Boron isotopic geochemistry of karst groundwater in Guiyang City, China

Boron has two stable isotopes （^10B and ^11B） with relative abundances of about 20% and 80%, respectively. Boron isotopic ratios in natural materials show a huge range of variations, from -70‰ to ＋60‰, when expressed with the classical δ^11B notation. Most of these isotopic variations occur at the surface of the Earth. Hence, boron isotopic composition can be used as a sensitive tracer in geochemical study, for instance, to identify the different sources of contamination and factors controlling the salinity of groundwater. During the last decade, boron isotopes have been used to discriminate between the influences of seawater intrusion and anthropogenic discharge. But few of those researches can precisely identify the different sources of contamination. We measured the boron concentrations and boron isotopic ratios of groundwater samples collected in Guiyang City, as well as the major ions. The results indicate that the major ion composition of the groundwater in the investigated area is mainly controlled by the interactions between water and the dominant rock i.e. carbonates. All the water compositions are characterized by high concentrations of Ca^2＋, Mg^2＋, HCO3^-, SO4^2-, and NO3^-, which are the dominant contaminants. Both dissolved boron concentrations and isotopic ratios show large variations among the ground waters, from 2 μg/L to 90 μg/L and from -6‰ to ＋26‰, respectively. The boron concentrations and isotopic ratios indicate that the river across the studied city has been seriously contaminated by urban discharge. Boron concentrations of fiver water samples varied from 20 μg/L to 140 μg/L, with an average δ^11B value of ＋2.0‰. Using boron isotopic compositions and different geochemical indices allowed us to clearly identify and distinguish the two major sources of contamination, agricultural activity and urban wastewater. Both of the two sources are characterized by high boron concentrations but their boron isotopic compositions significantly differ.     

Soil carbon stock of the Central-East Asia in the climate warming

Water samples from the Wujiang River, a typical karst river system, were analyzed for major ion concentrations and δ^34S values of dissolved sulfate in order to identify the sources of sulfate, quantify the sulfate export flux and understand the role of sulfur cycling in chemical weathering rate of carbonate. Spatial variations in sulfate concentration and sulfur isotopic composition of tributaries over the catchment area are obvious, allowing to decipher S sources between rocks and atmosphere. According to the variations in sulfate concentration and isotopic composition, it is inferred that sulfate ions in the upper-reach river waters may have three sources, rain water, sulfate resultant from oxidation of pyrite in coal, and sulfate from sulfide deposits. In the lower reaches, the S isotopic composition of the samples lies mainly on a mixing trend between evaporite sulfate and rainwater sulfate, the contribution of sulfate from oxidation of pyrite being lesser. A pronounced seasonal variation in both content and isotopic composition of sulfate characterizes the Wujiang River. The average sulfate concentration of the waters is 0.65 mmol/L in winter, 0.17 mmol/L higher than that in summer. River water δ^34S values range from -15.7‰ to 18.9‰ in winter, while the δ^34S values of river waters in summer vary to a lesser extent than in winter, from -11.5‰ to 8.3‰. The δ^34S values of the main stream range from -6.7‰ to -3.9‰ in summer, averaging 3‰ lower than in winter. This indicates that in summer, when the discharge increases, the contribution of a source enriched in light isotopes to the atmosphere or the oxidation of pyrite in coal is more important.     

High-resolution sedimentary record of lead in the coastal mud of the East China Sea in the past one hundred and fifty years

In the East China Sea （ECS）, there are some mud areas, including the south coastal mud area, the north coastal mud area, and the mud area to the southwest of Cheju Island. X-ray fluorescence （XRF） techniques and Thermal Ionization Mass Spectrometry （TIMS） were used to study the high-resolution sedimentary record of Pb concentrations and Pb stable isotopic compositions in the past one hundred and fifty years in the coastal mud of the ECS. Pb concentrations of a ^210Pb dating S5 core in the study area have increased rapidly since 1980, and reached the maximal value with 65.08 μg/g in 2000, corresponding to the fast economic development of China since the implementation of the ＂Reform and Open Policy＂ in 1978; ^206Pb/^207Pb ratios generally had stabilized at 1.195 from 1860 to 1966, and decreased gradually from 1966 to 2000, indicating that the anthropogenic source Pb contribution to the ECS has increased gradually since 1966, especially since 1980. Pb concentrations decreased distinctly from 2000 to 2003 and ^206Pb/^207Pb ratios increased from 2001 to 2003, corresponding closely to the ban of lead gasoline from 2000 in China. From 1950 to 2003, there occurred four distinct decrease events of ^206Pb/^207Pb, possibly responding to the Changjiang River （Yangtze River） catastrophic floods in 1998, 1991, 1981 and 1954; from 1860 to 1966, there were two decrease periods of ^206Pb/^207Pb, which may respond to the catastrophic floods of Changjiang River in 1931 and 1935, and 1870. As a result of the erosion and drowning by the catastrophic floods, the anthropogenic lead accumulated in soil and water environments over a long period of time was brought into the Changjiang River, then part of them was finally transported into the ECS, which leads to changes in Pb stable isotopic composition.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons in finegrained sediments of the East China Sea

The nearshore mud area along the Changjiang （Yangtze River） estuary and the coast of Zhejiang and Fujian provinces, and the distal mud area to the southeast of Cheju Island, Korea are the modem accumulative centers, thus, being the ＂sinks＂ of pollutants such as Polycyclic Aromatic Hydrocarbons （PAHs） in the East China Sea （ECS）. PAHs of surface sediment samples from the mud areas of the ECS and a ^210Pb dating sediment core collected using a gravity core from the coastal mud area in the ECS were quantified by GC/MSD with the internal standard materials.     

Carbon and Oxygen Isotopic Characteristics of REE—Fluorocarbonate Minerals and Their Genetic Implications,Bayan Obo Deposit,Inner Mongloia,China

REE－fluorocarbonates as major REE minerals in the Bayan Obo deposit,the largest REE deposit in the world,were analyzed for their stable isotopic compositions,The δ^13 C and δ^18 O values of huanghoite,cebaite and bastnaesite from late-stage veins vary in the ranges of 7.8--4.0‰ and 6.7-9.4‰,respectively,These data are relatively similar to those of bastnaesites from banded ores:δ^13C-5.6--5.2‰ andδ^18O3.6-5.5‰.The REE fluorocarbonates from both late-staege veins and banded ores are characterized by lower δ^13 C and δ^18O values,especially the δ^18O values of bastnaesites from banded ores.Compared with them,the disseminated bastnaesits the dolomite-type ores possess rather highδ^13 C and δ^18O values,i.e.,-2.1-0.4‰ and 8.6-12.9‰ respectively.The high values are typical of the sedimentary host dolomite rocks as well as of the dolomite-type-ores.The carbon and oxygen isotopic characteristics of REE fluorocarbonate minerals provide new evidence for the hypothesis on the origin of Bayan Obo deposit-epigenetic hydrothermal metasomatism.     

Stable isotopes （S, Cl） and hydrochemical variations in a karstic ground water system, Guiyang, SW China

A groundwater system in a karstic terrain is easily subject to pollution and its remediation is difficult once contaminated by human activities. The groundwater samples collected in both winter and summer seasons at Guiyang, SW China, show a wide range of variations in chemical composition and dominance of Ca^2＋, Mg^2＋, SO4^2-, and HCO3^- ions. The anthropogenic inputs include Cl^-, NO3^-, SO4^2-, Na^＋, and K^＋, as judged from the relationships between different elemental ratios and sewage samples. Cl^- concentrations of all water samples in the study area vary from 0 to 3.9 mmol/L in winter and are higher than in summer. In most of the samples, SO4^2- concentrations are high, ranging from 0.1 to 11 mmol/U The studies show that the cycling of sulfur plays an important role in controlling water chemistry and fate of contaminants in groundwater. In order to understand the source of SO4^2- and the geochemical cycling of some elements in the karstic groundwater environment, we have carried out a study on the variations of S and Cl isotope compositions, in addition to other isotopic tracers such as ^87Sr/^86Sr and δ^13C studied previously. The δ^37Cl values of the groundwater samples present a seasonal variation, ranging from 0.00‰ to ＋2.03‰ in winter and from -1.46‰ to ＋0.29‰ in summer. The surface water samples show a similar range of variations as observed for groundwater. Two rainwater samples collected at Guiyang have a distinct isotopic signature （mean value is -3‰） compared to the δ^37Cl values reported in literature. These results indicate that ground water is mainly derived from precipitation and suggest a fast recharge of the karst system by surface water.     

Tourmaline geochemistry and boron isotopic variations as a guide to fluid evolution in the Qiman Tagh W-Sn belt,East Kunlun,China

The Qiman Tagh W-Sn belt lies in the westernmost section of the East Kunlun Orogen, NW China, and is associated with early Paleozoic monzogranites, tourmaline is present throughout this belt. In this paper we report chemical and boron isotopic compositions of tourmaline from wall rocks, monzogranites, and quartz veins within the belt, for studying the evolution of ore-forming fluids. Tourmaline crystals hosted in the monzogranite and wall rocks belong to the alkali group, while those hosted in quartz veins belong to both the alkali and X-site vacancy groups. Tourmaline in the walk rocks lies within the schorl-dravite series and becomes increasingly schorlitic in the monzogranite and quartz veins. Detrital tourmaline in the wall rocks is commonly both optically and chemically zoned,with cores being enriched in Mg compared with the rims. In the Al-Fe-Mg and Ca-Fe-Mg diagrams,tourmaline from the wall rocks plots in the fields of Al-saturated and Ca-poor metapelite, and extends into the field of Li-poor granites, while those from the monzogranite and quartz veins lie within the field of Li-poor granites. Compositional substitution is best represented by the MgFe_(-1), Al(NaR)_(-1), and AlO(Fe(OH))_(-1) exchange vectors. A wider range of δ~(11)B values from -11.1‰ to -7.1‰ is observed in the wall-rock tourmaline crystals, the B isotopic values combining with elemental diagrams indicate a source of metasediments without marine evaporates for the wall rocks in the Qiman Tagh belt. The δ~(11)B values of monzogranite-hosted tourmaline range from -10.7‰ and-9.2‰, corresponding to the continental crust sediments, and indicate a possible connection between the wall rocks and the monzogranite. The overlap in δ~(11)B values between wall rocks and monzogranite implies that a transfer of δ~(11)B values by anataxis with little isotopic fractionation between tourmaline and melts. Tourmaline crystals from quartz veins have δ~(11)B values between -11.0‰ and-9.6‰, combining with the elemental diagrams and geological features, thus indicating a common granite-derived source for the quartz veins and little B isotopic fractionation occurred. Tourmalinite in the wall rocks was formed by metasomatism by a granite-derived hydrothermal fluid, as confirmed by the compositional and geological features.Therefore, we propose a single B-rich sedimentary source in the Qiman Tagh belt, and little boron isotopic fractionation occurred during systematic fluid evolution from the wall rocks, through monzogranite, to quartz veins and tourmalinite.     

B, Sr, O and H Isotopic Compositions of Formation Waters from the Bachu Bulge in the Tarim Basin

In order to elucidate the origin and migration of basinal brines in the Bachu Bulge, Tarim Basin, we have carried out analyses on chemical composition, and boron, hydrogen and oxygen isotopes of formation waters together with the XRD of clay minerals from the Paleozoic strata. The waters show Ca, B, Li and Sr enrichment and SO4 depletion in the Carboniferous and Ordovician and K enrichment in part of the Ordovician relative to seawater. The relationship between δD and δ^18O shows that all the data of the waters decline towards the Global Meteoric Water Line with the intersection of them close to the present-day local meteoric water, suggesting that modern meteoric water has mixed with evaporated seawater. The ^87Sr/^86Sr ratios range from 0.7090 to 0.7011, significantly higher than those of the contemporary seawater. The δ^11B values range from ＋19.7 to ＋32.3‰, showing a decrease with the depth and B concentrations. The results suggest that isotopically distinct B and Sr were derived from external sources. However, since the percentages of illite are shown to increase with depth among clay minerals in the study area, i.e., illite is due to precipitation rather than leaching during deeper burial, it is unlikely for illite to have contributed a significant amount of B to the waters. Thus, B with low δ^11B values is interpreted to have been added mainly from thermal degradation of kerogen or the basalts in the Cambrian and Lower Ordovician.     

Origin of Halite in the Lanping–Simao Basin, Southeastern Tibetan Plateau, China: Evidence from Sr and Cl Isotopes

The Lanping?Simao Basin is located on the southeastern Tibetan Plateau, China, and contains massive evaporites. The origin of evaporites in the basin has been hotly debated because of the strong transformation by tectonic movement. Forty halite samples from borehole MK-3 in the Mengyejing area of the basin were collected and analyzed using XRD, Cl-Sr isotopes and chemical compositions to trace the origin of the evaporites in the basin. The Br × 103/Cl ratios of the halite samples are between 0 and 0.55, most of which are synchronized with the law of seawater evaporation and at the stage of halite precipitation from seawater, indicating that the evaporites are mainly of marine origin. The 87Sr/86Sr ratios range from 0.707489 to 0.711279; after correction, the 87Sr/86Sr 145 Ma ratios range from 0.704721 to 0.707611, equivalent with the 87Sr/86Sr ratios of seawater at 145 Ma, indicating a marine origin. The decay of 87Rb in the evaporite during deposition, change of the depositional environment and the unsealed environment at a later period resulted in the present 87Sr/86Sr ratios of some samples being high. The δ37Cl value compositions range from ?0.38‰ to 0.83‰, which is consistent with the δ37Cl value composition of the world marine halite (?0.6‰ to 0.4‰), further confirming that seawater is the main origin. In addition, the high δ37Cl value of some samples at the boundary of the upper and lower evaporite layers might be related to the influence of δ37Cl-rich brine and the incomplete dissolution of the halite.     

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China: Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of ?7.8‰ and ?53.0‰ for δ18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater (less than a depth of 150 m) in desert plateau range from ?10.6‰ to ?6.0‰ with an average of ?8.4‰ for δ18O and from ?85‰ to ?46‰ with an average of ?63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters (greater than a depth of 275 m) fall in ranges from ?11.6‰ to ?8.8‰ with an average of ?10.2‰ for δ18O and from ?89‰ to ?63‰ with an average of ?76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of 14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.     

Detrital,metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry

The boron isotopic composition of zoned tourmaline in two metasediments from the island of Syros, determined by secondary-ion mass spectrometry (SIMS), reflects the sedimentary and metamorphic record of the rocks. Tourmaline from a silicate-bearing marble contains small (≤20 μm) detrital cores with highly variable δ ¹¹B values (−10.7 to +3.6‰), pointing to a heterogeneous protolith derived from multiple sources. The sedimentary B isotopic record survived the entire metamorphic cycle with peak temperatures of ∼500°C. Prograde to peak metamorphic rims are homogeneous and similar among all analysed grains (δ ¹¹B ≈ +0.9‰). The varying δ ¹¹B values of detrital cores in the siliceous marble demonstrate that in situ B isotope analysis of tourmaline by SIMS is a potentially powerful tool for provenance studies not only in sediments but also in metasediments. A meta-tuffitic blueschist bears abundant tourmaline with dravitic cores of detrital or authigenic origin (δ ¹¹B ≈ −3.3‰), and prograde to peak metamorphic overgrowth zones (−1.6‰). Fe-rich rims, formed during influx of B-bearing fluids under retrograde conditions, show strongly increasing δ ¹¹B values (up to +7.7‰) towards the margins of the grains. The δ ¹¹B values of metamorphic tourmaline from Syros, formed in mixed terrigenous–marine sediments, reflect the B signal blended from these two different sources, and was probably not altered by dehydration during subduction.     

Biogeochemistry of the Russian Arctic. Kara Sea: Research results under the SIRRO project, 1995–2003

The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions aboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO₂ were examined throughout the whole sea area at more than 200 sites. The δ¹³C varies from −22 and −24‰ where Atlantic waters enter the Kara Sea and in the North-eastern part of the water area to −27‰ in the Yenisei and Ob estuaries. The value of δ¹³C of the plankton is only weakly correlated with the δ¹³C of the organic matter from the sediments and is lower by as much as 3–4‰. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the riverwaters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the off-shore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from −29 to −35‰ in the riverine part, from −28 to −27‰ in the estuaries, and from −27.0 to −25% in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO₂ concentrations, and long-distance CO₂ supply to the sea with riverwaters. The data obtained on the isotopic composition of CO₂ in the surface waters of the Kara Sea were used to map the distribution of δ¹³C_{CO 2}. The complex of hydrocarbon gases extracted from the waters included methane, C₂–C₅, and unsaturated C₂₌–C₄₌ hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3–5 μl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with δ¹³C from −105 to −90‰ first occurs in the sediments at depths of 40–200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the δ¹³C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (δ¹³C from −25 to −60‰) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea. Original Russian Text ? E.M. Galimov, L.A. Kodina, O.V. Stepanets, G.S. Korobeinik, 2006, published in Geokhimiya, 2006, No. 11, pp. 1139–1191.     

Salt Waters of the Northern Apennine Foredeep Basin (Italy): Origin and Evolution

The salt waters from the Emilia-Romagna sector of the Northern Apennine Foredeep have been investigated using major and trace element and stable isotope (δ²H, δ¹⁸O, δ³⁷Cl, δ⁸¹Br and ⁸⁷Sr/⁸⁶Sr ratio). Ca, Mg, Na, K, Sr, Li, B, I, Br and SO₄ vs. Cl diagrams suggest the subaerial evaporation of seawater beyond gypsum and before halite precipitation as primary process to explain the brine’s salinity, whereas saline to brackish waters were formed by mixing of evaporated seawater and water of meteoric origin. A diagenetic end-member may be a third component for mud volcanoes and some brackish waters. Salinization by dissolution of (Triassic) evaporites has been detected only in samples from the Tuscan side of the Apennines and/or interacting with the Tuscan Nappe. In comparison with the seawater evaporation path, Ca–Sr enrichment and Na–K–Mg depletion of the foredeep waters reveal the presence of secondary processes such as dolomitization–chloritization, zeolitization–albitization and illitization. Sulfate concentration, formerly buffered by gypsum-anhydrite deposition, is heavily lowered by bacterial and locally by thermochemical reduction during burial diagenesis. From an isotopic point of view, data of the water molecule confirm mixing between seawater and meteoric end-members. Local ¹⁸O-shift up to +11‰ at Salsomaggiore is related to water–rock interaction at high temperature (≈150°C) as confirmed by chemical (Mg, Li, Ca distribution) and isotopic (SO₄–H₂O) geothermometers. ³⁷Cl/³⁵Cl and ⁸¹Br/⁷⁹Br ratios corroborate the marine origin of the brines and evidence the diffusion of halogens from the deepest and most saline aquifers toward the surface. The ⁸⁷Sr/⁸⁶Sr ratio suggests a Miocene origin of Sr and rule out the hypothesis of a Triassic provenance of the dissolved components for the analyzed waters issuing from the Emilia-Romagna sector of the foredeep. Waters issuing from the Tuscan side of the Apennines and from the Marche sector of the foredeep show higher ⁸⁷Sr/⁸⁶Sr ratios because of the interaction with siliciclastic rocks.     

Isotopic Approach to Determining the Fate of Ammonium Regenerated from Sediments in a Eutrophic Sub-estuary of Waquoit Bay,MA

We measured fluxes of NH₄⁺ and NO₃⁻ and δ¹⁵N of NH₄⁺, sediment, and porewater NH₄⁺ from incubated sediment cores along a nitrate gradient and in different seasons from Childs River, MA. NH₄⁺ flux was low at the downstream site with the lowest concentration of organic matter (high salinity) but otherwise did not differ along the estuary. The δ¹⁵N of regenerated NH₄⁺ ranged from +6.1‰ to +15.3‰ but did not vary significantly with season or salinity; the mean for the entire estuary was +10.4 ± 0.5‰. Based on differences between the δ¹⁵N of regenerated NH₄⁺ and sediment, and expected isotopic fractionation due to remineralization, we concluded that nitrification occurred after remineralization of NH₄⁺. Differences between the δ¹⁵N of regenerated NH₄⁺ and the δ¹⁵N of porewater NH₄⁺ provided further evidence of nitrification. We estimated that 11% to 48% of remineralized NH₄⁺ underwent coupled nitrification–denitrification before release into the water column. In spite of losses to denitrification, NH₄⁺ flux released 1.4 mol N m⁻² year⁻¹ to the water column and could provide 42% of phytoplankton nitrogen requirements.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Using dual-isotope data to trace the origin and processes of dissolved sulphate: a case study in Calders stream (Llobregat basin,Spain)

Whereas most of the reported δ³⁴S values of dissolved sulphate are positive in the Llobregat basin, Calders stream, which is a tributary of the Llobregat River, is characterised by negative values. Stream waters, sampled monthly between 1997 and 1998, and quarterly in 1999, show an overall increase in δ³⁴S from −10‰ to 0‰, coupled with an increase in Na and Cl concentration. On the other hand, the oxygen isotopic composition of dissolved sulphate, δ¹⁸O, displayed an opposite trend with a slight decrease, from +9‰ to +6‰. Detailed sampling up stream in November 2000 indicated that, contrary to most of the surficial waters of the Llobregat basin with a δ³⁴S_SO4 mainly controlled by evaporites, in Calders stream, sulphate is derived from pyrite oxidation. The dual-isotope approach, coupled with chemical data, allowed us to identify the contribution of ³⁴S-rich sulphate effluents from anthropogenic sources, while mixing models, calculated between natural and anthropogenic sources, enabled us to estimate their contribution. Sudden increases of δ³⁴S and δ¹⁸O of dissolved sulphate in stream waters are believed to be caused by a sulphate reduction process related to oil spillage. The long-term enrichment in δ³⁴S, coupled with a decrease in δ¹⁸O_SO4, from Jan-97 to Aug-99, is interpreted as a progressive increase in the contribution of pig manure.     

Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

Hydrothermal gold mineralization at the Hira Buddini gold mine,India: constraints on fluid evolution and fluid sources from boron isotopic compositions of tourmaline

We determined the boron isotope and chemical compositions of tourmaline from the Hira Buddini gold deposit within the Archean Hutti-Maski greenstone belt in southern India to investigate the evolution of the hydrothermal system and to constrain its fluid sources. Tourmaline is a minor but widespread constituent in the inner and distal alteration zones of metabasaltic and metadacite host rocks associated with the hydrothermal gold mineralization. The Hira Buddini tourmaline belongs to the dravite–schorl series with variations in Al, Fe/(Fe+Mg), Ca, Ti, and Cr contents that can be related to their host lithology. The total range of δ¹¹B values determined is extreme, from −13.3‰ to +9.0‰, but 95% of the values are between −4 and +9‰. The boron isotope compositions of metabasalt-hosted tourmaline show a bimodal distribution with peak δ¹¹B values at about −2‰ and +6‰. The wide range and bimodal distribution of boron isotope ratios in tourmaline require an origin from at least two isotopically distinct fluid sources, which entered the hydrothermal system separately and were subsequently mixed. The estimated δ¹¹B values of the hydrothermal fluids, based on the peak tourmaline compositions and a mineralization temperature of 550°C, are around +1 and +10‰. The isotopically lighter of the two fluids is consistent with boron released by metamorphic devolatilization reactions from the greenstone lithologies, whereas the ¹¹B-rich fluid is attributed to degassing of I-type granitic magmas that intruded the greenstone sequence, providing heat and fluids to the hydrothermal system. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Recharge source and hydrogeochemical evolution of shallow groundwater in a complex alluvial fan system,southwest of North China Plain

Many cities around the world are developed at alluvial fans. With economic and industrial development and increase in population, quality and quantity of groundwater are often damaged by over-exploitation in these areas. In order to realistically assess these groundwater resources and their sustainability, it is vital to understand the recharge sources and hydrogeochemical evolution of groundwater in alluvial fans. In March 2006, groundwater and surface water were sampled for major element analysis and stable isotope (oxygen-18 and deuterium) compositions in Xinxiang, which is located at a complex alluvial fan system composed of a mountainous area, Taihang Mt. alluvial fan and Yellow River alluvial fan. In the Taihang mountainous area, the groundwater was recharged by precipitation and was characterized by Ca–HCO₃ type water with depleted δ¹⁸O and δD (mean value of −8.8‰ δ¹⁸O). Along the flow path from the mountainous area to Taihang Mt. alluvial fan, the groundwater became geochemically complex (Ca–Na–Mg–HCO₃–Cl–SO₄ type), and heavier δ¹⁸O and δD were observed (around −8‰ δ¹⁸O). Before the surface water with mean δ¹⁸O of −8.7‰ recharged to groundwater, it underwent isotopic enrichment in Taihang Mt. alluvial fan. Chemical mixture and ion exchange are expected to be responsible for the chemical evolution of groundwater in Yellow River alluvial fan. Transferred water from the Yellow River is the main source of the groundwater in the Yellow River alluvial fan in the south of the study area, and stable isotopic compositions of the groundwater (mean value of −8.8‰ δ¹⁸O) were similar to those of transferred water (−8.9‰), increasing from the southern boundary of the study area to the distal end of the fan. The groundwater underwent chemical evolution from Ca–HCO₃, Na–HCO₃, to Na–SO₄. A conceptual model, integrating stiff diagrams, is used to describe the spatial variation of recharge sources, chemical evolution, and groundwater flow paths in the complex alluvial fan aquifer system.     

Genetic identification of natural gases from shallow reservoirs in some oil- and gas-bearing basins of China

Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.