anthropogenic activities or unique geological characteristics. The δ³⁴S-SO₄ ^2? of collected karst groundwater sample fell into a range of ?6.8 to 21.5 ‰, with a mean value of 5.6 ‰. In dolomite aquifer, the δ³⁴S-SO₄ ^2? value ranges from ?4.3 to 11.0 ‰, and in limestone aquifer, it ranged from ?6.8 to 21.5 ‰. The groundwater samples from different land use types showed distinctive δ³⁴S-SO₄ ^2? value. The δ³⁴S-SO₄ ^2? value of groundwater samples had range of ?6.8 to 16.7 ‰ (mean 4.0 ‰, n = 11) in cultivated land areas, 1.5–21.5 ‰ (mean 7.2 ‰, n = 20) in forested land areas, and ?4.3 to 0.8 ‰ (mean ?1.7 ‰, n = 2) in coalmine areas. The δ³⁴S-SO₄ ^2? values of groundwater samples collected from factory area and town area were 2.2 and 9.9 ‰, respectively. According to the δ³⁴S information of potential sulfate sources, this paper discussed the possible sulfate sources of collected karst groundwater samples in Chongqing. The variations of both δ³⁴S and 1/SO₄ ^2? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sulfide mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) contributed to sulfate in karst groundwater. The influence of oxidation of sulfide mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread. For protecting, sustaining, and utilizing the groundwater resources, the sewage possibly originating from urban, mine or industrial area must be controlled and treated, and the use of fertilizer should be limited.     

Sulphur isotopes in carbonatites and associated silicate rocks from the Superior Province, Canada

Thirty-five S isotope analyses obtained from six carbonatite complexes from the Superior Province, Canadian Shield, ranging in age from 1,897 Ma to 1,093 Ma, have δ³⁴S_CDT values of between ?4.5‰ and +3.4‰. Pyrrhotite, chalcopyrite and pyrite mineral separates were used. Each complex possesses its own distinct range and mean S isotope composition. The range for Schryburt Lake is: ?4.5‰ to ?3.4‰ ( mean?=??3.9‰), for Big Beaver House: ?3.6‰ to ?1.5‰ (mean?=??2.2‰), for Cargill: ?1.5‰–+0.5‰ (mean?=??0.7‰), for Spanish River: ?0.1‰–+0.1‰ (mean?=?0.0‰), and for Firesand River: +1.3‰–+3.4‰ (mean?=?+1.7‰). A single sample from Carb Lake yielded a δ³⁴S_CDT value of +2.8‰. Differences in isotope compositions can be related to isotope effects brought about during melt generation and emplacment, such as variations in fo₂ and temperature. The different S and C isotope data for most complexes, however, suggest that the parental melts could have been generated from a heterogeneous mantle source, although process-driven changes cannot be completely ruled out.     

Chemical and isotopic examination of produced waters from the BP-Wolf lake in situ combustion pilot

The chemical and isotopic compositions of co-produced waters can be used to monitor the processes that take place during in situ combustion. Anticipated processes include mixing of waters, production of CO₂, production of high concentrations of dissolved sulphate and variations in water chemistry associated with heated zones. Water sources include pore waters in oil-bearing strata, waters in overlying or underlying aquifers, water condensed from previously injected steam, and waters associated with combustion. Waters from all sources may mix during production and interpretation of the combustion process can be refined by an understanding of water sources. Produced fluids from the BP-Wolf Lake pilot site in Alberta have been examined to evaluate the effectiveness of the chemical composition of water and the isotopic compositions of aqueous species for monitoring in situ combustion.Produced waters do not show simple conservative mixing behaviour. This suggests that multiple sources of water and other processes, including water-rock reactions, act to modify water compositions. At least three sources of produced waters can be recognized and these are interpreted to be formation water, injected steam and waters that have low Cl and high HCO₃ due to combustion. It is not possible to distinguish waters in the oil-bearing formation from regional waters present in aquifers that underlie the stimulated intervals. Dissolved aqueous species, such as SiO₂, Na, K (as Na/K) and Cl can be used to monitor the approach of the combustion front. Sulphate has been suggested as an indicator of approaching combustion and, although sulphate concentrations rise as combustion approaches a producing well, this indicator is not reliable in all cases. The use of all the above chemical parameters is recommended for detection of combustion zones during operation.The isotope composition of produced waters confirms that there has been significant water-rock interaction during combustion. Carbon isotope compositions of HCO₃ that range from −8 to −25% δ¹³C show that oil oxidation is a major contributor of CO₂ at high temperatures, but CO₂ produced by carbonate mineral dissolution becomes more significant as temperature decreases. Sulphate concentrations in waters produced during combustion can be an order of magnitude higher than those observed during steam stimulation. Both the oil (bitumen) and pyrite (FeS₂) are significant sulphur sources. Typically, the sulphur in both phases is in a reduced state and is available through oxidation associated with combustion. The δ³⁴S of dissolved sulphate in produced waters does not unequivocally identify either of the two major sources of sulphur. However, the relatively depleted δ³⁴ values for SO₄ suggest that the high sulphate concentrations generally associated with the approach of the combustion front result from the oxidation of pyrite.     

新疆焉耆盆地水环境氢氧同位素特征及其指示作用

根据焉耆盆地开都河水及其两岸地下水中的氢氧稳定同位素资料及氘过量参数(d)值,分析了焉耆盆地内不同水体的δ(D)、δ(18O)和d值的分布规律,并得到地下水的主要补给来源及其与开都河水的相互作用关系;地下水的δ(D)在-87.60‰～-61.82‰间,δ(18O)在-10.90‰～-9.73‰间;开都河水的δ(D)在-71.95‰～-58.58‰间,δ(18O)在-9.57‰～-8.64‰间。结果表明:焉耆盆地内地下水和地表水同源于山区的降水和冰雪融水,且经历了较强的蒸发作用;地下水与地表水之间的直接水力联系较弱,深层地下水主要接受开都河水在洪积扇区的入渗补给,浅层地下水主要接受河流引水灌溉入渗;不同深度地下水之间的水力联系较为密切,为统一的地下水系统。     

Stable isotope study of base metal deposits from the Eastern High Atlas,Morocco

Tertiary epigenetic lead ± zinc and copper mineralizations occur in the Mesozoic carbonate cover and stibnite, barite and copper mineralization in the Precambrian to Palaezoic basement in the Eastern High Atlas, Morocco. The carbon isotope data from host carbonates range from +3 to -1‰ PDB. The data are typical for marine carbon. There is no difference between surrounding dolomites and younger vein dolomites. The oxygen isotopic composition of the samples is enriched in ¹⁶O; the range is from -3 to -11‰ PDB with respect to that of carbonates in equilibrium with marine water. It is postulated that the isotopic composition was changed during dolomitization being caused by transition of connate formation waters diluted to some degree by meteoritic water. The bacteriogenically reduced sulphur from syngenetic sulphides and Mesozoic marine sulphate mobilized during Tertiary orogenesis are thought to be the source of H₂S and SO₄. Cambro-Ordovicien sulphate is also supposed to be the source of sulphur in the Jebel Zelmou barite deposit in the basement. Isotopic composition of lead from galenas in the Tertiary deposits from the Mesozoic cover are strikingly homogenous. Model ages vary between 230–180 Ma. It is suggested that important mobilization processes are responsible for Tertiary metallogeny in Morocco.

     

Spatial characteristics of water quality,stable isotopes and tritium associated with groundwater flow in the Hutuo River alluvial fan plain of the North China Plain

The groundwater flow system and the flow velocity in the alluvial fan plain of the Hutuo River, China, have been studied, with an emphasis on relating geochemical characteristics and isotopes factors. Seven stretches of one river, six springs and 31 wells, with depths ranging from 0 m (river waters) to 150 m, were surveyed. The groundwater has a vertical two-layer structure with a boundary at about 80–100 m depth, yielding an upper and a lower groundwater layer. The δ¹⁸O and δD values range from ?10.56 to ?7.05‰ and ?81.83 to ?59‰, respectively. The groundwater has been recharged by precipitation, and has not been subjected to significant evaporation during infiltration into the aquifer in the upper layer. Using a tritium model, the groundwater flow in the alluvial fan plain showed horizontal flow velocity to be greater than vertical velocity. Groundwater in the upper layer is characterized by Ca–HCO₃ type. From the spatial distribution characteristics of the stable isotope and chemical composition of the groundwater, agricultural irrigation was considered to have an influence on the aquifer by causing excessive groundwater abstraction and irrigation return.     

Tracing stable isotope values from meteoric water to groundwater in the southwestern part of the Chad basin

The southwestern Chad basin is a semi-arid region with annual rainfall that is generally less than 500 mm and over 2,000 mm of evapotranspiration. Surface water in rivers is seasonal, and therefore groundwater is the perennial source of water supply for domestic and other purposes. Stable isotope has been measured for rainwater, surface water and groundwater samples in this region. The stable isotope data have been used to understand the inter-relationships between the rainwater, surface water, shallow and deep groundwater of this region. This is being used in a qualitative sense to demonstrate present day recharge to the groundwater. Stable isotope in rainwater for the region has an average value of –4‰ δ¹⁸O and –20‰ δ²H. Surface water samples from rivers and Lake Chad fall on the evaporation line of this average value. The Upper Zone aquifer water samples show stable isotope signal with a wide range of values indicating the complex character of the aquifer Zone with three distinguishable units. The wide range of values is attributable to waters from individual unit and/or mixture of waters of different units. The Middle and Lower aquifers Zones’ waters show similar stable isotopes values, probably indicating similarity in timing and/or mechanism of recharge. These are palaeowaters probably recharged under a climate that is different from today. The Upper Zone aquifer is presently being recharged as some of its waters show stable isotope compositions similar to those of average rainfall waters of the region.     

An “On-Line” Method for Oxygen Isotope Exchange Between Gas-Phase CO<Subscript>2</Subscript> and Water

An “on-line” mixing system has been developed and evaluated for continuous oxygen isotope exchange between gas-phase CO₂ and liquid water. The system is composed of three basic parts: equipment and materials used to introduce water and gas into a mixing reservoir, the mixing and exchange reservoir, and a vessel used to separate gas and water phases exiting the system. A series of experiments were performed to monitor the isotope exchange process over a range of temperatures (5–40 °C) and CO₂ partial pressures (202–15,200 Pa). Isotopic exchange was evaluated using CO₂ having δ¹⁸O values of 30.4 and 37.8 ‰ and waters of two distinct oxygen isotope compositions (?6.5 to ?5 and 6 to 7.5 ‰). Isotope ratios were determined by isotope ratio mass spectrometry and cavity ring-down spectroscopy. CO₂ did not reach oxygen isotope equilibrium under the conditions described here. However, oxygen isotope exchange rate constants were determined at different temperatures and regressed to yield the expression k (h^?1) = 0.020 × T (°C) + 0.28. Using this expression, the residence time required to reach oxygen isotope equilibrium may be estimated for a given set of environmental conditions (e.g., δ¹⁸O value of water, temperature). System parameters can be modified to achieve a specific δ¹⁸O value for CO₂. Consequently, the exchange system described here has the ability to deliver a constant flow of CO₂ at a desired oxygen isotope composition. This ability is attractive for a variety of applications such as experiments that utilize flow-through reactors and environmental chambers or require static chemical conditions.     

同位素技术解析安阳河与地下水相互作用

河流与地下水相互作用研究是水文学研究的难点和热点。安阳河与地下水相互作用研究,对于安阳市水资源科学开发与管理具有重要意义。安阳河冲洪积扇地表水与地下水转化率为17%～27%。潜水位标高为80 m,向下游逐渐变成多层含水层（水位40 m）。当地降水环境同位素监测数据表明,当地大气降水线与全球大气降水线接近平行,表明该线代表本地区大气降水的氢氧同位素特征。地表水同位素值较集中,2016年8月δ18O值变化范围为-9‰~-8.7‰,δD值变化范围为-65‰~-63‰,2017年1月δ18O值变化范围为-8.5‰~-8.2‰,δD值变化范围为-63‰~-61‰,河水水化学类型为HCO3·SO4—Ca型,表明流域内地表水的同位素值受距离的影响较小。地下水稳定同位素值变化较大,2016年8月δ18O值范围为-10.4‰~-5.5‰,δD值范围为-75‰~-46‰,2017年1月δ18O值范围为-10.2‰~-5.4‰,δD值范围为-75‰~-45‰,即从接近降水值到最大值形成一条“蒸发”线。河流出山口一带地下水同位素值呈现最大蒸发值,表明地表水补给地下水,地下水化学类型为HCO3·SO4·Cl—Ca,存在明显人为污染成分。下游为大气降水补给浅层地下水,中深层地下水主要来源于中游侧向径流,水化学类型主要为HCO3—Ca·Mg型,综合分析表明,安阳河中下游（冲洪积扇）地带“三水”转换积极,并影响其水质、水量。     

涞源北盆地地下水氢氧同位素特征及北海泉形成模式

拒马源泉群作为拒马河的源头,受到了较多专家和学者的关注。但这些研究多集中在地下水的水化学、水位动态、泉流量等特征上,对地下水氢氧同位素特征的分析几乎没有,且对北海泉的成因解释多为粗略的定性概述。为了说明涞源北盆地地下水的氢氧同位素特征,详细揭示北海泉的形成模式,首次系统地采集了不同含水岩组的地下水样品,测定了水样的氢氧同位素组分。结果表明:样品点δD和δ18O值均落在区域大气降水线上或附近,大气降水是研究区地下水的主要补给来源;白云岩、灰岩含水岩组高程效应较明显,径流途径长,松散含水层径流途径短,受蒸发作用较强;白云岩、灰岩含水岩组和松散含水层氘盈余d值分别为6.0‰～11.6‰、4.2‰～11.2‰、3.8‰～8.0‰,较大气降水大部分偏小,表明岩溶水和松散孔隙水经历了不同的流动过程;白云岩、灰岩含水岩组从补给区向排泄区各自流动过程中,在小西庄、香炉屯村附近断裂带发生沟通混合,然后在向盆地中心径流过程中受断层阻水上升,上升过程中又接受了松散孔隙水的补给,最后在松散岩层中出露成泉,形成北海泉。在孔隙水混入前,两者的平均补给比例大约为48.4%～57.6%和42.4%～51.6%。     

Sulphur source and genesis of polymetallic sulphide occurrences of the Ofoten district in the Central–North Norwegian Caledonides: evidence from sulphur isotopic studies

Fourteen stratiform, stratabound and vein-type sulphide occurrences in the Upper Allochthon of the Central–North Norwegian Caledonides have been studied for their sulphur, oxygen and hydrogen isotope composition. Depositional ages of host rocks to the stratabound and stratiform sulphide occurrences range from 590 to 640?Ma. The sulphides and their host rocks have been affected by polyphase deformation and metamorphism with a peak temperature of 650?°C dated to 432?Ma. A total of 104 sulphide and 2 barite samples were analysed for δ³⁴S, 16 whole-rock and quartz samples for δ¹⁸O and 12 samples of muscovite for δD. The overall δ³⁴S values range from ?14 to +31‰ with the majority of sampled sulphides lying within a range of +4 to +15‰. In most cases δ³⁴S within each hand specimen behaves in accordance with the equilibrium fractionation sequence, δ³⁴S_gn<δ³⁴S_cp<δ³⁴S_sph<δ³⁴S_py. A systematic increase in δ³⁴S from the vein sulphides (?8‰) through schist/amphibolite-hosted (+6‰) and schist-hosted (+7 to +12‰) to dolomite-hosted (+12 to +31‰) occurrences is documented. The δ³⁴S averages of the stratiform schist-hosted sulphides are 17 to 22‰ lower than in the penecontemporaneous seawater sulphate. The Bjørkåsen (+4 to +6‰) occurrence is a volcanogenic massive sulphide (VMS) transitional to sedimentary massive sulphide (SMS), exhalative, massive, pyritic deposit of Cu–Zn–Pb sulphides formed by fluids which obtained H₂S via high-temperature reduction of seawater sulphate by oxidation of Fe²⁺ during the convective circulation of seawater through underlying rock sequences. The Raudvatn, volcanic-hosted, disseminated Cu sulphides (+6 to +8‰) obtained sulphur via a similar process. The Balsnes, stratiform, ‘black schist’-hosted, pyrite–pyrrhotite occurrence (?6 to ?14‰) is represented by typical diagenetic sulphides precipitated via bacteriogenic reduction of coeval (ca. 600?Ma) seawater sulphate (+25 to +35‰) in a system open to sulphate supply. The δ³⁴S values of the Djupvik–Skårnesdalen (+7 to +12‰), Hammerfjell (+5 to 11‰), Kaldådalen (+10 to +12‰) and Njallavarre (+7 to +8‰) stratiform, schist-hosted, massive and disseminated Zn–Pb (±Cu) sulphide occurrences, as well as the stratabound, quartzite-hosted, Au-bearing arsenopyrite occurrence at Langvatnet (+7 to +11‰), suggest that thermochemically reduced connate seawater sulphate was a principal sulphur source. The Sinklien and Tårstad, stratabound, dolomite- and dolomite collapse breccia-hosted, Zn (±Cu–Pb) sulphides are marked by the highest enrichment in ³⁴S (+20 to +31‰). The occurrences ?are?assigned to the Mississippi-Valley-type deposits.?High δ³⁴S values require reduction/replacement of contemporaneous (ca. 590?Ma) evaporitic sulphate (+23 to +34‰) with C_org-rich fluids in a closed system. The Melkedalen (+12 to +15‰), stratabound, fault-controlled, Cu–Zn sulphide deposit is hosted by the ca. 595?Ma dolomitised Melkedalen marble. The deposit is composed of several generations of ore minerals which formed by replacement of host dolomite. Polyphase hydrothermal fluids were introduced during several reactivation episodes of the fault zone. The positive δ³⁴S values with a very limited fractionation (<3‰) are indicative of the sulphide-sulphur generated through abiological, thermochemical reduction of seawater sulphate by organic material. The vein-type Cu (±Au–W) occurrences at Baugefjell, Bugtedalen and Baugevatn (?8 to ?4‰) are of hydrothermal origin and obtained their sulphur from igneous sources with a possible incorporation of sedimentary/diagenetic sulphides. In a broad sense, all the stratiform/stratabound, sediment-hosted, sulphide occurrences studied formed by epigenetic fluids within two probable scenarios which may be applicable separately or interactively: (1) expulsion of hot metal-bearing connate waters from deeper parts of sedimentary basins prior to nappe translation (late diagenetic/catagenetic/epigenetic fluids) or (2) tectonically driven expulsion in the course of nappe translation (early metamorphic fluids). A combination of (1) and (2) is favoured for the stratabound, fault-controlled, Melkedalen and Langvatnet occurrences, whereas the rest are considered to have formed within option (1). The sulphides and their host rocks were transported from unknown distances and thrust on to the Fennoscandian Shield during the course of the Caledonian orogeny. The displaced/allochthonous nature of the Ofoten Cu–Pb–Zn ‘metallogenetic province’ would explain the enigmatically high concentration of small-scale Cu–Pb–Zn deposits that occur only in this particular area of the Norwegian Caledonides.     

Trace element contents and C-O isotope geochemistry of the different originated magnesite deposits in Lake District (Southwestern Anatolia), Turkey

Vein-stockwork magnesite in the Madenli area, sedimentary huntite-magnesite in the A?a??t?rtar area, and lacustrine hydromagnesite in the Salda Lake area are located in the Bey?ehir-Hoyran and Lycian nappe rocks around Isparta and Burdur, Southwest Anatolia. The aim of this study is to understand trace element contents and carbon-oxygen isotope ratios in different originated magnesite, magnesite bearing huntite, and hydromagnesite deposits. Also, the element contents and isotope ratios of the magnesite occurrences are to compare with each other and similar magnesite occurrences in Turkey and world. It is found that the Madenli magnesite occurrences in the ?arkikaraa?aç ophiolites, A?a??t?rtar magnesite bearing huntite deposits in the lacustrine rocks of the Miocene-Pliocene, and the Salda hydromagnesite deposits in lacustrine basin on the Ye?ilova ophiolites. The paragenesis contains a common carbonate mineral magnesite, less calcite, serpentine, smectite, dolomite, and talc in the Madenli magnesite occurrences, mostly huntite and locally magnesite, dolomite, calcite, illite, quartz, and smectite in the A?a??t?rtar huntite-magnesite occurrences, and only hydromagnesite mineral in the Salda Lake hydromagnesite occurrences. Vein and stockwork Madenli magnesite deposits were recognized by higher total iron oxide concentrations (mean 1.10 wt%) than sedimentary A?a??t?rtar magnesite bearing huntite (mean 0.13 wt%) and lacustrine Salda hydromagnesite (mean 0.22 wt%) deposits. It is suggested that high Fe content (up to 5%) in the magnesite associated with ultramafic rocks than those from sedimentary environments (≤1% Fe). Based on average Ni, Co, Ba, Sr, As and Zr contents in the magnesite deposits, average Ni (134.63 ppm) and Co (15.19 ppm) contents in the Madenli magnesite and Salda hydromagnesite (36.85 ppm for Ni, 3.15 ppm for Co) have higher values than A?a??t?rtar huntite + magnesite (7.67 ppm for Ni and 0.89 ppm for Co). Average Ni-Co contents of these deposits can have close values depending on ophiolite host rock. Average Ba values of the Madenli (108.09 ppm) and A?a??t?rtar (115.88 ppm) areas are higher than those of Salda hydromagnesite (13.15 ppm). Sediment-hosted A?a??t?rtar magnesite-huntite deposits have the highest Sr contents (mean 505.81 ppm) as reasonably different from ultrabasic rock-related Madenli magnesite (mean 38.76 ppm) and Salda hydromagnesite (mean 36.70 ppm). The highest Sr content of sedimentary A?a??t?rtar deposits reveals that Sr is related to carbonate rocks. As and Zr contents have the highest average values (As 52.76 ppm and Zr 9.67 ppm) in the A?a??t?rtar deposits different from Madenli magnesite (As 0.54 ppm and Zr 1.67 ppm) and Salda hydromagnesite (As 0.5 ppm and Zr 2.58 ppm) deposits. High As and Zr concentrations in the A?a??t?rtar magnesite-huntite deposits may come from volcanic rocks in near country rocks. The δ ¹³C (PDB) isotope values vary between ?10.1 and ?11.4‰ in the Madenli magnesite, 7.8 to 8.8‰ for huntite, 1.7 to 8.3‰ for huntite + magnesite and 4.0‰ for limestone + magnesite in the A?a??t?rtar huntite-magnesite deposits, and 4.4 to 4.9‰ for Salda Lake hydromagnesite. The sources of the CO₂ are hydrothermal solutions, meteoric waters, groundwater dissolved carbon released from fresh water carbonates and marine limestone, soil CO₂, and plant C3 in the Madenli magnesite, and may be deep seated metamorphic reactions in limestone and shales of rich in terms of organic matter. The sources of CO₂ in A?a??t?rtar huntite and Salda hydromagnesite were meteoric water, groundwater dissolved inorganic carbon, fresh water carbonates, and marine limestone. The δ ¹⁸O (SMOW) isotope composition ranges from 26.8 to 28.1‰ in the Madenli magnesite, 30.4 to 32.4‰ for huntite and 29.8 to 35.5‰ for huntite + magnesite and 26.9‰ for limestone + magnesite in the A?a??t?rtar area, and 36.4 to 38.2‰ in the Salda Lake hydromagnesite. The Salda Lake hydromagnesite has heavier oxygen isotopic values than others. The sources of oxygen in the Madenli magnesite deposits are hydrothermal solutions, meteoric water, freshwater carbonates, and marine limestone, but the sources of oxygen of the A?a??t?rtar magnesite-huntite are meteoric water, fresh water carbonates, and marine limestone. The Salda Lake hydromagnesite has very high δ¹⁸O isotope values indicating a strong evaporitic environment. Magnesium (Mg⁺²) and silica are released by disintegration of very weathered-serpentinized ultrabasic rocks of all magnesite deposits and from partly dolomite and dolomitic limestone in the A?a??t?rtar magnesite bearing huntite deposits. In the A?a??t?rtar area, calcium (Ca⁺²) for huntite mineralization is provided by surrounding carbonate rocks. Based on isotopic data, host rocks, petrographic properties of the Madenli magnesite can be described as an ultramafic-associated hydrothermal vein mineralization corresponding to “Kraubath type” deposits, but A?a??t?rtar ve Salda Lake deposits are sedimentary mineralization (lacustrine/evaporitic) corresponding to “Bela Stena type” deposits. The estimated temperature using average δ¹⁸O isotope values is about 33.51 °C for Madenli magnesite, 48.33 °C for A?a??t?rtar huntite-magnesite, and 25 °C for Salda hydromagnesite. Based on isotope data, we can be say that the Madenli magnesite, A?a??t?rtar magnesite-huntite, and Salda hydromagnesite occur at low to moderate-low temperature water and alkaline (pH 8.5–10.5) under surface or near-surface conditions.     

The origin of sulphur in gypsum and dissolved sulphate in the Central Namib Desert,Namibia

This study investigates the sulphur source of gypsum sulphate and dissolved groundwater sulphate in the Central Namib Desert, home to one of Africa's most extensive gypsum (CaSO₄·2H₂O) accumulations. It investigates previously suggested sulphate precursors such as bedrock sulphides and decompositional marine biogenic H₂S and studies the importance of other potential sources in order to determine the origin of gypsum and dissolved sulphate in the region. An attempt has been made to sample all possible sulphur sources, pathways and types of gypsum accumulations in the Central Namib Desert. We have subjected those samples to sulphur isotopic analyses and have compiled existing results. In addition, ionic ratios of Cl/SO₄ are used to determine the presence of non-sea-salt (NSS) sulphur in groundwater and to investigate processes affecting groundwater sulphate. In contrast to previous work, this study proposes that the sulphur cycle, and the formation of gypsum, in the Namib Desert appears to be dominated by the deposition of atmospheric sulphates of phytoplanktonic origin, part of the primary marine production of the Benguela upwelling cells. The aerosol sulphates are subjected to terrestrial storage within the gypsum deposits on the hyper-arid gravel plain and are traceable in groundwater including coastal sabkhas. The hypothesis of decompositional marine biogenic H₂S or bedrock sulphide sources, as considered previously for the Namib Desert, cannot account for the widespread accumulation of gypsum in the region. The study area in the Central Namib Desert, between the Kuiseb and Omaruru rivers, features extensive gypsum accumulations in a ca. 50–70 km wide band, parallel to the shore. They consist of surficial or shallow pedogenic gypsum crusts in the desert pavement, hydromorphic playa or sabkha gypsum, as thin isolated pockets on bedrock ridges and as discrete masses of gypsum selenite along some faults. The sulphur isotopic values (δ³⁴S ‰CDT) of these occurrences are between δ³⁴S +13.0 and +18.8‰, with lower values in proximity to sulphuric ore bodies (δ³⁴S +3.1 and +3.4‰). Damaran bedrock sulphides have a wide range from δ³⁴S −4.1 to +13.8‰ but seem to be significant sources on a local scale at the most. Dissolved sulphate at playas, sabkhas, springs, boreholes and ephemeral rivers have an overall range between δ³⁴S +9.8 and +20.8‰. However, they do not show a systematic geographical trend. The Kalahari waters have lower values, between δ³⁴S +5.9 and +12.3‰. Authigenic gypsum from submarine sediments in the upwelling zone of the Benguela Current between Oranjemund and Walvis Bay ranges between δ³⁴S −34.6 to −4.6‰. A single dry atmospheric deposition sample produced a value of δ³⁴S +15.9‰. These sulphur isotopic results, complemented by meteorological, hydrological and geological information, suggest that sulphate in the Namib Desert is mainly derived from NSS sulphur, in particular oxidation products of marine dimethyl sulphide CH₃SCH₃ (DMS). The hyper-arid conditions prevailing along the Namibian coast since Miocene times favour the overall preservation of the sulphate minerals. However, sporadic and relatively wetter periods have promoted gypsum formation: the segregation of sulphates from the more soluble halite, and the gradual seaward redistribution of sulphate. This study suggests that the extreme productivity of the Benguela Current contributes towards the sulphur budget in the adjacent Namib Desert.     

Characterizing groundwater recharge using oxygen and hydrogen isotopes: a case study in a temperate forested region,South Korea

In the cool temperate region of South Korea, oxygen and hydrogen isotopes of groundwater, lake water, and precipitation were studied to determine the season of groundwater recharge. All the groundwater samples, irrespective of season, on δ¹⁸O–δ²H scale plotted along the summer precipitation, suggesting summer precipitation largely modulates recharge. The deuterium excess values of groundwater (d-excess) show clear seasonal difference, higher in winter (> 18‰) and lower in summer (< 10‰). And its resemblance to the summer precipitation d-excess value further suggests dominant role of summer precipitation in groundwater recharge. Based on the mass balance equation, with end-member d-excess values of seasonal precipitation and groundwater as input variables, groundwater is composed of 66% summer and 34% winter precipitation. Despite the study area being heavily forested, summer rainfall contribution higher than winter suggests that evapotranspiration effect is minimal in the region; may be due to thin sand–gravel-based porous soil overlying highly weathered granitic rock system.     

Sulphur cycling in organic-rich marine sediments from a Scottish fjord

In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ³⁴S and δ¹⁸O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ¹⁸O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ³⁴S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ³⁴S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ¹⁸O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ¹⁸O of the sulphate to 14‰ at 20 cm depth with no further change in the δ³⁴S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ³⁴S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ³⁴S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.     

The utilization of boron and strontium isotopes for the assessment of boron contamination of the Cecina River alluvial aquifer (central-western Tuscany,Italy)

The groundwater B concentration in the alluvial aquifer of the upper Cecina River basin in Tuscany, Italy, often exceeds the limit of 1 mg L⁻¹ set by the European Union for drinking water. On the basis of hydrogeological and geochemical observations, the main source of the B contamination of groundwater has been attributed to past releases into streams of exhausted, B-rich geothermal waters and/or mud derived from boric acid manufacturing in Larderello. The releases were discontinued 25–30 years ago.This study confirms that the B dissolved in groundwater is anthropogenic. In fact, the δ¹¹B values of groundwater B match the range −12.2‰ to −13.3‰ of the Turkish B mineral (colemanite) processed in boric acid manufacturing, in the course of which no significant isotopic effects have been observed. This isotopic tracing of the Cecina alluvial aquifer occurs just below the confluence of the Possera Creek, which carries the B releases from Larderello. Strontium isotope ratios support this conclusion.At about 18 km from the Possera Creek confluence, the groundwater δ¹¹B drops to much more negative values (−22‰ to −27‰), which are believed to be produced by adsorption–desorption interactions between dissolved B and the aquifer matrix. The δ¹¹B of B fixed in well bottom sediments shows a similar variation. At present, desorption is prevailing over adsorption because the releases of B-rich water have ceased. A theoretical model is suggested to explain the isotopic trends observed.Thus, B isotopes appear to be a powerful tool for identifying the origin of B contamination in natural waters, although isotopic effects associated with adsorption–desorption processes may complicate the picture, to some extent.