Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

As an alternative to isotope ratio mass spectrometry (IRMS), the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and the capacity for field‐based application for the analysis of the stable isotopes of water. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in incorrect results for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every 2 h for 24–48 h) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic compositions of the extracted water from these samples were measured using both an IRMS and an IRIS instrument. The results show that the mean discrepancies between the IRMS and IRIS approaches for δ¹⁸O and δD, respectively, were: –5.6‰ and ?75.7‰ for leaf water; –4.0‰ and ?23.3‰ for stem water; –3.4‰ and ?28.2‰ for root water; ?0.5‰ and –6.7‰ for xylem water; –0.06‰ and ?0.3‰ for xylem flow; and ?0.1‰ and 0.3‰ for soil water. The order of the discrepancy was: leaf > stem ≈ root > xylem > xylem flow ≈ soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling at nighttime did not remove the observed deviations. Copyright © 2011 John Wiley & Sons, Ltd.     

Geographical traceability of wheat and its products using multielement light stable isotopes coupled with chemometrics

The present study was aimed to investigate the variation of stable isotopic ratios of carbon, nitrogen, hydrogen, and oxygen in wheat kernel along with different processed fractions from three geographical origins across 5 years using isotope ratio mass spectrometry (IRMS). Multiway ANOVA revealed significant differences among region, harvest year, processing, and their interactions for all isotopes. The region contributed the major variability in the δ¹³C ‰, δ²H ‰, δ¹⁵N ‰, and δ¹⁸O‰ values of wheat. Variation of δ¹³C ‰, δ¹⁵N ‰, and δ¹⁸O ‰ between wheat whole kernel and its products (break, reduction, noodles, and cooked noodles) were ?0.7‰, and no significant difference was observed, suggesting the reliability of these isotope fingerprints in geographical traceability of wheat‐processed fractions and foods. A significant influence of wheat processing was observed for δ²H values. By applying linear discriminant analysis (LDA) to the whole dataset, the generated model correctly classified over 91% of the samples according to the geographical origin. The application of these parameters will assist in the development of an analytical control procedure that can be utilized to control the mislabeling regarding geographical origin of wheat kernel and its products.     

Measurements of nitrogen isotope composition of plants and surface soils along the altitudinal transect of the eastern slope of Mount Gongga in southwest China

The natural abundances of stable nitrogen isotopes in plants and soils have been viewed as recorders that can be used to reconstruct paleoclimate and ecological processes or to indicate the biogeochemical cycle of nitrogen in nature. This study systematically measured the nitrogen isotope composition (δ¹⁵N) in plants and surface soils along an altitudinal transect of elevation range of 1200 to 4500 m on the eastern slope of Mount Gongga in southwest China. The influences of photosynthetic pathways on plant δ¹⁵N as well as the effects of temperature and precipitation on δ¹⁵N altitudinal trends in plants and surface soils are discussed. Across this altitude transect, the δ¹⁵N values of C₃ and C₄ plants on Mount Gongga range between ?9.87‰ and 7.58‰ with a mean value of ?1.33‰, and between ?3.98‰ and 4.38‰ with a mean value of ?0.25‰, respectively. There is an evident δ¹⁵N difference between C₃ plants and C₄ plants. If, however, you only compare C₄ plants with those C₃ plants growing at the same altitudinal range, no significant difference in δ¹⁵N exists between them, suggesting that photosynthetic pathway does not have an influence on the plant δ¹⁵N values. In addition, we found that C₃, C₄ plants and surface soil (0–5 cm depth) all trend significantly towards more negative δ¹⁵N with increasing elevation. Furthermore, this study shows that the mean annual temperature and the mean annual precipitation positively and negatively correlate with δ¹⁵N in C₃ and C₄ plants, respectively. This indicates that precipitation and temperature are the main controlling factors of the δ¹⁵N variation in plants with altitude. We propose that lower δ¹⁵N values of plants and soils at higher altitude should be attributed to lower mineralization and lower net nitrification rates induced by low temperature and abundant rainfall. Copyright © 2010 John Wiley & Sons, Ltd.     

Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

The use of isotope ratio infrared spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has many advantages over traditional isotope ratio mass spectrometry (IRMS), it may also be prone to errors that do not impact upon IRMS analyses. Of particular concern is the potential for contaminants in the water sample to interfere with the spectroscopy, thus leading to erroneous stable isotope data. Water extracted from plant and soil samples may often contain organic contaminants. The extent to which contaminants may interfere with IRIS and thus impact upon data quality is presently unknown. We tested the performance of IRIS relative to IRMS for water extracted from 11 plant species and one organic soil horizon. IRIS deviated considerably from IRMS for over half of the samples tested, with deviations as large as 46‰ (δ²H) and 15.4‰ (δ¹⁸O) being measured. This effect was reduced somewhat by using activated charcoal to remove organics from the water; however, deviations as large as 35‰ (δ²H) and 11.8‰ (δ¹⁸O) were still measured for these cleaned samples. Interestingly, the use of activated charcoal to clean water samples had less effect than previously thought for IRMS analyses. Our data show that extreme caution is required when using IRIS to analyse water samples that may contain organic contaminants. We suggest that the development of new cleaning techniques for removing organic contaminants together with instrument‐based software to flag potentially problematic samples are necessary to ensure accurate plant and soil water analyses using IRIS. Copyright © 2010 John Wiley & Sons, Ltd.     

Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water

Plant water extracts typically contain organic materials that may cause spectral interference when using isotope ratio infrared spectroscopy (IRIS), resulting in errors in the measured isotope ratios. Manufacturers of IRIS instruments have developed post-processing software to identify the degree of contamination in water samples, and potentially correct the isotope ratios of water with known contaminants. Here, the correction method proposed by an IRIS manufacturer, Los Gatos Research, Inc., was employed and the results were compared with those obtained from isotope ratio mass spectrometry (IRMS). Deionized water was spiked with methanol and ethanol to create correction curves for δ(18)O and δ(2)H. The contamination effects of different sample types (leaf, stem, soil) and different species from agricultural fields, grasslands, and forests were compared. The average corrections in leaf samples ranged from 0.35 to 15.73‰ for δ(2)H and 0.28 to 9.27‰ for δ(18)O. The average corrections in stem samples ranged from 1.17 to 13.70‰ for δ(2)H and 0.47 to 7.97‰ for δ(18)O. There was no contamination observed in soil water. Cleaning plant samples with activated charcoal had minimal effects on the degree of spectral contamination, reducing the corrections, by on average, 0.44‰ for δ(2)H and 0.25‰ for δ(18)O. The correction method eliminated the discrepancies between IRMS and IRIS for δ(18)O, and greatly reduced the discrepancies for δ(2)H. The mean differences in isotope ratios between IRMS and the corrected IRIS method were 0.18‰ for δ(18)O, and -3.39‰ for δ(2)H. The inability to create an ethanol correction curve for δ(2)H probably caused the larger discrepancies. We conclude that ethanol and methanol are the primary compounds causing interference in IRIS analyzers, and that each individual analyzer will probably require customized correction curves.     

Does natural weathering change the stable isotope composition (2H, 13C, 15N, 18O and 34S) of cattle hair?

Stable isotope analysis of hair has found applications in many fields of science because it provides a temporally resolved, fairly stable isotopic archive of mammalian individuals. We investigated whether this hair archive is modified by natural weathering while attached to a living animal. We analyzed the tail switch hairs of one suckler cow, sampled seven times over a period of four annual summer pasture–winter stall feeding cycles. We compared relative isotope ratios (δ²H, δ¹³C, δ¹⁵N, δ¹⁸O and δ³⁴S) of sections of hair that grew simultaneously but were exposed to natural weathering conditions over different periods of time. Natural wear caused a loss of mass of approx. 0.13% day^–1, with no apparent effect of environmental conditions. Changes in δ²H, δ¹³C, δ¹⁵N and δ¹⁸O were below the detection limit, indicating that hair is a reliable archive for the isotopes of these elements. In contrast, δ³⁴S values increased during the grazing period by about 1 ‰, with exposure to UV radiation appearing to have a major influence on this result. The δ³⁴S values decreased during the subsequent stall period, probably due to abrasion. Seasonal variation in δ³⁴S may indicate alternating environments that differ in their weathering conditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography–isotope‐ratio mass spectrometry of benzene polycarboxylic acids

Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well‐established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound‐specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography–combustion–isotope ratio mass spectrometry (GC‐C‐IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post‐analysis correction for the accurate measurement of δ¹³ C values, leading to increased measurement error. Here, we describe a method for δ¹³ C isotope ratio measurement and quantification of BPCAs from soil‐derived PyOM, based on ion‐exchange chromatography (IEC‐IRMS). The reproducibility of the δ¹³ C measurement of individual BPCAs by IEC‐IRMS was better than 0.35‰ (1σ). The δ¹³ C‐BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³ C‐abundance, produced accurate and precise δ¹³ C measurements. Analysis of samples that differed in δ¹³ C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ¹³ C‐BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ¹³ C‐BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways. Copyright © 2011 John Wiley & Sons, Ltd.     

The effects of α-cellulose extraction and blue-stain fungus on retrospective studies of carbon and oxygen isotope variation in live and dead trees

Tree‐ring carbon and oxygen isotope ratios from live and recently dead trees may reveal important mechanisms of tree mortality. However, wood decay in dead trees may alter the δ¹³C and δ¹⁸O values of whole wood obscuring the isotopic signal associated with factors leading up to and including physiological death. We examined whole sapwood and α‐cellulose from live and dead specimens of ponderosa pine (Pinus ponderosa), one‐seed juniper (Juniperous monosperma), piñon pine (Pinus edulis) and white fir (Abies concolor), including those with fungal growth and beetle frass in the wood, to determine if α‐cellulose extraction is necessary for the accurate interpretation of isotopic compositions in the dead trees. We found that the offset between the δ¹³C or δ¹⁸O values of α‐cellulose and whole wood was the same for both live and dead trees across a large range of inter‐annual and regional climate differences. The method of α‐cellulose extraction, whether Leavitt‐Danzer or Standard Brendel modified for small samples, imparts significant differences in the δ¹³C (up to 0.4‰) and δ¹⁸O (up to 1.2‰) of α‐cellulose, as reported by other studies. There was no effect of beetle frass or blue‐stain fungus (Ophiostoma) on the δ¹³C and δ¹⁸O of whole wood or α‐cellulose. The relationships between whole wood and α‐cellulose δ¹³C for ponderosa, piñon and juniper yielded slopes of ~1, while the relationship between δ¹⁸O of whole wood and α‐cellulose was less clear. We conclude that there are few analytical or sampling obstacles to retrospective studies of isotopic patterns of tree mortality in forests of the western United States. Published in 2011 by John Wiley & Sons, Ltd.     

Reducing and correcting for contamination of ecosystem water stable isotopes measured by isotope ratio infrared spectroscopy

Concern exists about the suitability of laser spectroscopic instruments for the measurement of the (18)O/(16)O and (2)H/(1)H values of liquid samples other than pure water. It is possible to derive erroneous isotope values due to optical interference by certain organic compounds, including some commonly present in ecosystem-derived samples such as leaf or soil waters. Here we investigated the reliability of wavelength-scanned cavity ring-down spectroscopy (CRDS) (18)O/(16)O and (2)H/(1)H measurements from a range of ecosystem-derived waters, through comparison with isotope ratio mass spectrometry (IRMS). We tested the residual of the spectral fit S(r) calculated by the CRDS instrument as a means to quantify the difference between the CRDS and IRMS δ-values. There was very good overall agreement between the CRDS and IRMS values for both isotopes, but differences of up to 2.3‰ (δ(18)O values) and 23‰ (δ(2)H values) were observed in leaf water extracts from Citrus limon and Alnus cordata. The S(r) statistic successfully detected contaminated samples. Treatment of Citrus leaf water with activated charcoal reduced, but did not eliminate, δ(2)H(CRDS) - δ(2)H(IRMS) linearly for the tested range of 0-20% charcoal. The effect of distillation temperature on the degree of contamination was large, particularly for δ(2)H values but variable, resulting in positive, negative or no correlation with distillation temperature. S(r) and δ(CRDS) - δ(IRMS) were highly correlated, in particular for δ(2)H values, across the range of samples that we tested, indicating the potential to use this relationship to correct the δ-values of contaminated plant water extracts. We also examined the sensitivity of the CRDS system to changes in the temperature of its operating environment. We found that temperature changes ≥4 °C for δ(18)O values and ≥10 °C for δ(2)H values resulted in errors larger than the CRDS precision for the respective isotopes and advise the use of such instruments only in sufficiently temperature-stabilised environments.     

Continuous analysis of δ18O and δD values of water by diffusion sampling cavity ring‐down spectrometry: a novel sampling device for unattended field monitoring of precipitation,ground and surface waters

A novel sampling device suitable for continuous, unattended field monitoring of rapid isotopic changes in environmental waters is described. The device utilises diffusion through porous PTFE tubing to deliver water vapour continuously from a liquid water source for analysis of δ¹⁸O and δD values by Cavity Ring‐Down Spectrometry (CRDS). Separation of the analysed water vapour from non‐volatile dissolved and particulate contaminants in the liquid sample minimises spectral interferences associated with CRDS analyses of many aqueous samples. Comparison of isotopic data for a range of water samples analysed by Diffusion Sampling‐CRDS (DS‐CRDS) and Isotope Ratio Mass Spectrometry (IRMS) shows significant linear correlations between the two methods allowing for accurate standardisation of DS‐CRDS data. The internal precision for an integration period of 3 min (standard deviation (SD) = 0.1 ‰ and 0.3 ‰ for δ¹⁸O and δD values, respectively) is similar to analysis of water by CRDS using an autosampler to inject and evaporate discrete water samples. The isotopic effects of variable air temperature, water vapour concentration, water pumping rate and dissolved organic content were found to be either negligible or correctable by analysis of water standards. The DS‐CRDS system was used to analyse the O and H isotope composition in short‐lived rain events. Other applications where finely time resolved water isotope data may be of benefit include recharge/discharge in groundwater/river systems and infiltration‐related changes in cave drip water. Copyright © 2011 John Wiley & Sons, Ltd.     

On the necessity of organic solvent extraction for carbon isotopic analysis of α-cellulose: implications for environmental reconstructions

α-cellulose is widely used as a target substance for isotope ratio analysis in environmental reconstructions. Its preparation includes three basic steps: organic solvent extraction, delignification and alkaline hydrolysis. Recent works have suggested omission of the first step. We have made a detailed comparison in carbon isotope ratio of α-cellulose with or without organic solvent extraction using 32 consecutive tree ring and 30 subfossil peat samples. These samples were exposed to three different chemical treatments: with organic solvent extraction as the first step (Cell_OE), without organic solvent extraction (Cell_NOE), and with organic solvent extraction as the final step (Cell_NOE/OE). The third treatment is used to test if organic extractives can be completely removed or if their solubility in organic solvents has been altered by delignification and alkaline hydrolysis. In tree rings and peat, δ¹³C_{C ell NOE} was always significantly different from δ¹³C_{C ell OE}, but the trends were not the same. In tree rings, δ¹³C_{C ell NOE} was always more negative than δ¹³C_{C ell OE} by ?0.31 ～ ?0.01‰. In contrast, δ¹³C_{C ell NOE} in peat could be more negative or more positive than δ¹³C_{C ell OE} by ?3.08 ～ 0.27‰. The third chemical treatment resulted in different patterns. For tree rings, δ¹³C_{C ell NOE/OE} was still more negative than δ¹³C_{C ell OE} by ?0.36 ～ ?0.08‰. However, the differences between δ¹³C_{C ell NOE/OE} and δ¹³C_{C ell OE} for peat varied in a more narrow range from ?0.58 to 0.61‰, compared to the differences between δ¹³C_{C ell NOE} and δ¹³C_{C ell OE}. These results exposed a complex chemical evolution behaviour and an incomplete removal of lipids during delignification and alkaline hydrolysis. The mean value, long-term trend and seesaw patterns for a tree ring or peat Cell_NOE series were significantly different from those for a Cell_OE series, indicating that omission of organic solvent extraction will lead to a biased inference of past environmental conditions.     

Silicon Isotope Fractionation in Maize and its Biogeochemical Significance

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.     

A new isolation procedure of nitrate from freshwater for nitrogen and oxygen isotope analysis

The nitrogen (δ¹⁵N) and oxygen isotope (δ¹⁸O) analysis of nitrate (NO₃^–) from aqueous samples can be used to determine nitrate sources and to study N transformation processes. For these purposes, several methods have been developed; however, none of them allows an accurate, fast and inexpensive analysis. Here, we present a new simple method for the isolation of nitrate, which is based on the different solubilities of inorganic salts in an acetone/hexane/water mixture. In this solvent, all major nitrate salts are soluble, whereas all other oxygen‐bearing compounds such as most inorganic carbonates, sulfates, and phosphates are not. Nitrate is first concentrated by freeze‐drying, dissolved in the ternary solvent and separated from insoluble compounds by centrifugation. Anhydrous barium nitrate is then precipitated in the supernatant solution by adding barium iodide. For δ¹⁸O analysis, dried Ba(NO₃)₂ samples are directly reduced in a high‐temperature conversion system to CO and measured on‐line using isotope ratio mass spectrometry (IRMS). For δ¹⁵N analysis, samples are combusted in an elemental analyzer (EA) coupled to an IRMS system. The method has been tested down to 20 µmol NO₃^– with a reproducibility (1SD) of 0.1‰ for nitrogen and 0.2–0.4‰ for oxygen isotopes. For nitrogen we observed a small consistent ¹⁵N enrichment of +0.2‰, probably due to an incomplete precipitation process and, for oxygen, a correction for the incorporation of water in the precipitated Ba(NO₃)₂ has to be applied. Apart from being robust, this method is highly efficient and low in cost. Copyright © 2011 John Wiley & Sons, Ltd.     

Diet discrimination factors are inversely related to δ15 N and δ13C values of food for fish under controlled conditions

A recent literature review reported negative relationships between diet discrimination factors (DDFs = X_fish – X_food; X = δ¹⁵N or δ¹³C) and the values of δ¹⁵N and δ¹³C in the food of wild organisms but there has been no laboratory‐based confirmation of these relationships to date. Laboratory reared guppies (Poecilia reticulata) fed a series of diets with a range of δ¹³C (?22.9 to ?6.6‰) and δ¹⁵N (6.5 to 1586‰) values were used to magnify diet‐tissue dynamics in order to calculate DDFs once the fish had achieved equilibrium with each of the diets. Values of DDFs range widely for δ¹⁵N (7.1 to ?849‰) and δ¹³C (1.1 to ?7.0‰) and showed a strong negative correlation with the stable isotope value in the food for δ¹⁵N (slope = ?0.59 ± 0.02, r² = 0.95) and δ¹³C (slope = ?0.56 ± 0.02, r² = 0.94). Based on these relationships, the magnitude of DDF change over environmentally relevant values of δ¹⁵N or δ¹³C would be significant and could confound the interpretation of stable isotopes in the environment. Using highly enriched experimental diets, our study adds to a growing number of studies that undermine the consistent trophic enrichment paradigm with results that demonstrate the currently poor mechanistic understanding of how DDFs arise. The results of our study highlight that the magnitude of the stable isotope values in prey must be considered when choosing DDF values. Future laboratory studies should therefore be directed at uncovering the mechanistic basis of DDFs and, like others before, we recommend the determination of diet‐dependent DDFs under laboratory conditions before modeling dietary proportions or calculating trophic positions. Copyright © 2010 John Wiley & Sons, Ltd.     

Stable isotope analysis of dissolved organic carbon in soil solutions using a catalytic combustion total organic carbon analyzer‐isotope ratio mass spectrometer with a cryofocusing interface

Stable carbon isotopes are a powerful tool to assess the origin and dynamics of carbon in soils. However, direct analysis of the ¹³C/¹²C ratio in the dissolved organic carbon (DOC) pool has proved to be difficult. Recently, several systems have been developed to measure isotope ratios in DOC by coupling a total organic carbon (TOC) analyzer with an isotope ratio mass spectrometer. However these systems were designed for the analysis of fresh and marine water and no results for soil solutions or ¹³C‐enriched samples have been reported. Because we mainly deal with soil solutions in which the difficult to oxidize humic and fulvic acids are the predominant carbon‐containing components, we preferred to use thermal catalytic oxidation to convert DOC into CO₂. We therefore coupled a high‐temperature combustion TOC analyzer with an isotope ratio mass spectrometer, by trapping and focusing the CO₂ cryogenically between the instruments. The analytical performance was tested by measuring solutions of compounds varying in the ease with which they can be oxidized. Samples with DOC concentrations between 1 and 100 mg C/L could be analyzed with good precision (standard deviation (SD) ≤0.6‰), acceptable accuracy, good linearity (overall SD = 1‰) and without significant memory effects. In a ¹³C‐tracer experiment, we observed that mixing plant residues with soil caused a release of plant‐derived DOC, which was degraded or sorbed during incubation. Based on these results, we are confident that this approach can become a relatively simple alternative method for the measurement of the ¹³C/¹²C ratio of DOC in soil solutions. Copyright © 2010 John Wiley & Sons, Ltd.     

Mass spectrometric analysis of the 13C/12C abundance ratios in vine plants and wines depending on regional climate factors (Krasnodar krai and Rostov oblast, Russia)

Distribution of ¹³C/¹²C isotopes in vegetative (roots, grapevine, leaves) and generative (berries) parts of vine plants of the West European genetically different varieties Cabernet Sauvignon and Aligoté growing on soils of Krasnodar krai and Rostov oblast, as well as autochthonous varieties Sibirkovy and Krasnostop Zolotovsky growing in Rostov oblast, has been studied using isotopic mass spectrometry methods. It has been shown that the variations of δ¹³C values in plant tissues and berries are related to the climatic conditions of plant growth: moisture (a sum of annual precipitation) and temperature (a sum of annual effective temperatures). The carbon isotope ratios of vegetative and generative parts of vine plants have been found to be noticeably affected by vine varieties. The different ¹³C contents in ethanol produced from wine of the Aligoté and Cabernet Sauvignon varieties grown in two Russian vineyard regions are due to vine growth conditions, variety attribution and wine production techniques. An analytically significant parameter determined as exemplified by the Aligoté and Cabernet Sauvignon varieties in fermentation of vine harvested in different seasons and in both vineyard regions was an increased ¹³C content in ethanol with respect to dry (non-volatile) residue in wine after distillation of ethanol. This characteristic has been determined by a systematic difference of about 1–2‰ between the δ¹³C value of ethanol and the dry residue. A relative constancy in the carbon isotope composition of ethanol and of the dry residue in the final product is the basis for determining the authenticity of grape wines by means of isotopic mass spectrometry irrespective of natural factors.     

Hydrogen and oxygen isotopes of water from inclusions in minerals: design of a new crushing system and on‐line continuous‐flow isotope ratio mass spectrometric analysis

An analytical line for stable isotope analyses of water recovered from fluid inclusions in minerals was built and successfully tested. The line is based on the principle of continuous‐flow analysis of water via high‐temperature reduction on glassy carbon. It includes a custom‐designed set of high‐efficiency crushers and a cryo‐focusing cell. This paper provides details of the line design and discusses strategies for line conditioning and mitigation of memory effects. The line allows measurements of hydrogen and oxygen isotopes during a single acquisition. The precision of the analyses depends on the amount of water released from the inclusions. The best results are obtained for samples containing at least 0.1–0.2 µL (0.06–0.11 µmol) H₂O. For such samples precision is better than 1.5‰ for δD and 0.5‰ for δ¹⁸O (1σ). Smaller amounts of water can be measured but at lower precision. Analyses of modern calcite formed under stable conditions in a deep cave allowed assessment of the accuracy of the analyses. The δD values measured in fluid inclusions of this working standard match the δD value of the parent water, and the oxygen isotope values agree within ca. 0.5‰. This indicates that fluid inclusions trapped in calcite at near‐ambient temperatures (e.g. speleothems and low‐temperatures phreatic calcite) faithfully preserve the original isotopic composition of the parent waters. Copyright © 2009 John Wiley & Sons, Ltd.     

Stable carbon isotopes as an indicator for soil degradation in an alpine environment (Urseren Valley,Switzerland)

Analyses of soil organic carbon (SOC) content and stable carbon isotope signatures (δ¹³C) of soils were assessed for their suitability to detect early stage soil erosion. We investigated the soils in the alpine Urseren Valley (southern central Switzerland) which are highly impacted by soil erosion. Hill slope transects from uplands (cambisols) to adjacent wetlands (histosols and histic to mollic gleysols) differing in their intensity of visible soil erosion, and reference wetlands without erosion influence were sampled. Carbon isotopic signature and SOC content of soil depth profiles were determined. A close correlation of δ¹³C and carbon content (r > 0.80) is found for upland soils not affected by soil erosion, indicating that depth profiles of δ¹³C of these upland soils mainly reflect decomposition of SOC. Long‐term disturbance of an upland soil is indicated by decreasing correlation of δ¹³C and SOC (r ≤ 0.80) which goes in parallel with increasing (visible) damage at the site. Early stage soil erosion in hill slope transects from uplands to adjacent wetlands is documented as an intermediate δ¹³C value (?27.5‰) for affected wetland soil horizons (0–12 cm) between upland (aerobic metabolism, relatively heavier δ¹³C of ?26.6‰) and wetland isotopic signatures (anaerobic metabolism, relatively lighter δ¹³C of ?28.6‰). Carbon isotopic signature and SOC content are found to be sensitive indicators of short‐ and long‐term soil erosion processes. Copyright © 2009 John Wiley & Sons, Ltd.     

Error assessment of nitrogen and oxygen isotope ratios of nitrate as determined via the bacterial denitrification method

Currently, bacterial denitrification is becoming the accepted method for δ¹⁵N‐ and δ¹⁸O‐NO determination. However, proper correction methods with international references (USGS32, USGS34 and USGS35) are needed. As a consequence, it is important to realize that the corrected isotope values are derived from a combination of several other measurements with associated uncertainties. Therefore, it is necessary to consider the propagated uncertainty on the final isotope value. This study demonstrates how to correctly estimate the uncertainty on corrected δ¹⁵N‐ and δ¹⁸O‐NO values using a first‐order Taylor series approximation. The bacterial denitrification method errors from 33 batches of 561 surface water samples varied from 0.2 to 2.1‰ for δ¹⁵N‐NO and from 0.7 to 2.3‰ for δ¹⁸O‐NO, which is slightly wider than the machine error, which varied from 0.2 to 0.6‰ for δ¹⁵N‐N₂O and from 0.4 to 1.0‰ for δ¹⁸O‐N₂O. The overall uncertainties, which are composed of the machine error and the method error, for the 33 batches ranged from 0.3 to 2.2‰ for δ¹⁵N‐NO and from 0.8 to 2.5‰ for δ¹⁸O‐NO. In addition, the mean corrected δ¹⁵N and δ¹⁸O values of 132 KNO₃‐IWS (internal working standard) measurements were computed as 8.4 ± 1.0‰ and 25.1 ± 2.0‰, which is a slight underestimation for δ¹⁵N and overestimation for δ¹⁸O compared with the accepted values (δ¹⁵N = 9.9 ± 0.3‰ and δ¹⁸O = 24.0 ± 0.3‰). The overall uncertainty of the bacterial denitrification method allows the use of this method for source identification of NO. Copyright © 2010 John Wiley & Sons, Ltd.