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The study of mixed natural gas can clarify the specific sources of natural gas accumulation and provide the basis for the exploitation of natural gas resources. Analysis of gas compositions and carbon isotopic ratios of different components of mixed natural gas shows that the carbon isotopic fractionation of methane and ethane from different sources has a small difference after mixing. This conclusion is derived from the experimental data in Table 1, 0.88 is the average of all Ro values. Well DN8 and DN9 produced light oil with a density between 0.75 and 0.82 g/cm3 and viscosity between 1.63 and 3.3 MPa. Generally, in the high maturity stage of organic matter, the carbon isotopic fractionation values of methane and ethane of natural gas from a single source should display a difference of at least 4.0% to 5.0%. The δ13C value of methane and ethane in well DN8 are only 1.6%. It is considered that the mixing of natural gas from different sources causes this phenomenon. [ABSTRACT FROM AUTHOR]

Isotope technology is widely used in geochemical mechanisms analysis; however, studies on the origin of pit lake water by isotopes in coal concentration areas in grassland are rare. In this study, 20 groups of water samples were collected, which were subjected to chemical analysis to determine the hydrogeochemical characteristics of pit lake water. The mechanisms of pit lake water formation and recharge–evaporation were ascertained through principal component analysis and the Rayleigh fractionation model. The results indicate that the phreatic water is least affected by evaporation, followed by confined water, surface water and pit lake water. The ionic composition of surface water, phreatic water and most of the confined water is mainly affected by leaching, some confined water can be recharged by surface or phreatic water; while the ionic composition of pit lake water is dominantly affected by evaporation (69.4 %) and is less affected by groundwater recharge (17.1 %) and human activities (11.5 %). The pit lake water is recharged by precipitation, phreatic water and the lateral runoff of confined water; however, the proportion of phreatic and confined water recharge is small. The evaporative loss of the pit lake water is 40–61 % of the initial water body. [ABSTRACT FROM AUTHOR]

We estimated δ13C of the C–H–O fluid produced by the decomposition of stearic acid at high-pressure and high-temperature conditions (10 and 17 GPa, 800–1600°C) from δ13C of the solid carbon products and the initial stearic acid. The δ13C of the stearic acid and the recovered graphite/diamond were −28.0‰ and −27.08 to −29.35‰, respectively. Then, the δ13C of the coexisting C–H–O fluid was estimated to be −26.3 to −29.2‰ based on the stoichiometry of the decomposition reaction C18H36O2 → 10C + 8CH4 + 2H2O. In the studied P-T-t conditions, carbon isotope fractionation through the stearic acid decomposition is as small as < 3‰. This means that the δ13C of the C–H–O fluid is almost identical to that of the initial stearic acid and can be a useful tracer of carbon source for diamond forming reaction such as in fluid/carbonate systems. [ABSTRACT FROM AUTHOR]

The oceans, serving as some of the most extensive reservoirs of mercury (Hg) on Earth, play an essential role in the global Hg biogeochemical circulation, as a sink for atmospheric deposits and surface runoff while simultaneously emitting Hg to the atmosphere. Clarifying the mechanisms during cycling of Hg in marine ecosystems is a crucial segment in elucidating global Hg behavior and assessing its risks to wildlife and humans. The stable Hg isotope technique has emerged as a powerful tool for identifying potential sources and certain processes of Hg. Herein, the research advances in marine Hg biogeochemical cycling were reviewed from an isotopic tracing perspective, including sources of marine Hg, isotopic fingerprints across various marine media, and applications of Hg isotopes in pathways, transport, and transformation mechanisms associated with marine environments. The knowledge gaps and challenges were further discussed in the development of ultratrace level and species-specific isotopic analytical methods, the isotope fractionation mechanisms in reactions and processes, and the integration of multiple approaches and cross disciplines. These future studies would advance our understanding of Hg behavior in oceanic environments, its authentic function, and interactions with other ecosystems in the global Hg cycle, and evaluate its response to environmental changes. [ABSTRACT FROM AUTHOR]

After the atmosphere, the ocean is the most well-mixed and homogeneous global geochemical reservoir. Both physical and biological processes generate elemental and isotope variations in seawater. Contrasting geochemical behaviors cause elements to be susceptible to different fractionation mechanisms, with their isotopes providing unique insights into the composition and evolution of the ocean over the course of geological history. Supplementing the traditional stable isotopes (H, C, O, N, S) that provide information about ocean processes and past environmental conditions, radiogenic isotope (Sr, Nd, Os, Pb, U) systems can be used as time markers, indicators of terrestrial weathering, and ocean water mass mixing. Recent instrumentation advances have made possible the measurement of natural stable isotope variations produced by both mass-dependent and mass-independent fractionation for an ever-increasing number of metal elements (e.g. Li, B, Mg, Si, Ca, V, Cr, Fe, Ni, Cu, Zn, Se, Mo, Cd, Tl, U). The major emphasis in this review is on the isotopic composition of the light elements based on a comparatively large literature. Unlike O, H and S, the stable isotopes of C, N and Si do not have a constant isotopic composition in the modern ocean. The major cations Ca, Mg, and Sr fixed in carbonate shells provide the best proxies for reconstruction of the composition of the ocean in the past. Exhibiting large isotope enrichments in ocean water, B and Li are suitable for the investigation of water/rock interactions and can act as monitors of former oceanic pH. The bioessential elements Zn, Cd, and Ni are indicators of paleoproductivity in the ocean. Characteristic isotope enrichments or depletions of the multivalent elements V, Cr, Fe, Se, Mo, and U record the past redox state of the ocean/atmosphere system. Case studies describe how isotopes have been used to define the seawater composition in the geological past. [ABSTRACT FROM AUTHOR]

Isotope fractionation of fatty acids can reflect the metabolic pathway of fatty acids in organisms, but few studies have been conducted. In this study, stable carbon isotope fractionation of fatty acids in sea cucumber (Apostichopus japonicus) was conducted by feeding experiments of comparing the fatty acid profile and δ13C of fatty acids in body wall to diet. The results showed that the fractionation of δ13C of fatty acids in A. japonicus was −1.588–7.403‰. The fractionation of δ13C of saturated fatty acids (SFAs), monounsaturated fatty acids (MUFAs), and polyunsaturated fatty acids (PUFAs) was 1.098–7.403‰, −1.588–2.778‰, and −1.559–5.614‰, respectively. The degree of fractionation of δ13C of SFAs was greater than that of unsaturated fatty acids (UFAs). We simulated the possible metabolic process of fatty acids in A. japonicus based on fatty acid profile and δ13C of fatty acids, indicating that the combination of these two methods could be potentially used in the study of fatty acid metabolism in marine benthic animal of A. japonicus. Our finding provides a new technique for the metabolic pathways of biomolecules in organisms. [ABSTRACT FROM AUTHOR]

The changes in δ13CH4 and δ12C1H32H during sulphate-dependent anaerobic oxidation of methane (AOM) were described using dynamic modelling. The batch sulphate-dependent AOM at the nearly linear dynamics of methane oxidation with different enriched cultures originating from three marine sediments was simulated. The traditional Rayleigh equation for carbon and hydrogen stable isotopes in methane was derived from the basic dynamic isotope equation. The general and reduced models, taking into account the reaction stoichiometry and based on balances of chemical elements and their isotopes, describes a redistribution of stable isotope values in the sulphate-dependent AOM process. It was shown that AOM is the first and rate-limiting step in the whole AOM + SR (sulphate reduction) process. The different fractionation factors of carbon and hydrogen isotopes in methane were obtained for three marine sediments. It was concluded that during incubation the highest concentration of methanotrophic archaea might be responsible for the lowest fractionation factors of stable isotopes of carbon and hydrogen in methane. The interpretation of this phenomenon was suggested. Different concentrations of methanotrophic archaea can lead to variations of isotope fractionation factors. [ABSTRACT FROM AUTHOR]

In the present study we investigated the isotope effects associated with water loss from closed low-density polyethylene (LDPE) bottles via diffusion at temperatures between 4 and 60 °C. While at low temperatures (4 and 10 °C) no substantial diffusional loss of water was observed within storage time, a pronounced loss was found for the experiments at room temperature and 60 °C. The latter was associated with a substantial increase in δ18O, δ17O, and δ2Η values, and a decrease in the deuterium excess. The magnitude of the isotope effects essentially depended on the extent of water evaporation from the closed bottles through the LDPE membrane. [ABSTRACT FROM AUTHOR]

Radiocarbon activity (a14C) and 13C composition (δ13C) were measured in hygrophyte and mesophyte (land) mosses collected in the natural habitat of the Plitvice Lakes and along the Zrmanja and Krupa Rivers (typical continental and Mediterranean climates, respectively), Croatia. a14C and δ13C values of mosses, of atmospheric CO2 and dissolved inorganic carbon (DIC) were compared with contemporary data and with data from 30 years ago at the Plitvice Lakes when 14C activity of atmospheric CO2 was ∼30% higher. A positive correlation between a14Cmoss and δ13Cmoss was observed for all data reflecting the change of carbon isotopic composition in DIC along the water flows and in atmospheric CO2 regardless of the climatic regions and historic period. Fraction of the atmospheric carbon in moss (ω atm. C ) and carbon fractionation factor from aquatic CO2 (DIC) to moss tissue (ε moss / g − aq ) were calculated for each individual moss. Three species of mosses had ωatm.C ∼ 0 % implying that they turn to anabiosis during dry periods. The relation ε moss / g − aq vs. ω atm. C differentiates true aquatic and amphiphyte mosses. The first had a statistically significant negative correlation between ε moss / g − aq and ω atm. C . The amphiphyte mosses had lower ε moss / g − aq with higher water flow rates. [ABSTRACT FROM AUTHOR]

There has been extensive research on the effects of evaporation on the isotopic ratio of lacustrine and marine water bodies; however, there are limited data on how ablation or sublimation from lake or sea ice influences the isotopic ratio of the residual water body. This is a challenging problem because there remains uncertainty on the magnitude of fractionation during sublimation and because ablation can involve mixed-phase processes associated with simultaneous sublimation, melting, evaporation, and refreezing. This uncertainty limits the ability to draw quantitative inferences on changing hydrological budgets from stable isotope records in arctic, Antarctic, and alpine lakes. Here, we use in situ measurements of the isotopic ratio of water vapor along with the gradient diffusion method to constrain the isotopic ratio of the ablating ice from two lakes in the McMurdo Dry Valleys, Antarctica. We find that during austral summer, the isotopic fractionation of ablation was insignificant during periods of boundary layer instability that are typical during midday when latent heat is highest. This implies that the loss of mass during these periods did not yield any isotopic enrichment to the residual lake mass. However, fractionation increased after midday when the boundary layer stabilized and the latent heat flux was small. This diurnal pattern was mirrored on synoptic timescales, when following warm and stable conditions latent heat flux was low and dominated by higher fractionation for a few days. We hypothesize that the shifting from negligible to large isotopic fractionation reflects the development and subsequent exhaustion of liquid water on the surface. The results illustrate the complex and nonlinear controls on isotopic fractionation from icy lakes, which implies that the isotopic enrichment from ablation could vary significantly over timescales relevant for changing lake volumes. Future work using water isotope fluxes for longer periods of time and over additional perennial and seasonal ice-covered lake systems is critical for developing models of the isotopic mass balance of arctic and Antarctic lake systems. [ABSTRACT FROM AUTHOR]

Based on pioneering work reported in the 1980s by Martin and co-workers, experimental investigation of the site-specific, natural (2H/1H) isotope fractionation in bioproducts by natural abundance deuterium 1D-NMR (NAD 1D-NMR) spectroscopy is the method of choice to understand the enzymatic mechanisms leading to their synthesis or transformation, but also to determine their geographical or botanical origins. This approach, known as 2H-SNIF-NMRTM method, is also an effective tool in the fight against the counterfeiting of molecules of economical interests. However, the use of achiral isotropic solvents has two significant disadvantages that reduce accessible isotopic information: a rate of overlap of signals generally too high for complex analytes and the absence of spectral discrimination of enantiotopic directions in prochiral compounds. Both drawbacks can be overcome by replacing liquid solvents with chiral liquid crystals (CLCs). In this review, we overview the theoretical basis and the analytical advantages of anisotropic NAD (ANAD) 2D-NMR using polypeptide-based, lyotropic CLCs as enantiodiscriminating ordered NMR solvents. We discuss how and why ANAD 2D-NMR can provide a robust alternative to the conventional method of determining isotopic ratios (2H/1H)i, particularly when applied to long-chain fatty acids or homogeneous triglycerides. Various applicative aspects are presented. [ABSTRACT FROM AUTHOR]

For many years after the discovery of the two stable isotopes of boron (10B,11B) in 1920 they were not used as tracers in the soil–plant system due to analytical constraints. However, with the advent of inductively coupled plasma mass spectrometry in the early 1980s, it became possible to measure precisely the natural variations of the B isotopes in biological systems. Nevertheless, up to the present time there is very little information in the literature on δ11B variations in soils, plants, fertilizers and foodstuffs. Therefore, information on the potential of δ11B as a tracer of B dynamics in natural- and agro-ecosystems remains limited. The relative abundance of the boron isotope (δ11B) in soils, plants and nutrient sources, and applications of variations in the natural abundance of 11B as a tracer of anthropogenic sources of nitrate contamination of water and the provenance of agricultural products are reviewed. [ABSTRACT FROM AUTHOR]

Saltpetre (KNO3; potassium nitrate) is one of the major ingredients of gunpowder. Simplex saltpetre (total 126 samples) together with gunpowder (total 93 samples) commodities which are currently prevailing in local markets as used for wildlife hunting and rocket festivals (local name in Lao: Boun Ban Fai) were collected from throughout Lao PDR. Dual isotopic composition of nitrates (δ15N, δ18O) was analyzed by the microbial denitrification method. Binary plotting of the data was conducted to characterize the mode of formation. In Lao PDR, almost all the commodities were imported from neighbouring Thailand, and to a lesser extent from Israel. Binary plotting of δ15N vs. δ18O of nitrates shows their intrinsic origin manufactured by Haber–Bosch and subsequently Ostwald processes. We observed an inverse correlation (δ15Nnitrate: up to + 12 ‰; δ18Onitrate: down to + 15 ‰), deviating from the reservoir values (free air) of δ15N (dinitrogen; up to 0 ‰) and δ18O (oxygen; +23.5 ‰), interpreted this as an indication of isotope fractionation during manufacture. The most plausible interpretation for this is the fractionation associated with formation of NO following NO2 and finally NO3 products. A nearly comparable inverse relationship is also observed for nitrates in pyrotechnics manufactured in China. [ABSTRACT FROM AUTHOR]

Comparing two different techniques applied for the extraction of marine pore water samples from sediments, the well-established whole round (WR) method and the more recent Rhizon method, in terms of their effects on stable calcium isotope ratios in extracted pore waters, we recognize a systematic offset between the two sampling methods. Higher δ44/40Ca values are associated with lower Ca concentrations for the Rhizon sampling technique and lower δ44/40Ca values are associated with higher Ca concentrations for the corresponding WR-derived pore water samples. Models involving Rayleigh fractionation and mixing calculation suggest that the observed offset is most likely caused by a combined process of CaCO3 precipitation and ion exchange taking place during Rhizon sampling-induced CO2 degassing. Changing pressure, extraction time or extraction yield during WR pressing does not lead to a variation in δ44/40Ca, indicating that no Ca isotope fractionation takes place during the sampling of pore water. On the basis of analytical and modelling results, WR samples appear to provide δ44/40Ca values that are more representative of the 'true' pore water isotopic composition. While the difference between the sampling techniques is close to the present-day analytical precision of Ca isotope analysis, it may become more relevant with increasing analytical precision in the future. [ABSTRACT FROM AUTHOR]

Elemental and isotopic pattern of n(87Sr)/n(86Sr) and δ88Sr/86SrSRM987 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/86SrSRM987 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/86SrSRM987 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/86SrSRM987 signature as an additional geochemical tracer. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

This paper examines the nitrogen isotope fractionation factors (α) associated with the volatilisation of ammonia from water under controlled conditions at two pH values (8.5 and 9.2). This experiment assumed the continuous removal of ammonia at a single purge rate of 10 mL air min−1. The fractionation resulting from the removal of total ammonia from the water into an acid trap was named the observed isotope fractionation factor (αobs), and it was measured as 1.019 (±0.0025) at pH 8.5 and 1.030 (±0.0025) at pH 9.2. The observed isotope fractionation factor includes the equilibrium isotope fractionation factor (αeq) and the kinetic isotope fractionation factor (αkin), each one mathematically derived from the experimental data. The equilibrium and kinetic isotope fractionation factors were estimated as αeq = 1.036 (±0.0014) and αkin = 1.050 (±0.003), respectively. Our results are compared to other previously measured and estimated fractionation factors. [ABSTRACT FROM AUTHOR]

We described mathematically the process of peat methanization in a boreal mesotrophic fen. Gaseous and dissolved CH4 and CO2 as well as their δ13C signatures were considered in the dynamic equations for incubation bottles. In accordance with the model, acetate, H2, and CO2 were produced during cellulose hydrolysis and acidogenesis. 13C/12C in CO2 was a key variable reflecting dynamic changes in the rates of cellulose hydrolysis and acidogenesis, acetoclastic and hydrogenotrophic methanogenesis. As CO2 is the substrate in hydrogenotrophic methanogenesis, δ13C-CO2 increased from the start till the dissolved hydrogen concentration became very low. Thereafter, the rate of acetoclastic methanogenesis with the significant current acetate concentration dominated over the rate of hydrogenotrophic methanogenesis leading to the decreasing δ13C-CO2 and the increasing δ13C-CH4. The model was validated by describing the system’s dynamics under strong and weak inhibition of acetoclastic and hydrogenotrophic methanogenesis by methyl fluoride, respectively. During peat methanization at the lowered temperature of 10 °C, the processes of hydrogenotrophic methanogenesis and homoacetogenesis competing for H2 may occur. However, based on dynamics of the carbon isotope signatures, especially on dynamics of δ13C-CO2, the model showed no significant contribution of homoacetogens in peat methanization. [ABSTRACT FROM AUTHOR]

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2 ‰ for δ2H and 1 ‰ for δ18O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8 ‰ for δ2H and 4 ‰ for δ18O. In (3), PWS water was enriched relative to CE water by 3 ‰ for δ2H and 0.9 ‰ for δ18O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams). [ABSTRACT FROM AUTHOR]

We used pore water samplers (PWS) to sample for isotope analysis (1) only water, (2) soil under laboratory conditions, and (3) soil in the field comparing the results with cryogenic extraction (CE). In (1) and (2), no significant differences between source and water extracted with PWS were detected with a mean absolute difference (MAD) always lower than 2 ‰ for δ2H and 1 ‰ for δ18O. In (2), CE water was more enriched than PWS-extracted water, with a MAD respect to source water of roughly 8 ‰ for δ2H and 4 ‰ for δ18O. In (3), PWS water was enriched relative to CE water by 3 ‰ for δ2H and 0.9 ‰ for δ18O. The latter result may be due to the distinct water portions sampled by the two methods. Large pores, easily sampled by PWS, likely retain recent, and enriched, summer precipitation while small pores, only sampled by CE, possibly retain isotopically depleted water from previous winter precipitation or irrigation inputs. Accuracy and precision were greater for PWS relative to CE. PWS is therefore suggested as viable tool to extract soil water for stable isotope analysis, particularly for soils used in this study (sandy and silty loams). [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

On the Qinghai–Tibetan Plateau, isotopic signatures in soil–atmosphere CH4fluxes were investigated in nine grasslands and three wetlands. In the grasslands, the fractionation factor for soil CH4uptake,αsoil, was much smaller than the usually reported value of 0.9975–1.0095. Stepwise multiple variation analysis indicates thatαsoilis higher for higher soil water contents but is lower for higher C/N ratios of soil surface biomass. In the three wetlands, the soil-emittedδ13C–CH4was similar (−55.3 ± 5.5 ‰ and −53.0 ± 5.5 ‰) in two bogs separated by >1000 km but was lower (−63.4 ± 6.3 ‰) in a marsh. Environmental factors related to intrasite variations in soil-emittedδ13C–CH4include the soil C/N ratio, oxidation–reduction potential, soil C concentration and soil water contents. Geographical isotopic surveys revealed environmental constraints on the CH4consumption pathways in grasslands and the biome type-specific consistency in CH4production pathways in wetlands. [ABSTRACT FROM AUTHOR]

This study provides the first characterization of the variability of bromine and chlorine stable isotopic composition in evaporites, associated residual brines, and shoreline gases in terrestrial evaporative saline lakes. The lakes investigated here are groundwater discharge locations, and include both potash-rich alkaline lakes and sodic-dominated neutral pH lakes at a variety of salinities and evaporative stages. The chlorine and bromine isotope systems behave consistently different during evaporative salt precipitation, with37Cl more enriched in the salt than in the fluid, but81Br more enriched in the fluid compared with the precipitated salt. The81Br concentration of shore off-gassing was even smaller than mineral precipitate compositions. The trends observed for bromine isotopes are surprising compared with published laboratory studies, indicating that a process besides inorganic mineral precipitation is affectingδ81Br. Additional processes explored include diffusion, salt deflation, microbial and photolytic conversion to the gas phase, and oxidative bromination of organic matter. Dedicated to Professor Peter Fritz on the occasion of his 80th birthday [ABSTRACT FROM PUBLISHER]

Plants that absorb silicon may induce isotope fractionation that causes relative abundance changes in biogeochemical processes in organisms and environment. Silicon isotopes (28Si, 29Si, and 30Si) were determined with high precision using multicollector inductively coupled plasma mass spectrometer. In the present study, the silicon isotope composition was determined in maize and corresponding soil was collected from Zhejiang Province, China. The δ30Si values were from −2.7 to 3.3‰ in the plant tissues. The isotope fractionation between precipitated and dissolved silicon was 0.9976 and the silicon isotope fractionation in the plants was appeared to be Rayleigh-like process. The fractionation factors between the whole plants and the soil–water-soluble fractions were estimated to be 0.9989, indicating the presence of biochemical silicon isotope fractionation. The active uptake of silicon appeared to play an important role through which the heavy silicon isotopes were preferentially absorbed and transferred to the aboveground plant tissues. However, the roles of a passive mechanism for silicon uptake could not be ruled out through which the light silicon isotopes preferentially precipitated in various plant tissues. [ABSTRACT FROM AUTHOR]

Cryogenic vacuum extraction is the well-established method of extracting water from soil for isotopic analyses of waters moving through the soil–plant–atmosphere continuum. We investigate if soils can alter the isotopic composition of water through isotope memory effects, and determined which mechanisms are responsible for it. Soils with differing physicochemical properties were re-wetted with reference water and subsequently extracted by cryogenic water distillation. Results suggest some reference waters bind tightly to the soil and not all of this tightly bound water is removed during cryogenic vacuum extraction. Kinetic isotopic fractionation occurring when reference water binds to the soil is likely responsible for the18O-depletion of re-extracted reference water, suggesting an enrichment of the tightly bound soil water pool. Further re-wetting of cryogenically extracted soils indicates an isotopic memory effect of tightly bound soil water on water added to the soil. The data suggest tightly bound soil water can influence the isotopic composition of mobile soil water. Findings show that soils influence the isotope composition of soil water by (i) kinetic fractionation when water is bound to the soil and (ii) equilibrium fractionation between different soil water pools. These findings could be relevant for plant water uptake investigations and complicate ecohydrological and paleohydrological studies. [ABSTRACT FROM PUBLISHER]

Soil samples containing water with known stable isotopic compositions were prepared. The soil water was recovered by using vacuum/heat distillation. The experiments were held under different conditions to control rates of water evaporation and water recovery. Recoveries, δ18O and δ2H values of the soil water were determined. Analyses of the data using a Rayleigh distillation model indicate that under the experimental conditions only loosely bound water is extractable in cases where the recovery is smaller than 100 %. Due to isotopic exchange between vapour and remaining water in the micro channels or capillaries of the soil matrix, isotopic fractionation may take place under near-equilibrium conditions. This causes the observed relationship between δ2H and δ18O of the extracted water samples to have a slope close to 8. The results of this study may indicate that, in arid zones when soil that initially contains water dries out, the slope of the relationship between δ2H and δ18O values should be close to 8. Thus, a smaller slope, as observed by some groundwater and soil water samples in arid zones, may be caused by evaporation of water before the water has entered the unsaturated zone. [ABSTRACT FROM AUTHOR]

Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH3, CO2and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios (13C/12C) were obtained in size-segregated aerosol particles. The carbon (13C/12C) and nitrogen (15N/14N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution ofδ13C andδ15N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool. [ABSTRACT FROM AUTHOR]

We examined multiple natural abundance isotope ratios of human hair to assess biological variability within and between geographic locations and, further, to determine how well these isotope values predict location of origin. Sampling locations feature differing seasonality and mobile populations as a robust test of the method. Serially-sampled hair from Cambridge, MA, USA, shows lower δ2H and δ18O variability over a one-year time course than model-predicted precipitation isotope ratios, but exhibits considerable differences between individuals. Along a ∼13° north-south transect in the eastern USA (Brookline, MA, 42.3 ° N, College Park, MD, 39.0 ° N, and Gainesville, FL, 29.7 ° N) δ18O in human hair shows relatively greater differences and tracks changes in drinking water isotope ratios more sensitively than δ2H. Determining the domicile of humans using isotope ratios of hair can be confounded by differing variability in hair δ18O and δ2H between locations, differential incorporation of H and O into this protein and, in some cases, by tap water δ18O and δ2H that differ significantly from predicted precipitation values. With these caveats, randomly chosen people in Florida are separated from those in the two more northerly sites on the basis of the natural abundance isotopes of carbon, nitrogen, hydrogen, and oxygen. [ABSTRACT FROM AUTHOR]

For the first time, the dual isotope approach was applied to trace the sources of impacts and to identify the governing biogeochemical processes in a river network in the tropical deltaic region of the Red River (Vietnam). Our long term surveys concluded that water in this river network was severely impacted by anthropogenic activities. Analysis has shown strong spatio-temporal variation of nitrate isotopes; ranges of δ15N–and δ18O–were from −5 to 15 ‰ and from −10 to 10 ‰, respectively. Average values of δ15N–and δ18O–in the dry season, when fertilizer is applied, were 3.54 and 3.15 ‰, respectively. In the rainy season, the values changed to 6.41 and −2.23 ‰, respectively. Denitrification and biological assimilation were active throughout the year, but were especially enhanced during fertilization time. Mineralization of domestic organic matter and consequent nitrification of mineralizedwere the dominant processes, particularly during the rainy period. [ABSTRACT FROM AUTHOR]

We estimated the stable isotopic composition of water from the subglacial Lake Vostok using two different sets of samples: (1) water frozen on the drill bit immediately after the first lake unsealing and (2) water frozen in the borehole after the unsealing and re-drilled one year later. The most reliable values of the water isotopic composition are: −59.0 ± 0.3 ‰ for oxygen-18, −455 ± 1 ‰ for deuterium and 17 ± 1 ‰ ford-excess. This result is also confirmed by the modelling of isotopic transformations in the water which froze in the borehole, and by a laboratory experiment simulating this process. A comparison of the newly obtained water isotopic composition with that of the lake ice (−56.2 ‰ for oxygen-18, −442.4 ‰ for deuterium and 7.2 ‰ ford-excess) leads to the conclusion that the lake ice is very likely formed in isotopic equilibrium with water. In turn, this means that ice is formed by a slow freezing without formation of frazil ice crystals and/or water pockets. This conclusion agrees well with the observed physical and chemical properties of the lake's accreted ice. However, our estimate of the water's isotopic composition is only valid for the upper water layer and may not be representative for the deeper layers of the lake, so further investigations are required. [ABSTRACT FROM AUTHOR]

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteriaMethylosinus sporiumstrain 5 (NCIMB 11126) andMethylocaldum gracilestrain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu2+), copper-limited (0.3 µM Cu2+) or copper-regular (1.1 µM Cu2+) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [1]M. gracileinitially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereasM. sporiumexpresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidationυmwas proved to be equal to 4.0 and 1.3 mM mM−1h−1forM. sporiumunder copper-rich and copper-limited conditions, respectively, and 0.5 mM mM−1h−1forM. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in13C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental data presented in the two-dimensional plot of hydrogen versus carbon stable isotope signatures. [ABSTRACT FROM PUBLISHER]

We celebrate the contribution of Jochen Hoefs to the development of stable isotope (bio)geochemistry on the occasion of his 75th birthday. [ABSTRACT FROM AUTHOR]

As calculated from data archived in the IAEA-WMO Global Network of Isotopes in Precipitation programme, the amount-weighted local meteoric water line for the Pacific coast of central Panama is:δ2H = 7.63(±0.08) × δ18O + 6.51(±0.49). Amount-weighted mean isotopic values were regressed against the sea surface temperature (SST) fields of the adjacent tropical oceans. A negative correlation of precipitation isotope composition with Caribbean SSTs is observed only for the early wet season (May–June), whilst the mid-summer dry period is characterized by positive correlation with eastern Pacific SSTs, similar to the late wet season (October–November). The negative response of May–June rainfall isotopic composition to Caribbean SSTs is explained by a SST-mediated change in stratiform rain fraction from organized convective systems proximal to the Inter Tropical Convergence Zone (ITCZ). The positive correlation for the rest of the wet season, when the organized convective zone of ITCZ and its attached stratiform belt are distant from the Pacific coast of Panama, is interpreted as simple evaporative temperature effect on isotopic fractionation. [ABSTRACT FROM AUTHOR]

Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag3PO4and BiPO4are enriched in18O relative to AgPO4, and the three phosphates are consistently depleted in18O relative to Ba3[PO4]2; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of18O relative to hydroxyapatite. The valence, radii and coordination of metal cations play a quantitative role in dictating the18O/16O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag3PO4–H2O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag3PO4has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite–water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate–water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates. [ABSTRACT FROM AUTHOR]

Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in18O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0–1200 °C. The calculated fractionation factors for double carbonate–water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2and CaMg[CO3]2against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2and CO2are much closer to theoretical predictions for the cerussite–CO2system than for the magnesite–CO2system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates. [ABSTRACT FROM AUTHOR]

Stable isotope analysis is a fundamental tool in food origin and authenticity testing. Its use in livestock production requires knowledge of isotope discrimination between product and diet. Here, we report13C discrimination (13Δ) for milk, milk components (fat, casein and lactose) and faeces in eight lactating dairy cows, which grazed pasture or were fed fresh pasture herbage in the stall. Cows were supplemented with grain maize at 1.72 kg d−1(dry matter). Feed components were collected daily, and faeces, milk fat, casein, lactose and whole milk 4 times per week during an 8-week-long sampling period. Carbon isotope composition (δ13C) of each sample was analysed.δ13C was lowest in milk fat (−29.8 ‰) and highest in casein (−26.4 ‰). Compared to the diet, whole milk was depleted in13C (13Δ = 0.4 ‰) due to a strong13C-depletion of fat (13Δ = 2.2 ‰), which was not fully compensated by the13C-enrichment of casein (13Δ = −1.1 ‰) and lactose (13Δ = −0.7 ‰). Faeces were also depleted in13C (13Δ =1.7 ‰). Influences of feeding environment (stall vs. pasture) and herbage quality were minor (<0.4 ‰). A review of literature data shows large variation between studies. We consider that the present results are superior, as they are based on a much larger data set regarding the number of cows and milkings (totaln = 256) with greater detail in analyses of diet and milk products. Also, the study covered both stall- and pasture-feeding scenarios in realistic settings with long periods of equilibration. This is the first comprehensive analysis of13C discrimination between diet and all main milk components (as well as faeces). Thus, the results will improve the use of stable isotope analyses in regard to authenticity testing and proof of origin. [ABSTRACT FROM AUTHOR]

In this paper, hydrochemistry and boron isotopes are successfully applied to elucidate hydrogeological processes by the use of natural tracers. The hydrochemical analysis identifies four end-members in the hydrochemical evolution of groundwater from the North Chianan plain groundwater district. A few groundwater contain extraordinary chlorine concentrations of up to 48,000 mg l−1. However, the hydrochemistry of groundwater only reveals that high saline water is a dominant factor in groundwater hydrochemistry. It is thought that these groundwater experienced precipitation of carbonates during seawater evaporation that did not involve the precipitation of gypsum. Boron isotopes are very efficient tracers in determining the source of salinisation. The boron isotopes reveal the results of mixing of evaporated seawater and water–sediment interaction. In general, the boron isotope ratio of the groundwater is controlled by a two-end-member mixing system, which is composed of evaporated seawater (isotopically heavy) and fresh surface water (isotopically light). Due to a long lagoonal period in the coastal plain, the groundwaters in the downstream area generally have high Cl/B ratios and relatively heavy boron isotope ratios while those in the upstream area are composed of low Cl/B and light boron isotopes. However, there is not a resolvable mixing trend between the Cl/B ratio and the isotopic composition of boron. It is probably obscured by a highly variable boron isotope ratio in fresh surface water and through fractionation associated with water–rock interaction. Both factors would decrease the boron isotope ratio but one effect cannot be distinguished from the other. [ABSTRACT FROM AUTHOR]

The high geochemical reactivity of boron and the large relative mass difference between10B and11B lead to significant boron isotope fractionation in nature. So far the measured range of boron isotope composition (δ11B) varies between –70 and +75‰. The negative δ11B values are found in non-marine evaporite borate minerals and tourmalines, whereas positive δ11B values are common in salt lake brines and evaporated seawater. Since the 1980s, with improved measurement methods, applications of boron isotope analysis have increased rapidly. At present, boron isotopes are successfully applied to reconstruct ancient marine environments, to determine depositional environments and ore genesis, to trace groundwater pollution and seawater intrusion, and to study continental erosion. This paper summarises the methods for boron isotope analysis, the mechanisms of boron isotope fractionation and the distribution of boron isotopes in nature, reviews the achievements and the problems of boron isotopes in geochemical applications, and proposes research directions of boron isotopes in geochemical fields. [ABSTRACT FROM PUBLISHER]

Vanadium (V) in the sea squirt (Ciona savignyi) from Onagawa Bay, Miyagi, Japan, was isolated and purified through adsorption on a diamine resin and anion and cation exchanges after the dissolution of sea squirt samples with nitric acid and hydrogen peroxide. The 50V/51V isotope ratio of V thus obtained was mass-spectrometrically determined to be from 2.51×10−3 to 2.55×10−3 with the average of 2.53×10−3 by the thermal ionisation technique. This value agreed with those of vanadyl chloride and vanadyl nitrate both prepared from vanadyl sulphate (Wako Pure Chemical Industries, Ltd., Japan) and of V in coastal seawater (Shimokita Peninsula, Aomori, Japan) within experimental uncertainties (standard deviation of±0.04), which suggested that no appreciable V isotope fractionation occurs accompanying V uptake by the sea squirt from sea water. [ABSTRACT FROM AUTHOR]

Dissimilatory sulphate reduction (DSR) leads to an overprint of the oxygen isotope composition of sulphate by the oxygen isotope composition of water. This overprint is assumed to occur via cell-internally formed sulphuroxy intermediates in the sulphate reduction pathway. Unlike sulphate, the sulphuroxy intermediates can readily exchange oxygen isotopes with water. Subsequent to the oxygen isotope exchange, these intermediates, e.g. sulphite, are re-oxidised by reversible enzymatic reactions to sulphate, thereby incorporating the oxygen used for the re-oxidation of the sulphur intermediates. Consequently, the rate and expression of DSR-mediated oxygen isotope exchange between sulphate and water depend not only on the oxygen isotope exchange between sulphuroxy intermediates and water, but also on cell-internal forward and backward reactions. The latter are the very same processes that control the extent of sulphur isotope fractionation expressed by DSR. Recently, the measurement of multiple sulphur isotope fractionation has successfully been applied to obtain information on the reversibility of individual enzymatically catalysed steps in DSR. Similarly, the oxygen isotope signature of sulphate has the potential to reveal complementary information on the reversibility of DSR. The aim of this work is to assess this potential. We derived a mathematical model that links sulphur and oxygen isotope effects by DSR, assuming that oxygen isotope effects observed in the oxygen isotopic composition of ambient sulphate are controlled by the oxygen isotope exchange between sulphite and water and the successive cell-internal oxidation of sulphite back to sulphate. Our model predicts rapid DSR-mediated oxygen isotope exchange for cases where the sulphur isotope fractionation is large and slow exchange for cases where the sulphur isotope fractionation is small. Our model also demonstrates that different DSR-mediated oxygen isotope equilibrium values are observed, depending on the importance of oxygen isotope exchange between sulphite and water relative to the re-oxidation of sulphite. Comparison of model results to experimental data further leads to the conclusion that sulphur isotope fractionation in the reduction of sulphite to sulphide is not a single-step process. [ABSTRACT FROM AUTHOR]

The isotope ratios of various sulphur components (total sulphur content in the sediment, sulphate and H2S in the pore-water) were measured in a number of cores from recent marine sediments taken from the Kieler Bucht (Kiel Bay) region in the western Baltic Sea. Additionally, the quantitative contents of total sulphur, sulphate, sulphide, chloride, organic carbon, iron and water in the sediment and in the pore-water solutions, respectively, were determined. These investigations provided the following results: 1. The sulphur contained in the sediment (∼ 0.3–2% of the dry sample) was for the most part introduced only after sedimentation. This confirms the deliberations of Kaplan et al. [The Distribution and Isotopic Abundance of Sulfur in Recent Marine Sediments off Southern California, Geochim. Cosmochim. Acta 27, 297 (1963)]. The organic substance contributes to the sulphur content of the sediment only to an insignificant degree (in our samples with ∼5–10% of the total sulphur). 2. The sulphate in the pore-waters has been identified as a source for sulphur in the sediment. During normal sedimentation, the exchange of sulphate by diffusion significant for changes in the sulphur content goes down to a sediment depth of 4–6 cm. In this process, the sulphate consumed by reduction and formation of sulphide or pyrite is mostly replaced. The uppermost sediment layer thus represents a partially open system for the total sulphur. The diagenesis of the sulphur is allochemical. At depths below 4–6 cm, we are dealing with a closed system. The further diagenesis of sulphur here is isochemical. 3. The isotope values of the sediment sulphur are influenced primarily by sulphur which comes into the sediment by diffusion and which is bound by subsequent bacteriological reduction as either sulphide or pyrite. As a consequence of the prevailing reduction of 32S and reverse-diffusion of sulphate into the open sea water, a 32S enrichment takes place in the uppermost layer of the sediment. The δ34S values in the sediment range in general between−15 and−35‰, while seawater sulphate is+20‰. No relationship could be established between sedimentological or chemical changes and isotope ratios. In the cores, successive sandy and clayish layers showed no change in the δ34S values. However, the sedimentation rate seems to influence δ34S values. In one core with relatively low sedimentation rates, the δ34S values varied between−29 and−33‰, while cores with higher sedimentation rates showed values between−17 and−24‰. 4. As sediment depth increases, the pore-water sulphate shows, as expected, decreasing concentrations (in a depth of 30–40 cm, we found between 20 and 70% of the seawater values), and increasing δ34S values (in one case reaching more than+60‰). The concentration of sulphide in the pore-water increases, however, with sediment depth (to various extents, reaching 80 mg S per litre in one case). The δ34S values of the pore-water sulphide in all cores show increases paralleling the sulphate sulphur, with a nearly constant δ difference of 50–60‰ in all cores. This seems to confirm the genetic relationship between the two components. [ABSTRACT FROM AUTHOR]

Stable sulphur isotope fractionation was investigated during reduction of thiosulphate and elemental sulphur at 28°C by growing batch cultures of the sulphur- and thiosulphate-reducing bacteria Dethiosulfovibrio marinus (type strain DSM 12537) and Dethiosulfovibrio russensis (type strain DSM 12538), using citrate as carbon and energy source. The cell-specific thiosulphate reduction rate in the growth phase was 7.4±3.9 fmol cell−1 d−1. The hydrogen sulphide produced was enriched in 32S by 10.3±1 ‰ compared with total thiosulphate sulphur, close to previous experimental results observed for other sulphate- and non-sulphate-reducing bacteria. Elemental sulphur reduction yields sulphur isotope enrichment factors between−1.3 and−5.2 ‰ for D. russensis and−1.7 and−5.1 ‰ for D. marinus. The smaller fractionation effects are observed in the exponential growth phase (cellular rates between 5 and 70 fmol S° cell−1 d−1) and enhanced discrimination under conditions of citrate depletion and cell lysis (cellular rates between 0.3 and 3 fmol S° cell−1 d−1). [ABSTRACT FROM AUTHOR]

A mine dump aquifer in the Lusatian lignite mining district, Germany, is contaminated with acid mine drainage (AMD). The only natural process that can counteract the effects of the contamination is bacterial sulphate reduction. The technical measures chosen to handle the contamination include the injection of glycerol into the aquifer to supply electron donors and to accelerate the growth and activity of sulphate-reducing bacteria. An initial assessment of the hydrochemical conditions in the aquifer showed that sulphate concentrations are subject to alteration due to flow-related processes. Consequently, the decision whether sulphate reduction is occurring in the investigated aquifer section was based on the stable isotopic composition of dissolved sulphate and sulphide, which were used in combination with sulphate concentrations. The significant enrichment of both heavy sulphur and heavy oxygen in the remaining sulphate pool and a characteristic isotope fractionation pattern are a clear evidence for the activity of sulphate-reducing bacteria utilising the injected glycerol as an electron donor. This activity seemed to intensify over the observation period. The spatial distribution of sulphate reduction activity, however, appeared to be highly inhomogeneous. Rather than occurring ubiquitously, sulphate reduction activity seemed to concentrate in a defined reaction zone. Regardless of the inhomogeneous distribution, the overall turnover of sulphate during the period of investigation proves the applicability of this enhanced natural attenuation method to handle the restoration of aquifers contaminated with AMD. [ABSTRACT FROM AUTHOR]

We report calculated values of isotope fractionation factors between chlorine, bromine and sulphide hydrated anions and respective gaseous compounds: hydrogen chloride, hydrogen bromide, molecular chlorine and bromine and hydrogen sulphide. For the calculation of the reduced partition function ratios (β-factors) of hydrated Cl−, Br− and S2− anions, we used a model of a cluster composed of the considered ion surrounded by two shells of H2O molecules. Only the electrostatic interaction between ion and water molecules treated as electric dipoles was taken into account. The β-factors for the gaseous compounds (HCl, Cl2, HBr, Br2 and H2S) were calculated from vibrational frequencies reported by Urey and Greiff [Isotopic Exchange Equilibria, J. Am. Chem. Soc. 57, 321 (1935)] and Schauble et al. [Theoretical Estimates Equilibrium Chlorine-Isotope Fractionation, Geochim. Cosmochim. Acta 67, 3267 (2003)]. Low-temperature isotope fractionation between chlorine-hydrated anion and hydrogen chloride attains 1.55–1.68‰ (this work), which is in good agreement with experimental data (1.4–1.8‰) [Z.D. Sharp, J.D. Barnes, T.P. Fischer and M. Halick, An Experimental Determination of Chlorine Isotope Fractionation in Acid Systems and Applications to Volcanic Fumaroles, Geochim. Cosmochim. Acta 74, 264 (2010)]. The predicted isotope fractionations for hydrated bromine and HBr, Br2 gases are very small, 1000 ln α, do not exceed 0.8‰; thus, the expected variations of bromine isotope composition in aqua-gas systems will require enhanced precision for their detection. In contrast, the sulphur isotope fractionation between H2S gas and S2− attains 6.0‰ at room temperature and drops nearly linearly to 3.1‰ at 350°C. [ABSTRACT FROM AUTHOR]

A new analytical method is presented for the compound-specific carbon and nitrogen isotope ratio analysis of a thermo-labile nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by gas chromatograph coupled to an isotope ratio mass spectrometer (GC-IRMS). Two main approaches were used to minimise thermal decomposition of the compound during gas chromatographic separation: programmed temperature vaporisation (PTV) as an injection technique and a high-temperature ramp rate during the GC run. δ15N and δ13C values of RDX measured by GC-IRMS and elemental analyser (EA)-IRMS were in good agreement within a standard deviation of 0.3‰ and 0.4‰ for nitrogen and carbon, respectively. Application of the method for the isotope analysis of RDX during alkaline hydrolysis at 50°C revealed isotope fractionation factors ε carbon = −7.8‰ and ε nitrogen = −5.3‰. [ABSTRACT FROM AUTHOR]

Temporal variations in N concentration and δ15N value of annual tree rings (1 year of time resolution) of two Japanese Black Pine (Pinus thunbergii) and three Japanese Red Pine (Pinus densiflora) trees under current breeding activity of the Great Cormorant (Pharacrocorax carbo) and the Black-tailed Gull (Larus crassirostris), respectively, in central and northeastern Japan were studied. Both species from control sites where no avian input occurs show negative values (δ15N = around-4 ‰ to-2 ‰) which are common among higher plants growing under high rainfall regimes. The δ15N values of P. densiflora show uniformly positive values several years before and after the breeding event, indicating N translocation that moved the absorbed N of a given growth year to tree rings of the previous year while a clear historical value of soil N dynamics was kept intact in the annual rings of P. thunbergii. Long-term N trends inferred from tree rings must take into account tree species with limited translocation rates that can retain actual N annual acquisition. [ABSTRACT FROM AUTHOR]

Benzo 18-crown-6-ether resin was synthesised by the phenol condensation polymerisation process in porous silica beads, of which particle diameter was ca 60μ Calcium adsorption chromatography was performed with the synthesised resin packed in a glass column. The effluent was sampled in fractions, and the isotopic abundance ratios of 42Ca, 43Ca, 44Ca, and 48Ca against 40Ca were measured by a thermo-ionisation mass spectrometer. The enrichment of heavier calcium isotopes was observed at the front boundary of calcium adsorption chromatogram. The mass dependence of mutual separation of calcium isotopes was analysed by using the three-isotope-plots method. The slopes of three-isotope-plots indicate the relative values of mutual separation coefficients for concerned isotopic pairs. The results have shown the normal mass dependence; isotope fractionation is proportional to the reduced mass difference, (M - M')/MM', where M and M' are masses of heavy and light isotope, respectively. The mass dependence clarifies that the isotope fractionations are originated from molecular vibration. The observed separation coefficient ε is 3.1×10-3 for the pair of 40Ca and 48Ca. Productivity of enriched 48Ca by crown-ether-resin was discussed as the function of the separation coefficient and the height equivalent to the theoretical plate. [ABSTRACT FROM AUTHOR]

While the importance of environmental analyses based on isotope discrimination has been growing, uncertainties remain about underlying phenomena. Published results on the temperature dependence of carbon isotope fractionation during methane oxidation in various media show different trends. A decrease in fractionation is generally expected with temperature, but some data for methane oxidation in aqueous media show an inverse relationship. This apparent contradiction was probed by representing the first methane oxidation step as three elementary processes: the adsorption of methane on the bacterial cell wall, the desorption of methane from the wall, and the conversion of methane into methanol mediated by methane monooxygenase (MMO) enzymes. Assuming that the proportion of vacant adsorption sites is stationary, a formula for the composite fractionation factor α was obtained. It was shown that α not only expresses the fractionation that may occur in each elementary process, but that it also depends on the ratio of the kinetic rates for conversion into methanol and desorption. This result and experimental data were used to estimate the activation energy for the desorption of methane from methanotroph cell wall in aqueous medium (≈200 kJ/mol). Simple Rosso models of bacterial maximal-specific growth rate were then used to demonstrate that α and the isotope fractionation from the MMO-mediated conversion into methanol alone could vary in opposite ways as temperature changes, but that care must be exercised when using fitted relationships across wide temperature ranges. [ABSTRACT FROM AUTHOR]

Models that explain the oxygen isotope enrichment in leaf water (and biomass) treat the relationship between the kinetic fractionation that occurs during evapotranspiration and the stomatal conductance in an empirical way. Consequently, the isotopic enrichment is always predicted to decrease with increasing stomatal conductance, regardless of the experimental evidence to the contrary. We explain why and suggest an alternative method to reconcile theory and experiment. We support this with our experimental data on rice and groundnut plants. [ABSTRACT FROM AUTHOR]

The application of stable isotope ratio measurements has become an extremely useful tool for tracing the provenance of food products, thus ensuring that consumers receive products which comply with their labelled specifications. Recently, it has been shown that relative stable hydrogen isotope abundances (δ2H values) of wood lignin methoxyl groups have a distinct range that reflects the δ2H values of their meteoric source water. Furthermore, it has been suggested that the isotope information stored in methoxyl groups in plant matter generally might assist with determining the place of origin of plant material. We now have measured δ2H values of methoxyl groups from natural compounds in tubers of early potatoes (Solanum tuberosum) grown in different geographical locations. Tubers of early potatoes were collected from across Europe and regions close to the Mediterranean Sea between April and July 2004. The methoxyl groups from the potatoes were found to be highly depleted in 2H, relative to both their meteoric water and bulk biomass, and a systematic shift of the δ2H values between methoxyl groups and meteoric water was observed. A constant fractionation of-161±11‰. between methoxyl groups and modelled meteoric water is shown over a transaction covering the δ2H values of meteoric water from-95‰ in Northern Sweden to+25‰ in Egypt. From this information, early potato tubers from Middle Europe can be clearly distinguished from those of Mediterranean regions and from Northern Europe. Thus, we suggest that δ2H values of methoxyl groups have the potential to become an effective tool in assisting with the constraint of the geographical origin of potato tubers and other food stuffs. [ABSTRACT FROM AUTHOR]