Methane-derived carbonates in a native sulfur deposit: stable isotope and trace element discriminations related to the transformation of aragonite to calcite

Abstract Stable isotope ((13)C, (18)O, (34)S) and trace element (Sr(2+), Mg(2+), Mn(2+), Ba(2+), Na(+)) investigations of elemental sulfur, primary calcites and mixtures of aragonite with secondary, post-aragonitic calcite from sulfur-bearing limestones have provided new insights into the geochemistry of the mineral forming environment of the native sulfur deposit at Machów (SE-Poland). The carbon isotopic composition of carbonates (δ(13)C = -41 to -47‰ vs. PDB) associated with native sulfur (δ(34)S = + 10 to + 15‰ vs. V-CDT) relates their formation to the microbiological anaerobic oxidation of methane and the reduction of sulfate derived from Miocene gypsum. From a comparison with experimentally derived fractionation factors the element ratios of the aqueous fluids responsible for carbonate formation are estimated. In agreement with field and laboratory observations, ratios near seawater composition are obtained for primary aragonite, whereas the fluids were relatively enriched in dissolved calcium during the formation of primary and secondary calcites. Based on the oxygen isotope composition of the carbonates (δ(18)O = -3.9 to -5.9‰ vs. PDB) and a secondary SrSO(4) (δ(18)O = + 20‰ vs. SMOW; δ(34)S = + 59‰ vs. V-CDT), maximum formation temperatures of 35°C (carbonates) and 47°C (celestite) are obtained, in agreement with estimates for West Ukraine sulfur ores. The sulfur isotopic composition of elemental sulfur associated with carbonates points to intense microbial reduction of sulfate derived from Miocene gypsum (δ(34)S ≈ + 23‰) prior to the re-oxidation of dissolved reduced sulfur species.     

Influence of Earthworms on the Sulfur Turnover in the Soil

Abstract

The effects of earthworm activity on the concentration and isotopic composition of total sulfur in soils was investigated using batch experiments. Two ecologically different lumbricid species, the anecic Lumbricus terrestris and the endogeic Aporrectodea caliginosa, were used. The earthworms were fed birch leaves, beech leaves, cattle manure or mixed plant litter. All food sources differed isotopically (δ³⁴S) from the soil (Parabraunerde). As a reference, one experiment was carried out without additional food.

The experimental results show, that both earthworm species influence the total S-content and the δ³⁴S-values in the soil by digestion of the different food sources. The differences in the total S-content of the earthworm tissues and in the S-isotopic composition of the casts can be attributed to the ecological differences between the earthworm species.     

Evaluation of the Sulfate Dynamics in Groundwater by Means of Environmental Isotopes

Abstract

Elevated sulfate concentrations and their heterogeneous distribution in the drinking water catchment area Torgau-Mockritz (Germany) were investigated by means of multiple isotope signatures such as δ³⁴S, δ¹⁸O-H₂O, δD, tritium, and ⁸⁵Kr. δ³⁴S values of the groundwater sulfate vary between -19…+ 37‰ CDT. No simple correlation exists between sulfate concentrations and δ³⁴S. Superimposition of different sulfur sources and mobilization processes combined with a complicated groundwater movement create a complex distribution pattern. The oxidation of reduced sedimentary sulfur has to be regarded as a main source of dissolved sulfate at least regionally. Tritium and ¹⁴C data revealed that old groundwater can be excluded as source for high sulfate contents. Correlated temporal variations in the concentrations of tritium and sulfate are observed in deeper sampling positions. Highly variable δ¹⁸O and δD, as detected in parts of the catchment area, indicate local influences of surface water infiltration into the aquifer. The spatial distribution of isotope signatures enables the identification of zones with descending younger water or hindered groundwater movement and hence provides useful hints for flow modeling.     

Field-deployable measurements of free-living individuals to determine energy balance: fuel substrate usage through δ13C in breath CO2 and diet through hair δ13C and δ15N values

Carbon isotopes of breath CO₂ vary depending on diet and fuel substrate used. This study examined if exercise-induced δ¹³C-CO₂ changes in substrate utilization were distinguishable from baseline δ¹³C-CO₂ variations in a population with uncontrolled diet, and compared hair isotope values and food logs to develop an isotope model of diet. Study participants included nine women with diverse Body Mass Index (BMI), age, ancestry, exercise history, and diet. Breath samples were collected prior to and up to 12?h after a 5- or 10?K walk/run. Indirect calorimetry was measured with a smartphone-enabled mobile colorimetric device, and a field-deployable isotope analyzer measured breath δ¹³C-CO₂ values. Diet was assessed by food logs and δ¹³C, δ¹⁵N of hair samples. Post-exercise δ¹³C-CO₂ values increased by 0.54?±?1.09‰ (1 sd, n?=?9), implying enhanced carbohydrate burning, while early morning δ¹³C-CO₂ values were lower than daily averages (p?=?0.0043), indicating lipid burning during overnight fasting. Although diurnal δ¹³C-CO₂ variation (1.90?±?0.77‰) and participant baseline range (3.06‰) exceeded exercise-induced variation, temporal patterns distinguished exercise from dietary isotope effects. Hair δ¹³C and δ¹⁵N values were consistent with a new dietary isotope model. Notwithstanding the small number of participants, this study introduces a novel combination of techniques to directly monitor energy balance in free-living individuals.     

Preface - Contributions to the 8th International Conference on Applications of Stable Isotope Techniques to Ecological Studies (ISOECOL), Brest,France, 20–24 August 2012

Abstract

The study is focused on the dolomite-limestone drinking water aquifers in the Bo? massif, as well as on the andesite-aquifer containing mineral water in the vicinity of Roga?ka Slatina. The catchment area is limited and both drinking and mineral waters are discharged from the same source. The increasing use of deeper aquifers means that natural springs and shallow wells have become sporadic. Consequently new techniques of investigating recharge and aquifer capacity are required which can augment classical hydrogeological methods.

Current research into the mineral and drinking water aquifers in the area of Roga?ka Slatina is based on measuring the isotopic composition of light elements, (H, C and O) as natural tracers. It can be concluded that all the groundwaters investigated are typically infiltrated meteoric water. The drinking waters are generally young and were infiltrated up to about ten years ago. The isotopic composition of oxygen is similar to recent precipitation (δ¹⁸O = -9.3 ± 1‰) and the drinking waters contain tritium. It was found that exploited mineral waters recharged aquifers during colder periods; they are only partly mixed with younger water as can be seen from the isotopic composition of oxygen and corrected ¹⁴C dating, which puts the mean ages at between around 100 and 8,000 years. With regard to the “nuclear period” (1960-64) with abnormally high tritium activities of precipitation, all the waters examined can be divided into at least three main infiltration groups depending on their measured tritium content: around 35 years old (> 80 T.U.), older (> 10 T.U.) and younger (10 to 60 T.U.). Detailed dating is possible following the above classification. Isotope exchange between rocks and water is negligible and therefore very deep circulation at the temperature conditions above 80°C does not occur. Dissolved inorganic carbon (DIC) in the drinking waters is the result of equilibrium reactions between carbonates and organically produced CO₂ (δ¹³C = - 14.5 ± ‰), while the high concentrations of DIC (δ¹³C = + 3 ±‰) and CO₂ observed in the mineral waters are generated by low-temperature decarbonatization processes and indicate the deep origin of CO₂, from where gas migrates into mineral water aquifers.

Correlation analyses between the parameters studied are performed. Useful conclusions concerning water circulation and the capacities of aquifer reservoirs are described which support the future optimal pumping of mineral and drinking water at the limited catchment area of Roga?ka Slatina and Bo?.     

The relative isotopic abundance (δ13C, δ15N) during composting of agricultural wastes in relation to compost quality and feedstock

Variations in the relative isotopic abundance of C and N (δ¹³C and δ¹⁵N) were measured during the composting of different agricultural wastes using bench-scale bioreactors. Different mixtures of agricultural wastes (horse bedding manure?+?legume residues; dairy manure?+?jatropha mill cake; dairy manure?+?sugarcane residues; dairy manure alone) were used for aerobic–thermophilic composting. No significant differences were found between the δ¹³C values of the feedstock and the final compost, except for dairy manure?+?sugarcane residues (from initial ratio of ?13.6?±?0.2?‰ to final ratio of ?14.4?±?0.2?‰). δ¹⁵N values increased significantly in composts of horse bedding manure?+?legumes residues (from initial ratio of +5.9?±?0.1?‰ to final ratio of +8.2?±?0.5?‰) and dairy manure?+?jatropha mill cake (from initial ratio of +9.5?±?0.2?‰ to final ratio of +12.8?±?0.7?‰) and was related to the total N loss (mass balance). δ¹³C can be used to differentiate composts from different feedstock (e.g. C₃ or C₄ sources). The quantitative relationship between N loss and δ¹⁵N variation should be determined.     

Sulfate Reduction in a Forested Catchment as Indicated by δ34S Values of Sulfate in Soil Solutions and Runoff

Abstract

In a forested catchment in the Fichtelgebirge mountains (NE-Bavaria, Germany) the long term SO₄ ^2- budget (average 1988–1994) indicated that about 40% of the input with throughfall (16.8 kg SO₄ ^2- S·ha^?1·yr^?1) was retained in the catchment. In order to identify processes acting as potential SO₄ ^2- sinks, δ³⁴S values of SO₄ ^2- in soil solutions and runoff were measured between May and November 1994. δ³⁴S values of the runoff and the fen were higher (5.8‰) than the δ³⁴S values of the soil solution of the oxic soils in the terrestrial area (3.9‰). Because there is no lithogenic S source within the catchment, it can be assumed that SO₄ ^2- deposition is the only S source in the catchment. Thus the results were interpreted as a result of SO₄ ^2- reduction within the catchment, because the uptake of ³²S is favoured during the dissimilatory SO₄ ^2- reduction and ³⁴S is consequently enriched in the soil solution. To estimate the amount of SO₄ ^2- reduced isotopic fractionation factors between ? 9‰ and ?46‰ were considered, resulting in SO₄ ^2- reduction rates of 1.8–9.3 kg SO₄ ²-S·ha^?1yr^?1. It was concluded that besides dissimilatory SO₄ ^2- reduction another sink exists in the catchment (e.g. SO₄ ^2- sorption in deep soil layers).     

Stable Carbon Isotope Fractionation in Lower Plants from the Schirmacher and Untersee Oases (Central Dronning Maud Land,East Antarctica)

Abstract

Lower plants (algae, lichens, mosses) from the Antarctic continent have been analysed for their stable carbon isotope composition. In contrast to lichens and mosses which exhibit quite normal δ¹³C-values the studied microbial benthos is characterized by an extremely low carbon isotope fractionation (δ¹³C-values up to ?1.4‰. vs. PDB). Limited CO₂ availability and bicarbonate uptake are probably the main factors responsible for this phenomenon.     

On the potential of Raman‐spectroscopy‐based carbonate mass spectrometry

The potential for using Raman spectroscopy to measure stable oxygen isotope ratios (¹⁸O/¹⁶O) in carbonates is evaluated by measuring the Raman spectra and isotope ratios of a suite of 60 synthesized, ¹⁸O‐enriched calcite crystals ranging in composition from natural abundance (0.2 mole‐% ¹⁸O) to 1.2 mole‐% ¹⁸O. We determined the Raman‐inferred isotopic ratios (R_Raman) by fitting curves to the ν₁ symmetric stretching peak at 1086 cm⁻¹ and the smaller satellite peak, associated with the ν₁ stretching mode of singly substituted carbonate groups (C¹⁶O₂¹⁸O) at 1065 cm⁻¹. The ratio of the two peak areas shows a 1:1 correspondence with the ¹⁸O/¹⁶O ratios derived from standard mass spectrometry methods, confirming that the relative intensities of the ν₁ symmetric stretching peaks is a direct measure of the isotopic ratio in the carbonates. The 1‐sigma uncertainties of the R_Raman values of the individual crystals were 0.00079 (384‰ PDB) and 0.00043 (210‰ PDB) for the four‐crystal sample means. This level of uncertainty is much too high to provide significant estimates of natural variability; however, there are multiple prospects for improving the accuracy and precision of the technique. Carbon isotope ratios in carbonates cannot be measured by our approach, but our results highlight the potential of Raman‐based isotope ratio measurement for C and other elements in minerals and organic compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

Using the 13C/12C carbon isotope ratio to characterise the emission sources of airborne particulate matter: a review of literature

ABSTRACT

Particulate matter (PM) from atmospheric aerosols contains carbons that are harmful for living organisms and the environment. PM can originate from vehicle emissions, wearing of vehicle components, and dust. Size and composition determine PM transport and penetration depth into the respiratory system. Understanding PM emission characteristics is essential for developing strategies to improve air quality. The number of studies on carbon isotope composition (¹³C/¹²C) of PM samples to characterise emission factors has increased. The goal of this review is to integrate and interpret the findings from ¹³C/¹²C carbon isotope ratio (δ¹³C, ‰) analyses for the most common types of emission sources. The review integrates data from 25 studies in 13 countries. The range of δ¹³C of PM from vehicle emissions was from ?28.3 to ?24.5?‰ and for non-vehicle anthropogenic emissions from ?27.4 to ?23.3?‰. In contrast, PM ranges for δ¹³C from biomass burning sources differed markedly. For C₃ plants, δ¹³C ranged from ?34.7 to ?25.4?‰ and for C₄ plants from ?22.2 to ?13.0?‰. The ¹³C/¹²C isotope analysis of PM is valuable for understanding the sources of pollutants and distinguishing vehicle emissions from biomass burning. However, additional markers are needed to further distinguish other anthropogenic sources.     

Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers,nitric acid,and reagent salts

Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ¹⁵N values of synthetic and natural nitrates were 0?±?2?‰ similar to the air N₂ from which they are derived. The δ¹⁸O values of synthetic nitrates were 23?±?3?‰, similar to air O₂, and natural nitrate fertilizer δ¹⁸O values (55?±?5?‰) were similar to those observed in atmospheric nitrate. The Δ¹⁷O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ¹⁷O values of 18?±?2?‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.     

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite,and the effect of ion (de)solvation

In this study, we present the experimental results for stable barium (Ba) isotope fractionation (¹³⁷Ba/¹³⁴Ba) during the transformation of aragonite (CaCO₃) and gypsum (CaSO₄·2H₂O) in Ba-bearing aqueous solution to witherite (BaCO₃) and barite (BaSO₄), respectively. The process was studied at three temperatures between 4 and 60?°C. In all cases, the transformation leads to a relative enrichment of the lighter ¹³⁴Ba isotope in the solid compared to the aqueous solution, with ^137/134Ba enrichment factors between –0.11 and ?0.17?‰ for BaCO₃, and –0.21 and –0.26?‰ for BaSO₄. The corresponding mass-dependent ^138/134Ba enrichment factors are ?0.15 to –0.23?‰ for BaCO₃, and –0.28 to –0.35?‰ for BaSO₄. The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80?°C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO₄ and BaCO₃ using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.     

Isotopic characteristics of meteoric waters in the Belgrade region

Abstract

The stable isotope composition of hydrogen (δ²H) and oxygen (δ¹⁸O) in monthly precipitation and river water (Sava River and Danube) samples in the Belgrade area gathered between 1992 and 2005 are determined. The local meteoric water line δ²H=7.8 (±0.2) δ¹⁸O+7.3(±1.6) (r ²=0.98, n=60, σ=0.52) for the whole period of observation is close to the global meteoric water line. The amount-weighted mean δ²H and δ¹⁸O values of precipitation were?65±27 ‰ and?9.4±3.4 ‰, respectively. Good correlation between δ¹⁸O values (r>rsim0.67) and ambient temperature and relative humidity was obtained. Stream-water data ranged from?94 to?60 ‰ for δ²H and from?11.0 to ～5.7 ‰ for δ¹⁸O with highly statistically significant difference (p>0.01) between the Sava River and the Danube. In addition, the isotopic compositions of local precipitation and adjacent river water at monitoring sites were compared. Obtained data will give an opportunity to improve the knowledge of mixing stream water and local groundwater, and assessment of potential groundwater risks and pressures in the Belgrade basin.     

Isotope (δ13C, δ15N, δ2H) diet–tissue discrimination in African grey parrot Psittacus erithacus: implications for forensic studies

Diet–tissue isotopic relationships established under controlled conditions are informative for determining the dietary sources and geographic provenance of organisms. We analysed δ¹³C, δ¹⁵N, and non-exchangeable δ²H values of captive African grey parrot Psittacus erithacus feathers grown on a fixed mixed-diet and borehole water. Diet–feather Δ¹³C and Δ¹⁵N discrimination values were +3.8?±?0.3?‰ and +6.3?±?0.7?‰ respectively; significantly greater than expected. Non-exchangeable δ²H feather values (?62.4?±?6.4?‰) were more negative than water (?26.1?±?2.5?‰) offered during feather growth. There was no positive relationship between the δ¹³C and δ¹⁵N values of the samples along each feather with the associated samples of food offered, or the feather non-exchangeable hydrogen isotope values with δ²H values of water, emphasising the complex processes involved in carbohydrate, protein, and income water routing to feather growth. Understanding the isotopic relationship between diet and feathers may provide greater clarity in the use of stable isotopes in feathers as a tool in determining origins of captive and wild-caught African grey parrots, a species that is widespread in aviculture and faces significant threats to wild populations. We suggest that these isotopic results, determined even in controlled laboratory conditions, be used with caution.     

Sauna,sweat and science II – do we sweat what we drink?

ABSTRACT

Inspired by a previous ‘Sauna, sweat and science’ study [Zech et al. Isot Environ Health Stud. 2015;51(3):439–447] and out of curiosity and enthusiasm for stable isotope and sauna research we aimed at answering the question ‘do we sweat (isotopically) what we drink’? We, therefore, pulse-labelled five test persons in a sauna experiment with beverages that were ²H-enriched at about +25,600?‰. Sweat samples were collected during six sauna rounds and the hydrogen isotope composition δ²H_sweat was determined using an isotope ratio mass spectrometer. Before pulse labelling, δ²H_sweat – reflecting by approximation body water – ranged from –32 to –22?‰. This is ～35?‰ enriched compared to usual mid-European drinking water and can be explained with hydrogen-bearing food as well as with the respiratory loss of ²H-depleted vapour. The absence of a clearly detectable ²H pulse in sweat after pulse labelling and δ²H_sweat results of ≤+250?‰ due to a fast ²H equilibration with body water are moreover a clearly negative answer to our research question also in a short-term consideration. Given that the recovery of the tracer based on an isotope mass balance calculation is clearly below 100?%, we finally answer the question ‘where did the rest of the tracer go?’     

Turnover of hydrogen isotopes in lake sturgeon blood: implications for tracking movements of wild populations

Naturally occurring deuterium (²H) in biota can be used to trace movement, migration and geographic origin of a range of organisms. However, to evaluate movements of animals using δ²H measurements of tissues, it is necessary to establish the turnover time of ²H in the tissues and the extent of isotopic discrimination from different environmental ²H sources to those tissues. We investigated the turnover of ²H in lake sturgeon (Acipenser fulvescens) blood by manipulating both environmental water δ²H and diet δ²H over a four-month period. The half-life of deuterium in lake sturgeon blood was 37.9 days after an increase in the environmental water δ²H of +714?‰. However, no clear turnover in blood ²H occurred over the same period in a separate trial following a change of ?63.8?‰ or +94.2?‰ in diet. These findings suggest that environmental water ²H exchanges much faster with blood than diets and that blood δ²H values can be used to trace movements of sturgeon and other fish moving among isotopically distinct waters.     

Analysis of n(87Sr)/n(86Sr), δ88Sr/86SrSRM987 and elemental pattern to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria

Elemental and isotopic pattern of n(⁸⁷Sr)/n(⁸⁶Sr) and δ⁸⁸Sr/⁸⁶Sr_SRM987 were used to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria. Therefore, shallow, artesian and thermal groundwaters of the investigated aquifer along with rainfall and rivers were analysed using (MC) ICP-MS. The n(⁸⁷Sr)/n(⁸⁶Sr) ratio and elemental pattern changed with aquifer depth as a result of progressing bedrock leaching and dissolution with increasing groundwater residence time. The n(⁸⁷Sr)/n(⁸⁶Sr) ratio of shallow groundwater below saline ponds of 0.71019?±?0.00044 was significantly different from thermal groundwater of 0.71205?±?0.00035 (U, k?=?2). In contrast to previous theories, this result suggested no recharge of saline ponds by upwelling paleo-seawater. Isotope pattern deconvolution revealed that rainfall accounted to about 60% of the n(⁸⁷Sr)/n(⁸⁶Sr) ratio of shallow groundwater below saline ponds. The δ⁸⁸Sr/⁸⁶Sr_SRM987 values of groundwater decreased from about 0.25 ‰ in most shallow, to predominantly negative values of about –0.24 ‰ in artesian groundwater. This result indicated leaching and dissolution of weathered minerals. In turn, the δ⁸⁸Sr/⁸⁶Sr_SRM987 of deep thermal groundwater showed positive values of about 0.12 ‰, which suggested removal of ⁸⁶Sr from solution by carbonate precipitation. These results highlight the potential of δ⁸⁸Sr/⁸⁶Sr_SRM987 signature as an additional geochemical tracer.     

Prospects and Limitations of an Isotope Tracer Technique for Understanding Sulfur Cycling in Forested and Agro-Ecosystems

Abstract

Applications of isotopically distinct sulfur compounds have recently been used for tracing the fate of added sulfur in whole catchments or sub-compartments therein. Basic principles, the analytical methodology, and data evaluation for this isotope tracer technique are briefly described. We recommend that δ³⁴S-values of applied and natural sulfur compounds in the investigated ecosystem should differ by more than 20‰ in order to successfully ascertain sulfur fluxes. Where possible, a high ratio of applied sulfur loads versus sulfur pool sizes in the ecosystem should also be realized in order to allow the assessment of sulfur transformations in the study area. Prospects and limitations of this isotope tracer technique are critically discussed by reviewing results from recently or currently conducted lysimeter and field experiments.     

Chromium isotopes tracking the resurgence of hexavalent chromium contamination in a past-contaminated area in the Friuli Venezia Giulia Region,northern Italy

The origin of a resurgent hexavalent chromium contamination in groundwater from a phreatic aquifer in the Friuli Venezia Giulia Region plain was investigated by chromium isotopic systematics. The area underwent a severe Cr(VI) contamination by industrial effluents in 1997, when Cr(VI) concentration in groundwater reached 4500?µg/L. In subsequent years the contamination naturally attenuated, totally disappearing in 2003. A renewal of water contamination was observed in 2008, Cr(VI) reaching 1560?µg/L. The δ⁵³Cr value in groundwater and extracts from sediments was measured in 2009–2011, and it ranges between ?3.21 and +0.21‰ and between ?4.71 and +1.26‰, respectively. Due to the lack of geogenic Cr-sources, these data are interpreted as evidence of the subsequent oxidation through Mn-oxides of the Cr(III) hosted in the aquifer and originated by the reduction of the original industrial chromates. Cr(III) is characterized by negative δ⁵³Cr, starting from the δ⁵³Cr value around zero of Cr(VI) in industrial effluents. Oxidation liberates soluble Cr(VI) which is transported by groundwater and permeated soils. The complex Cr-isotopic vs. concentration distribution reflects both the new Cr(VI) reduction and dilution processes in the aquifer system. From an environmental point of view, the data raise concerns regarding the potential impact of past Cr(VI)-contamination.     

Chlorine isotopic compositions of deep saline fluids in Ibusuki coastal geothermal region,Japan: using B–Cl isotopes to interpret fluid sources

We report chlorine stable isotopic compositions (δ³⁷Cl, expressed in ‰ relative to the standard mean ocean chloride) as well as δ²H and δ¹⁸O values of deep saline fluids taken at eight drill-holes reaching from 73 to 780?m below sea level in the Ibusuki coastal geothermal region, Japan. Analytical results show that the δ³⁷Cl values narrowly range between ?0.26 and +0.21?‰ with an analytical precision of ±0.06?‰. Except for one sample, the samples examined are negative in δ³⁷Cl value with varying Cl/B molar ratios from 117 to 1265. A correlation study between the Cl/B molar ratio and the δ³⁷Cl/δ¹¹B ratio indicates a hyperbola-type mixing of at least two Cl sources in the Ibusuki region. One of them depletes in ³⁷Cl with a higher value of Cl/B molar ratio; and the other one enriches in ³⁷Cl with a lower Cl/B molar ratio. The former is chemically identical to that of the deep brine, which is altered seawater through the seawater–hot rock interaction. The latter is chemically similar to gas condensate derived from the high-temperature (890?°C) vent of an island-arc volcano near the Ibusuki region.