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1.
Soil phosphate stable oxygen isotopes across rainfall and bedrock gradients   总被引:1,自引:0,他引:1  
The stable oxygen isotope compositions of soil phosphate (δ(18)O(p)) were suggested recently to be a tracer of phosphorus cycling in soils and plants. Here we present a survey of bioavailable (resin-extractable or resin-P) inorganic phosphate δ(18)O(p) across natural and experimental rainfall gradients, and across soil formed on sedimentary and igneous bedrock. In addition, we analyzed the soil HCl-extractable inorganic δ(18)O(p), which mainly represents calcium-bound inorganic phosphate. The resin-P values were in the range 14.5-21.2‰. A similar range, 15.6-21.3‰, was found for the HCl-extractable inorganic δ(18)O(p), with the exception of samples from a soil of igneous origin that show lower values, 8.2-10.9‰, which indicate that a large fraction of the inorganic phosphate in this soil is still in the form of a primary mineral. The available-P δ(18)O(p) values are considerably higher than the values we calculated for extracellular hydrolysis of organic phosphate, based on the known fractionation from lab experiments. However, these values are close to the values expected for enzymatic-mediated phosphate equilibration with soil-water. The possible processes that can explain this observation are (1) extracellular equilibration of the inorganic phosphate in the soil; (2) fractionations in the soil are different than the ones measured at the lab; (3) effect of fractionation during uptake; and (4) a flux of intercellular-equilibrated inorganic phosphate from the soil microbiota, which is considerably larger than the flux of hydrolyzed organic-P.  相似文献   

2.
Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on oxidation state. Arsenite [As(III)] can be oxidized to arsenate [As(V)] by both minerals and microbes in soil however, the interaction between these abiotic and biotic processes is not well understood. In this study, the time dependency of As(III) oxidation by two heterotrophic soil bacteria (Agrobacterium tumefaciens and Pseudomonas fluorescens) and a poorly crystalline manganese (Mn) oxide mineral (δ-MnO(2)) was determined using batch experiments. The apparent rate of As(V) appearance in solution was greater for the combined batch experiments in which bacteria and δ-MnO(2) were oxidizing As(III) at the same time than for either component alone. The additive effect of the mixed cell- δ-MnO(2) system was consistent for short (<1 h) and long (24 h) term coincubation indicating that mineral surface inhibition by cells has little effect the As(III) oxidation rate. Surface interactions between cells and the mineral surface were indicated by sorption and pH-induced desorption results. Total sorption of As on the mineral was lower with bacteria present (16.1 ± 0.8% As sorbed) and higher with δ-MnO(2) alone (23.4 ± 1%) and As was more easily desorbed from the cell-δ-MnO(2) system than from δ-MnO(2) alone. Therefore, the presence of bacteria inhibited As sorption and decreased the stability of sorbed As on δ-MnO(2) even though As(III) was oxidized fastest in a mixed cell-δ-MnO(2) system. The additive effect of biotic (As-oxidizing bacteria) and abiotic (δ-MnO(2) mineral) oxidation processes in a system containing both oxidants suggests that mineral-only results may underestimate the oxidative capacity of natural systems with biotic and abiotic As(III) oxidation pathways.  相似文献   

3.
Phosphorus (P) is considered the ultimate limiting nutrient for plants in most natural systems and changes in the distribution of inorganic and organic P forms during soil development have been well documented. In particular, microbial activity has been shown to be an important control on P cycling but its contribution in building up the pool of plant-available P during soil development is still poorly quantified. To determine the importance of different biological processes on P cycling, we analyzed the isotopic composition of oxygen in phosphate (δ(18)O-Pi) from the parent material, soil microorganisms, the available P pool, and from the vegetation along a 150-year soil chronosequence of a glacier forefield. Our results show that at all sites, δ(18)O-Pi of microbial Pi is within the range expected for the temperature-dependent equilibrium between phosphate and water. In addition, the isotopic signature of available Pi is close to the signature of microbial Pi, independently of the contribution of parent material Pi, vegetation Pi or Pi released from organic matter mineralization. Thus, we show that phosphate is cycled through soil microorganisms before being released to the available pool. This isotopic approach demonstrates for the first time in the field and over long time scales, and not only through controlled experiments, the role of the microbial activity in cycling of P in soils.  相似文献   

4.
We apply a triple isotope approach for nitrate that utilizes Δ(17)O as a conservative tracer, in combination with δ(18)O and δ(15)N, to assess source/sink dynamics of groundwater nitrate beneath alluvial washes in a semiarid urban setting. Other studies have used δ(18)O and δ(15)N to determine nitrate sources and cycling, but the atmospheric δ(18)O signature can be overprinted by biogeochemical processes. In this study, δ(18)O and δ(15)N values of nitrate were coupled with δ(17)O values of nitrate to quantify atmospheric nitrate inputs and denitrification amounts. Results show generally low groundwater nitrate concentrations (<0.2 mmol/L) throughout the basin; high nitrate concentrations (up to 1 mmol/L) with evidence for some denitrification were detected in areas where effluent was the predominant source of recharge to groundwater. Furthermore, the denitrification was inferred from elevated δ(18)O and δ(15)N values which were reinforced by increases in observed δ(17)O values. Finally, relatively low, but significant atmospheric nitrate concentrations were measured in groundwater (up to 6% of total nitrate). This study concludes that the triple isotope approach improves determination of the proportion of atmospheric nitrate and the significance of denitrification in natural waters, allowing us to develop a conceptual model of the biogeochemical processes controlling nitrogen in an urban setting.  相似文献   

5.
6.
Neat Scottish whiskies and the local source water used for and during whisky production have been analysed for their 2H and 18O isotopic composition by High Temperature Conversion–Isotope Ratio Mass Spectrometry (TC/EA–IRMS). With coefficients of determination R2 for δ2H and δ18O of 0.71 and 0.88, respectively, measured δ2H and δ18O values for water used in the production of Scottish whisky were found to be well correlated with the δ2H and δ18O values observed for the corresponding whiskies. By plotting bulk 2H against bulk 18O isotope abundance data of authentic whisky and counterfeit whisky samples it was possible to discriminate between samples of authentic whisky and samples of counterfeit whisky.  相似文献   

7.
In this review, we examine the variation in stable isotope signatures of the lighter elements (δ2H, δ13C, δ15N, δ18O, and δ34S) of tissues and excreta of domesticated animals, the factors affecting the isotopic composition of animal tissues, and whether stable isotopes may be used to differentiate organic and conventional modes of animal husbandry. The main factors affecting the δ13C signatures of livestock are the C3/C4 composition of the diet, the relative digestibility of the diet components, metabolic turnover, tissue and compound specificity, growth rate, and animal age. δ15N signatures of sheep and cattle products have been related mainly to diet signatures, which are quite variable among farms and between years. Although few data exist, a minor influence in δ15N signatures of animal products was attributed to N losses at the farm level, whereas stocking rate showed divergent findings. Correlations between mode of production and δ2H and δ18O have not been established, and only in one case of an animal product was δ34S a satisfactory marker for mode of production. While many data exist on diet–tissue isotopic discrimination values among domesticated animals, there is a paucity of data that allow a direct and statistically verifiable comparison of the differences in the isotopic signatures of organically and conventionally grown animal products. The few comparisons are confined to beef, milk, and egg yolk, with no data for swine or lamb products. δ13C appears to be the most promising isotopic marker to differentiate organic and conventional production systems when maize (C4) is present in the conventional animal diet. However, δ13C may be unsuitable under tropical conditions, where C4 grasses are abundant, and where grass-based husbandry is predominant in both conventional and organic systems. Presently, there is no universal analytical method that can be applied to differentiate organic and conventional animal products.  相似文献   

8.
The stable isotope composition of waters (delta2H, delta18O) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the delta2H and delta18O values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Carén at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher delta18O values (by approximately +2 per thousand delta18O relative to delta2H) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of 2H and 18O in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in 2H and 18O. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. In temperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II.  相似文献   

9.
Among the lighter elements having two or more stable isotopes (H, C, N, O, S), δ15N appears to be the most promising isotopic marker to differentiate plant products from conventional and organic farms. Organic plant products vary within a range of δ15N values of +0.3 to +14.6%, while conventional plant products range from negative to positive values, i.e. ?4.0 to +8.7%. The main factors affecting δ15N signatures of plants are N fertilizers, biological N2 fixation, plant organs and plant age. Correlations between mode of production and δ13C (except greenhouse tomatoes warmed with natural gas) or δ34S signatures have not been established, and δ2H and δ18O are unsuitable markers due to the overriding effect of climate on the isotopic composition of plant-available water. Because there is potential overlap between the δ15N signatures of organic and conventionally produced plant products, δ15N has seldom been used successfully as the sole criterion for differentiation, but when combined with complementary analytical techniques and appropriate statistical tools, the probability of a correct identification increases. The use of organic fertilizers by conventional farmers or the marketing of organic produce as conventional due to market pressures are additional factors confounding correct identification. The robustness of using δ15N to differentiate mode of production will depend on the establishment of databases that have been verified for individual plant products.  相似文献   

10.
Background and Aims: δ13C values from Vitis vinifera leaves, whole grape, seed, pulp, skin and/or grape must sugars have been investigated as an integrated marker of vine water status or intrinsic water-use efficiency during berry growth and across region of origin, vintage and variety. The use of 18O/16O isotopic ratio as a marker of water addition, vintage and geographical origin has also been studied. This paper examines the effect of irrigation and grapevine variety on δ18O and δ13C of grape must from eight varieties, all cultivated in the same vineyard to reduce the effects from other variables. Methods and Results: Stable isotope compositions of grape must water and sugar were determined by isotope ratio mass spectrometry. The result of the study showed statistically significant effects of irrigation and vine variety on both δ18O and δ13C. The effect of vintage on δ18O was only significant for non-irrigated vines. Conclusion: This research highlights the effect of variety and irrigation on δ13C and δ18O of grape. Significance of the Study: This is the first report to demonstrate that the varietal effect on δ13C and δ18O of grape is not due only to differences in the vegetative cycle of each variety. It further suggests that water exhibits a lower isotopic discrimination in the indigenous Spanish varieties studied than in non-indigenous varieties.  相似文献   

11.
The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatite-based in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 microM was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations < or = 4,700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 A. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios > or = 0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.  相似文献   

12.
We determined carbon and nitrogen contents (C and N contents) and stable carbon, nitrogen, and oxygen isotopic compositions (δ13C, δ15N, and δ18O) of polished rice in order to develop a simple method to discriminate its geographical origin. As a first attempt, we examined a single cultivar, Koshihikari rice, from 14 different cultivation areas including Australia (n = 1), Japan (n = 12), and USA (n = 1). For all rice samples, C and N contents and the isotopic compositions are consistent with those of general plant materials, being 37.2–40.0% (C content), 0.8–1.4% (N content), −27.1 to −25.4% (δ13C), +0.4 to +9.0% (δ15N), and +18.8 to +22.9% (δ18O). However, its cultivated area is clearly distinguished by a pentagonal radar plot based on the elemental and isotopic compositions. Thus, the comparison of C and N contents and δ13C, δ15N, and δ18O values would potentially be useful for rapid and routine discrimination of geographical origin of the polished rice.  相似文献   

13.
Relative carbon and nitrogen stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows; this diet and its δ-values depend on geographical and climatic factors. Milk from regions dominated by grassland typically shows relatively negative δ13C-values, while in regions dominated by crop cultivation the δ13C-values are more positive. The δ15N-values are influenced by factors such as soil conditions, the intensity of agricultural use and the climate. Casein in authentic milk samples is enriched in both 13C and 15N as compared to total milk, while the whey fraction is slightly enriched in 13C and depleted of 15N. The isotopic content of milk, casein and whey from one location have been measured throughout a period of longer than 1 year; variations are usually not greater than 1‰. In milk water, the 18O content was increased by between 2 and 6‰ as compared to ground water.  相似文献   

14.
Uranium binding to bone charcoal and bone meal apatite materials was investigated using U L(III)-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations < or = 5500 microg U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations > or = 5500 microg U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12,300 microg U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.  相似文献   

15.
Since 1986 the European Union has established official isotopic analysis methods for detecting the illegal addition of sugar and water to wine and to enable geographical traceability. In this paper we investigate the possibility of using analysis of the 18O/16O stable isotope ratio (expressed as δ18O) of ethanol to improve detection of the watering of wine and to determine the origin of ethanol. Sixty‐nine authentic wine samples from all over Italy, 59 spirits from fruit and cereals, 5 chemically synthesized ethanols, one concentrated and rectified must, one beet and one cane sugar, one fresh must, and 6 waters with increasing δ18O values were considered. Ethanol was recovered by distillation, using a Cadiot spinning band column, following the official OIV methods. The residual water was trapped by storing the distillate for at least 24 h on a molecular sieve. The 18O/16O ratio was measured using a pyrolyser interfaced with an isotope ratio mass spectrometer. The δ‐18O of ethanol is significantly related to the δ18O of the fermentation water and can be considered as a reliable internal reference. The values ranged from +24‰ to +36‰ in wine (years 2008 to 2012), +10‰ to +26‰ in fruit and cereal distillates, and from –2‰ to +12‰ in synthetic ethanol. The method was shown to be effective in improving detection of the watering of wine and determining the origin of ethanol (from grapes, other fruit, or synthesis), but not in detecting the addition of cane or beet sugar to wine.  相似文献   

16.
The regional origin of Chinese wines was investigated using two important complementary techniques, site‐specific natural isotopic fractionation nuclear magnetic resonance (SNIF‐NMR) and isotope ratio mass spectrometry (IRMS). Twenty samples from five different grape varieties were collected from north Xinjiang in 2009, along with 100 wine samples from five different regions during 2010–2013. The (D/H)I and (D/H)II in wine ethanol ranged from 95.10 to 102.86 ppm and from 115.99 to 126.39 ppm using SNIF‐NMR, respectively. The 13C/12C of wine ethanol and 18O/16O of wine water were detected using IRMS. The δ13C value (?23.36‰) in coastal regions was higher than that in continental regions (?27.75‰). The temperature is the key for δ13C value. The δ18O ranged from ?1.94 to 4.57‰. The δ18O values were only positive in north Xinjiang which had the arid climate and strong sunshine. No difference was found for isotope ratios for wines made from five different grape varieties in north Xinjiang. All data evaluated by principal component analysis and linear discriminant analysis showed that the best method to distinguish the regional wine origin correctly is a combination of (D/H)I, (D/H)II, R, δ13C and δ18O. Therefore, natural multi‐elemental isotope ratios are effective in contributing to wine quality control in the Chinese market.  相似文献   

17.
This study presents the determination and comparison of isotopic compositions of Hg in sediments, plankton, roach, and perch of two freshwater systems in the Lake Baikal-Angara River aquatic ecosystem: the man-made Bratsk Water Reservoir contaminated by Hg from a chlor-alkali factory and the noncontaminated Lake Baikal. Isotopic ratios of biota exhibit both significant mass-independent fractionation (MIF) (Δ(199)Hg from 0.20 to 1.87‰) and mass-dependent fractionation (MDF) (δ(202)Hg from -0.97 to -0.16‰), whereas sediments exhibit high MDF (δ(202)Hg from -1.99 to -0.83‰) but no MIF. δ(15)N and δ(13)C are correlated with methylmercury in organisms from both sites, indicating bioaccumulation and biomagnification through food webs of both regions. Combining this with isotopic composition of samples shows that δ(202)Hg increases with the trophic level of organisms and also with methylmercury in fish from Lake Baikal. This study demonstrates that MIF in fish samples from Bratsk Water Reservoir allow to trace anthropogenic Hg, since fish with the highest levels of Hg in muscle have the same isotopic composition as the sediment in which anthropogenic Hg was deposited. Less contaminated fish do not exhibit this anthropogenic signature accumulating relatively lower Hg amount from the contaminated sediments. This work reveals that Hg isotopic composition can be used to track the contribution of anthropogenic sources in fish from a contaminated lake.  相似文献   

18.
Interfacial electron transfer has been shown to occur between sorbed Fe(II) and structural Fe(III) in Fe oxides, but it is unknown whether a similar reaction occurs between sorbed Fe(II) and Fe(III)-bearing clay minerals. Here, we used the isotopic specificity of (57)Fe Mo?ssbauer spectroscopy to demonstrate electron transfer between sorbed Fe(II) and structural Fe(III) in an Fe-bearing smectite clay mineral (NAu-2, nontronite). Mo?ssbauer spectra of NAu-2 reacted with aqueous (56)Fe(II) (which is invisible to (57)Fe Mo?ssbauer spectroscopy) showed direct evidence for reduction of NAu-2 by sorbed Fe(II). Mo?ssbauer spectra using aqueous (57)Fe(II) showed that sorbed Fe(II) is oxidized upon sorption to the clay and pXRD patterns indicate that the oxidation product is lepidocrocite. Spectra collected at different temperatures indicate that reduction of structural Fe(III) by sorbed Fe(II) induces electron delocalization in the clay structure. Our results also imply that interpretation of room temperature and 77 K Mo?ssbauer spectra may significantly underestimate the amount of Fe(II) in Fe-bearing clays. These findings provide compelling evidence for abiotic reduction of Fe-bearing clay minerals by sorbed Fe(II), and require us to reframe our conceptual model for interpreting biological reduction of clay minerals, as well as contaminant reduction by reduced clays.  相似文献   

19.
Global models have indicated agriculturally impacted rivers and streams may be important sources of the greenhouse gas nitrous oxide (N(2)O). However, there is significant uncertainty in N(2)O budgets. Isotopic characterization can be used to help constrain N(2)O budgets. We present the first published measurements of the isotopic character of N(2)O emitted from low (2-4) order streams. Isotopic character of N(2)O varied seasonally, among streams, and over diel periods. On an annual basis, δ(18)O of emitted N(2)O (+47.4 to +51.4‰; relative to VSMOW) was higher than previously reported for larger rivers, but δ(15)N of emitted N(2)O (-16.2 to +2.4‰ among streams; relative to atmospheric N(2)) was similar to that of past studies. On an annual basis, all streams emitted N(2)O with lower δ(15)N than tropospheric N(2)O. Given these streams have elevated nitrate concentrations which are associated with enhanced N(2)O fluxes, this supports the hypothesis that streams are contributing to the accumulation of (15)N-depleted N(2)O in the troposphere.  相似文献   

20.
The objective of this study was to investigate seasonal variation in the C, N and S stable isotope composition of retail organic and conventional Irish beef. A total of 242 beef samples (127 organic, 115 conventional) was collected in a one-year survey and analysed by isotope ratio mass spectrometry. The δ13C time series in conventional beef was significantly non-random, with a pronounced seasonal positive shift of >2‰ between December and June, whilst δ13C in organic beef was less variable and significantly more negative. In conventional beef, δ15N was remarkably invariant (remaining close to 7‰) throughout the year, while organic beef was more variable and also significantly lower in δ15N. The S isotope composition (δ34S) exhibited a complex seasonal pattern in both types of beef. These results show that seasonal patterns can occur in the isotopic composition of beef, probably reflecting seasonality in animal feeding practices modulated by tissue turnover rates. Such seasonal variation needs to be considered in the isotopic authentication of beef and other animal-derived products.  相似文献   

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