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1.
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.  相似文献   

2.
In the present study, a combination of the stable carbon isotope ratio (13C/12C) with radiocarbon data (14C) allowed us to perform the aerosol source apportionment. Filter samples of PM1 were collected during the warm and cold periods in rural and urban sites in Lithuania. The 14C/12C ratio of total carbon (TC) was measured using the single stage accelerator mass spectrometer quantifying of fossil and non-fossil derived aerosol emissions. The δ13C value was measured using an elemental analyser interfaced with an isotope ratio mass spectrometer. We have found that the highest fraction of contemporary carbon (fc?=?0.82) was measured during a warm period in a rural location. A higher fraction of fossil fuel-derived carbon was observed for air masses transported from highly industrialized Western European regions during both seasons. Isotope mass balance calculations revealed that the traffic emissions composed 15 and 25?% in rural and urban sites, respectively, and did not change during either season. Input from coal-derived aerosol particles was estimated to be 15?% at an urban site during the cold period. The combination of the stable carbon isotope ratio with the radiocarbon data allowed us to distinguish coal, liquid fossil fuel combustion, and non-fossil derived aerosol particle emissions.  相似文献   

3.
Stable isotopes of water (δ2H, δ18O) and δ13CTIC were used as a tool to trace the recharge processes, natural carbon (organic and inorganic) source and dynamics in the aquifers of the central Gangetic basin, India. Stable isotope (δ2H, δ18O) record of groundwater (n?=?105) revealed that the groundwater of Piedmont was recharged by meteoric origin before evaporation, while aquifers of the older and younger alluvium were recharged by water that had undergone evaporation loss. River Ganges and its tributaries passing through this area have very little contribution in recharging while ponds play no role in the recharging of adjacent aquifers. The connectivity of shallow aquifers of aquitard formation (comprised of clay/sandy clay with thin patches of fine grey sand), i.e. 25–60?m below ground level (bgl) with the main upper aquifer (at a depth of >120?m?bgl) was found to be higher in older and younger alluvium. Negative values of δ13CTIC (median ?9.6 ‰; range ?13.2 to ?5.4 ‰) and high TIC (median 35?mM; range 31–46?mM) coupled with low TOC (median 1.35?mg/L; range 0.99–1.77?mg/L) indicated acceleration in microbial activity in the younger alluvium, especially in the active floodplain of river Ganges and its proximity.  相似文献   

4.
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.  相似文献   

5.
On the Qinghai–Tibetan Plateau, isotopic signatures in soil–atmosphere CH4 fluxes were investigated in nine grasslands and three wetlands. In the grasslands, the fractionation factor for soil CH4 uptake, αsoil, was much smaller than the usually reported value of 0.9975–1.0095. Stepwise multiple variation analysis indicates that αsoil is higher for higher soil water contents but is lower for higher C/N ratios of soil surface biomass. In the three wetlands, the soil-emitted δ13C–CH4 was 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-emitted δ13C–CH4 include the soil C/N ratio, oxidation–reduction potential, soil C concentration and soil water contents. Geographical isotopic surveys revealed environmental constraints on the CH4 consumption pathways in grasslands and the biome type-specific consistency in CH4 production pathways in wetlands.  相似文献   

6.
ABSTRACT

We studied natural and forestry-drained peatlands to examine the effect of over 34 years lowered water table on the δ13C values of vegetation, bulk peat and subsoil. In the seven studied sites, δ13C in the basal peat layer was 1.1 and 1.2?‰ lower than that of the middle-layer and surface layer, respectively. Furthermore, there was a positive correlation between the δ13C values of the basal and surface peat layers, possibly due to carbon (C) recycling within the peat column. In the same mire complex, natural fen peat δ13C values were lower than those of the nearby bog, possibly due to the dominance of vascular plants on fen and the generally larger share of recycled C in the fens than in the bogs. Furthermore, natural and 51 years previously drained fen and bog, on the opposite sides of a ditch on the same mire complex, showed no significant differences in δ13C values. Plant δ13C values were lower, while δ13C values of subsoil were higher in the drained than in the natural site of the fen.  相似文献   

7.
Some natural plant extract formulations (NPEFs, also referred to as essential oils) used in organic farming have been shown to contain synthetic pesticides. We obtained samples of four NPEFs (Muso, Hekiro, Kensogen-Ten, and Nurse Green) that were contaminated with the synthetic pyrethroid cypermethrin, and we used gas chromatography coupled with combustion, cryofocusing, and isotope ratio mass spectrometry to determine the stable carbon isotope ratios (δ13C) for the cypermethrin in the four NPEF samples, as well as in ten cypermethrin reagents and two commercial pesticide formulations (Agrothrin emulsion and Agrothrin water-dispersible powder). Our goal was to identify the source of the cypermethrin in the NPEFs. Cryofocusing markedly sharpened the cypermethrin peak and thus improved the accuracy and precision of the determined δ13C values. The δ13C values (±?SD) of the 16 cypermethrin samples ranged from ?28.3?±?0.2 to ?24.5?±?0.2?‰. Surprisingly, the four NPEFs showed similar δ13C values (?26.8 to ?27.3?‰), suggesting that the cypermethrin in all the samples came from the same source (either the same chemical reaction or the same primary material). This possibility was supported by previously published results. In addition, the δ13C values of the two commercial pesticides were similar to the values for the NPEFs, suggesting that the commercial pesticides had been diluted and sold as NPEFs.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
The aim of this study was to identify sources of carbon turnover using stable isotope mass balances. For this purpose, two pre-reservoirs in the Harz Mountains (Germany) were investigated for their dissolved and particulate carbon contents (dissolved inorganic carbon (DIC), dissolved organic carbon, particulate organic carbon) together with their stable carbon isotope ratios. DIC concentration depth profiles from March 2012 had an average of 0.33 mmol L–1. Increases in DIC concentrations later on in the year often corresponded with decreases in its carbon isotope composition (δ13CDIC) with the most negative value of –18.4?‰ in September. This led to a carbon isotope mass balance with carbon isotope inputs of ?28.5?‰ from DOC and ?23.4, ?31.8 and ?30.7?‰ from algae, terrestrial and sedimentary matter, respectively. Best matches between calculated and measured DIC gains were achieved when using the isotope composition of algae. This shows that this type of organic material is most likely responsible for carbon additions to the DIC pool when its concentrations and δ13CDIC values correlate negatively. The presented isotope mass balance is transferable to other surface water and groundwater systems for quantification of organic matter turnover.  相似文献   

11.
A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ2H) and stable oxygen (δ18O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ2H and δ18O values of this reference water are?2.0±0.4 and?2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ2H and δ18O values of Standard Light Antarctic Precipitation reference water are?428 and?55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty (U=2uc) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.  相似文献   

12.
Ontogenetic niche shifts in diet are a consequence of changes in body size or resource partitioning between age classes. To better resolve the feeding patterns of the Japanese scallop Mizuhopecten yessoensis, we examined the relative importance of age and size in the diet of this species using stable isotope ratios of carbon (δ13C) and nitrogen (δ15N) from 2006 to 2009. Contribution of food sources was quantified using an isotope mixing model by comparing the muscle tissue isotope ratios to those of suspended particulate organic matter (SPOM) and their zooplankton prey (e.g. micro- and meso-zooplankton). Unlike the δ13C values, which remained constant with age and size, muscle δ15N values were more positively correlated with age accounting for 69?% of variations than size with only 46?%. Increasing 15N values with age suggested that shifts in diet from SPOM to micro- and meso-zooplankton occurred during ontogeny in M. yessoensis. Results of the isotope mixing model indicated that SPOM contribution to scallop’s diet decreased from 68 to 8?% while those of zooplankton increased from 15 to 50?% with increasing age. This study concludes that age-related dietary shift explains the enrichment of 15N, as a result of predation on zooplankton by M. yessoensis.  相似文献   

13.
The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 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 Feisthauer S, Vogt C, Modrzynski J, Szlenkier M, Krüger M, Siegert M, Richnow HH. Different types of methane monooxygenases produce similar carbon and hydrogen isotope fractionation patterns during methane oxidation. Geochim Cosmochim Acta. 2011;75:11731184. doi: 10.1016/j.gca.2010.12.006[Crossref], [Web of Science ®] [Google Scholar]] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses 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 oxidation υm was proved to be equal to 4.0 and 1.3 mM mM?1 h?1 for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM?1 h?1 for M. 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 in 13C. 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.  相似文献   

14.
The isotopic compositions of carbon compounds in landfill leachate provide insights into the biodegradation pathways that dominate the different stages of waste decomposition. In this study, the carbon geochemistry of different carbon pools, environmental stable isotopes and compound-specific isotope analysis (CSIA) of leachate dissolved organic carbon (DOC) fractions and gases show distinctions in leachate biogeochemistry and methane production between the young area of active waste emplacement and the old area of historical emplacement at the Trail Road Landfill (TRL).

The active area leachate has low DOC concentrations (<200 mg l?1) dominated by fulvic acid (FA=160 mg l?1), and produces CH4 dominantly by CO2 reduction (D? excess=20.6‰). Leachate generated in the area of older waste has high DOC (>4770 mg l?1) dominated by FA (4482 mg l?1) and simple fatty acids (acetic=1008 mg l?1 and propionic=608 mg l?1), and produces CH4 by the acetate fermentation pathway (D? excess=9.8‰). CSIA shows an advanced degradation and a progressive accumulation of 13C of fatty acids in leachate from the older area. The enriched 13C value of FA (?20 and?26‰ for the older and active parts, respectively,) and of low molecular weight DOC (?8 and?27‰) as well as of the bulk DOC (?21 and?25‰) shows more advanced degradation in the older part of the landfill, which is consistent with the shift in the humic/FA ratios (0.05 and 0.18). The 13C enrichment of acetate (?12‰) above the 13C of DOC (?21‰) and of propionic acid (?19‰), in older leachate, suggests that this acetate has not evolved from the simple degradation of larger organic molecules, but by homoacetogenesis from the enriched dissolved inorganic carbon (DIC) pool (8‰) and H2, which produce a more enriched 13C of acetate. In contrast, the 13C of the minor acetate in the active area (?17‰) indicates that CO2-reducing bacteria must be the primary consumers of H2, which has resulted in enriched 13CDIC (10‰) and depleted 13CCH4 (?58‰).  相似文献   

15.
16.
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 δ2Hsweat was determined using an isotope ratio mass spectrometer. Before pulse labelling, δ2Hsweat – 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 δ2Hsweat 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?’  相似文献   

17.
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, CO2 and 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 of δ13C and δ15N 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.  相似文献   

18.
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.  相似文献   

19.
Abstract

A novel microcombustion technique for carbon isotopic analysis of nanogram amounts of carbon in non-volatile materials based on isotope ratio monitoring (irm) mass spectrometry is described. Liquid or solid samples placed in a quartz sleeve are combusted at 1000°C in a continuous stream of helium and oxygen. CO2 removed from the carrier gas stream by cryogenic trapping is transferred onto a GC column. Following GC separation, the CO2 is transferred via an open split to the ion source of a gas isotope ratio mass spectrometer. Reproducibility for samples >25 nmol carbon is <1‰. Problems associated with blanks from various sources and with reproducible deposition of small sample amounts led to variable accuracy, which was dependent on the compound class being analysed. Minimum sample size was in the range from 5 to 10 nmol carbon. Measurements of dissolved organic carbon (DOC) of groundwater from Germany yielded consistent values of δ13C = -28.8‰.  相似文献   

20.
The preferred tissue for analyses of fish stable isotope ratios for most researchers is muscle, the sampling of which typically requires the specimen to be sacrificed. The use of non-destructive methods in fish isotopic research has been increasing recently, but as yet is not a standard procedure. Previous studies have reported varying levels of success regarding the utility of non-lethally obtained stable isotope materials, e.g. fins, but none have accounted for the potential compounding effects of inorganic components of fin rays or lipids. Comparisons of carbon (δ13C) and nitrogen (δ15N) stable isotope ratios of muscle with adipose and caudal fin of two salmonids, Atlantic salmon (Salmo salar L.) and brown trout (Salmo trutta L.), revealed that caudal fin can be used as a non-destructive surrogate for muscle in stable isotope analysis, but that adipose fin, where available, is a better proxy. The use of a published model to inexpensively counteract the confounding effect of lipids, which are depleted in 13C, greatly improved the relationship between fish muscle and fins. However, efforts to account for the inorganic components of fin rays were counterproductive and required twice the biomass of fins clipped from each fish. As this experiment was conducted on wild fish, controlled laboratory studies are required to confirm these field observations.  相似文献   

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