Application of urea adduction technique to polluted urban aerosols for the determination of hydrogen isotopic composition of n-alkanes

We examined an applicability of an improved urea adduction technique for the determination of hydrogen isotopic composition (δD) of homologous series of n-alkanes present in polluted urban aerosols using GC/TC/IRMS. Unresolved complex mixture (UCM) of hydrocarbons that interferes with accurate isotope measurements of n-alkanes was removed from n-alkane fraction by a urea adduction method. Recoveries of C₂₀ to C₃₀ n-alkanes during the urea adduction procedure were greater than 90% when the concentrations of total n-alkanes exceed 6.1?µg?mL^?1. Our compound-specific D/H ratios confirm the absence of significant hydrogen isotope fractionation in n-alkanes during urea adduction and recovery of the purified n-alkane fraction. We applied this technique to the urban aerosols that contain a large quantity of UCM to measure δD of C₂₀ to C₃₅ n-alkanes in urban aerosols from Tokyo and Sapporo with an accuracy less than 10‰. We found that the δD values widely ranged from ?38 to ?179‰. Based on the δD values of individual n-alkanes in aerosol samples, we can obtain further information on the sources of aerosol n-alkanes and their source regions, and the atmospheric processes such as long-range transport and atmospheric mixing of air masses of different origin.     

2H/1H Ratio Analysis of Flavor Compounds by On‐Line Gas Chromatography Pyrolysis Isotope Ratio Mass Spectrometry (HRGC‐P‐IRMS): Benzaldehyde

Isotope ratio monitoring gas chromatography‐mass spectrometry of the ²H/¹H ratio by pyrolysis isotope ratio mass spectrometry (P‐IRMS) was used to analyze benzaldehyde originating from various sources. Based on the δ²H_SMOW value of an authentic reference sample determined with an elemental analyzer (EA), the range of reproducibility and linearity was checked. Correct (EA related) and reproducible data were obtained for sample amounts >0.6 μg benzaldehyde (on column). In another series of experiments, the influence of sample preparation, i. e. simultaneous distillation‐extraction (SDE) was found to be negligible. The following ranges of δ²H_SMOW values were determined for benzaldehyde using five types of samples, i. e. (i) synthetic (δ²H_SMOW –78 to –85‰, ex benzal chloride; +420 to +668‰, ex toluene) and ‘natural’ (including ‘ex‐cassia’) references (δ²H_SMOW –83 to –144‰); (ii) bitter almond oils (δ²H_SMOW –113 to –148‰); (iii) fruits (δ²H_SMOW –111 to –146‰); (iv) kernels (δ²H_SMOW –115 to –188‰); and (v) leaves (δ²H_SMOW –165 to –189‰).     

Simultaneous determination of δ15N and δ18O of N2O and δ13C of CH4 in nanomolar quantities from a single water sample

We have developed a rapid, sensitive, and automated analytical system to simultaneously determine the concentrations and stable isotopic compositions (δ¹⁵N, δ¹⁸O, and δ¹³C) of nanomolar quantities of nitrous oxide (N₂O) and methane (CH₄) in water, by combining continuous‐flow isotope‐ratio mass spectrometry and a helium‐sparging system to extract and purify the dissolved gases. Our system, which is composed of cold traps and a capillary gas chromatograph that use ultra‐pure helium as the carrier gas, achieves complete extraction of N₂O and CH₄ in a water sample and separation among N₂O, CH₄, and the other component gases. The flow path following exit from the gas chromatograph was periodically changed to pass the gases through the combustion furnace to convert CH₄ and the other hydrocarbons into CO₂, or to bypass the combustion furnace for the direct introduction of eluted N₂O into the mass spectrometer, for determining the stable isotopic compositions through monitoring the ions of m/z 44, 45, and 46 of CO and N₂O⁺. The analytical system can be operated automatically with sequential software programmed on a personal computer. Analytical precisions better than 0.2‰ and 0.3‰ and better than 1.4‰ and 2.6‰ were obtained for the δ¹⁵N and δ¹⁸O of N₂O, respectively, when more than 6.7 nmol and 0.2 nmol of N₂O, respectively, were injected. Simultaneously, analytical precisions better than 0.07‰ and 2.1‰ were obtained for the δ¹³C of CH₄ when more than 5.5 nmol and 0.02 nmol of CH₄, respectively, were injected. In this manner, we can simultaneously determine stable isotopic compositions of a 120 mL water sample with concentrations as low as 1.7 nmol/kg for N₂O and 0.2 nmol/kg for CH₄. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Improved online hydrogen isotope analysis of halite aqueous inclusions

We demonstrate an improved method based on continuous‐flow elemental analyser pyrolysis isotopic ratio mass spectrometry (CF‐EA‐PY‐IRMS) to measure the ²H/¹H ratios of water trapped in halite crystals. Two challenges to overcome are the low hydrogen concentration of samples (10‐50 μmol H₂·g^?1) and the high chloride concentration released when reacting halite in an elemental analyser. We describe an optimization procedure for determining the ²H/¹H ratio of this trapped water with an acceptable accuracy. This technique involves the use of a high‐temperature Cr reactor to quantitatively convert H₂O into H₂. The initial step was performed on halite crystals precipitated from a water reservoir where ²H/¹H ratios were monitored from its initial stage until the end of evaporation. The ²H/¹H isotopic analyses were automated online in continuous‐flow mode. Precision of the method was determined for those “synthetic” samples with hydrogen concentrations ranging from 0.2 to 0.5 wt%. ²H/¹H isotopic ratios of evaporating waters bracket the compositions of water inclusions. The formation of fluid inclusions is not instantaneous and records the isotopic signature of the residual waters across a time range during which the isotopic values of the water still evolve. This property explains why the δ²H_VSMOW standard deviation of ±5‰ (2σ) observed for 10‐mg aliquots of halite exceeds the instrumental error (about ±1.5‰ 2σ) determined on the basis of IAEA‐CH7, NBS 30, and NBS 22 references along with calibrated waters with and without added halite crystals. We also applied this method to Mesoproterozoic (1.4 Ga) and Neoproterozoic (0.8 Ga) halite samples with relatively low hydrogen concentrations (300‐1500 ppm). The measured δ²H_VSMOW values for Precambrian waters range from ?89‰ to ?54‰. We propose that this technique offers a new perspective and great potential for palaeoenvironmental reconstructions based on the ²H/¹H analyses of water trapped in halite.     

δD and δ13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry

This paper describes the establishment of a robust method to determine compound specific δD and δ(13)C values of volatile organic compounds (VOCs) in a standard mixture ranging between C(6) and C(10) and was applied to various complex emission samples, e.g. from biomass combustion and car exhaust. A thermal desorption (TD) unit was linked to a gas chromatography isotope ratio mass spectrometer (GC-irMS) to enable compound specific isotope analysis (CSIA) of gaseous samples. TenaxTA was used as an adsorbent material in stainless steel TD tubes. We determined instrument settings to achieve a minimal water background level for reliable δD analysis and investigated the impact of storage time on δD and δ(13)C values of collected VOCs (176 days and 40 days of storage, respectively). Most of the standard compounds investigated showed standard deviations (SD)<6‰ (δD) when stored for 148 days at 4 °C. However, benzene revealed occasionally D depleted values (21‰ SD) for unknown reasons. δ(13)C analysis demonstrated that storage of 40 days had no effect on VOCs investigated. We also showed that breakthrough (benzene and toluene, 37% and 7%, respectively) had only a negligible effect (0.7‰ and 0.4‰, respectively) on δ(13)C values of VOCs on the sample tube. We established that the sample portion collected at the split flow effluent of the TD unit can be used as a replicate sample for isotope analysis saving valuable sampling time and resources. We also applied TD-GC-irMS to different emission samples (biomass combustion, petrol and diesel car engines exhaust) and for the first time δD values of atmospheric VOCs in the above range are reported. Significant differences in δD of up to 130‰ were observed between VOCs in emissions from petrol car engine exhaust and biomass combustion (Karri tree). However, diesel car emissions showed a high content of highly complex unresolved mixtures thus a baseline separation of VOCs was not achieved for stable hydrogen isotope analysis. The ability to analyse δD by TD-GC-irMS complements the characterisation of atmospheric VOCs and is maybe used for establishing further source(s).     

Adaptation of continuous‐flow cavity ring‐down spectroscopy for batch analysis of δ13C of CO2 and comparison with isotope ratio mass spectrometry

Measurements of δ¹³C in CO₂ have traditionally relied on samples stored in sealed vessels and subsequently analyzed using magnetic sector isotope ratio mass spectrometry (IRMS), an accurate but expensive and high‐maintenance analytical method. Recent developments in optical spectroscopy have yielded instruments that can measure δ¹³CO₂ in continuous streams of air with precision and accuracy approaching those of IRMS, but at a fraction of the cost. However, continuous sampling is unsuited for certain applications, creating a need for conversion of these instruments for batch operation. Here, we present a flask (syringe) adaptor that allows the collection and storage of small aliquots (20–30 mL air) for injection into the cavity ring‐down spectroscopy (CRDS) instrument. We demonstrate that the adaptor's precision is similar to that of traditional IRMS (standard deviation of 0.3‰ for 385 ppm CO₂ standard gas). In addition, the concentration precision (±0.3% of sample concentration) was higher for CRDS than for IRMS (±7% of sample concentration). Using the adaptor in conjunction with CRDS, we sampled soil chambers and found that soil‐respired δ¹³C varied between two different locations in a piñon‐juniper woodland. In a second experiment, we found no significant discrimination between the respiration of a small beetle (~5 mm) and its diet. Our work shows that the CRDS system is flexible enough to be used for the analysis of batch samples as well as for continuous sampling. This flexibility broadens the range of applications for which CRDS has the potential to replace magnetic sector IRMS. Copyright © 2011 John Wiley & Sons, Ltd.     

Mammalian DNA δ15N exhibits 40‰ intramolecular variation and is unresponsive to dietary protein level

We report the first high‐precision characterization of molecular and intramolecular δ¹⁵N of nucleosides derived from mammalian DNA. The influence of dietary protein level on brain amino acids and deoxyribonucleosides was determined to investigate whether high protein turnover would alter amino acid ¹⁵ N or ¹³ C values. Pregnant guinea pig dams were fed control diets, or high or low levels of dietary protein throughout gestation, and all pups were fed control diets. The cerebellar DNA of offspring was extracted at 2 and 120 days of life, nucleosides isolated and δ¹⁵N and δ¹³C values characterized. Mean diet δ¹⁵N was 0.45 ± 0.33‰, compared with cerebellar whole tissue and DNA δ¹⁵N = +4.1 ± 0.7‰ and ?4.5 ± 0.4‰, respectively. Cerebellar deoxythymidine (dT), deoxycytidine (dC), deoxyadenosine (dA), and deoxyguanosine (dG) δ¹⁵N were +1.4 ± 0.4, –2.1 ± 0.9, –7.2 ± 0.3, and ?10.4 ± 0.5‰, respectively. There were no changes in amino acid or deoxyribonucleoside δ¹⁵N values due to dietary protein level. Using known metabolic relationships, we developed equations to calculate the intramolecular δ¹⁵N values originating from aspartate (asp) in purines (pur) or pyrimidines (pyr), glutamine (glu), and glycine (gly) to be δ¹⁵N_ASP‐PUR, δ¹⁵N_ASP‐PYR, δ¹⁵N_GLN, and δ¹⁵N_GLY +11.9 ± 2.3‰, +7.0 ± 2.0‰, –9.1 ± 2.4‰, and ?31.8 ± 8.9‰, respectively. A subset of twelve amino acids from food and brain had mean δ¹⁵N values of 4.3 ± 3.2‰ and 13.8 ± 3.1‰, respectively, and δ¹⁵N values for gly and asp were 12.6 ± 2.2‰ and 15.2 ± 0.8‰, respectively. A separate isotope tracer study detected no significant turnover of cerebellar DNA in the first six months of life. The large negative δ¹⁵N difference between gly and cerebellar purine N at the gly (7) position implies either that there is a major isotope effect during DNA synthesis, or that in utero gly has a different isotope ratio during rapid growth and metabolism from that in adult life. Our data show that cerebellar nucleoside intramolecular δ¹⁵N values vary over more than 40‰ and are not influenced by dietary protein level or age. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis of low‐concentration gas samples with continuous‐flow isotope ratio mass spectrometry: eliminating sources of contamination to achieve high precision

Developments in continuous‐flow isotope ratio mass spectrometry have made possible the rapid analysis of δ¹³C in CO₂ of small‐volume gas samples with precisions of ≤0.1‰. Prior research has validated the integrity of septum‐capped vials for collection and short‐term storage of gas samples. However, there has been little investigation into the sources of contamination during the preparation and analysis of low‐concentration gas samples. In this study we determined (1) sources of contamination on a Gasbench II, (2) developed an analytical procedure to reduce contamination, and (3) identified an efficient, precise method for introducing sample gas into vials. We investigated three vial‐filling procedures: (1) automated flush‐fill (AFF), (2) vacuum back‐fill (VBF), and (3) hand‐fill (HF). Treatments were evaluated based on the time required for preparation, observed contamination, and multi‐vial precision. The worst‐case observed contamination was 4.5% of sample volume. Our empirical estimate showed that this level of contamination results in an error of 1.7‰ for samples with near‐ambient CO₂ concentrations and isotopic values that followed a high‐concentration carbonate reference with an isotope ratio of ?47‰ (IAEA‐CO‐9). This carry‐over contamination on the Gasbench can be reduced by placing a helium‐filled vial between the standard and the succeeding sample or by ignoring the first two of five sample peaks generated by each analysis. High‐precision (SD ≤0.1‰) results with no detectable room‐air contamination were observed for AFF and VBF treatments. In contrast, the precision of HF treatments was lower (SD ≥0.2‰). VBF was optimal for the preparation of gas samples, as it yielded faster throughput at similar precision to AFF. Copyright © 2009 John Wiley & Sons, Ltd.     

Calcite‐CO2 mixed into CO2‐free air: a new CO2‐in‐air stable isotope reference material for the VPDB scale

In order to generate a reliable and long‐lasting stable isotope ratio standard for CO₂ in samples of clean air, CO₂ is liberated from well‐characterized carbonate material and mixed with CO₂‐free air. For this purpose a dedicated acid reaction and air mixing system (ARAMIS) was designed. In the system, CO₂ is generated by a conventional acid digestion of powdered carbonate. Evolved CO₂ gas is mixed and equilibrated with a prefabricated gas comprised of N₂, O₂, Ar, and N₂O at close to ambient air concentrations. Distribution into glass flasks is made stepwise in a highly controlled fashion. The isotopic composition, established on automated extraction/measurement systems, varied within very small margins of error appropriate for high‐precision air‐CO₂ work (about ±0.015‰ for δ¹³C and ±0.025‰ for δ¹⁸O). To establish a valid δ¹⁸O relation to the VPDB scale, the temperature dependence of the reaction between 25 and 47°C has been determined with a high level of precision. Using identical procedures, CO₂‐in‐air mixtures were generated from a selection of reference materials; (1) the material defining the VPDB isotope scale (NBS 19, δ¹³C = +1.95‰ and δ¹⁸O = ?2.2‰ exactly); (2) a local calcite similar in isotopic composition to NBS 19 (‘MAR‐J1’, δ¹³C = +1.97‰ and δ¹⁸O = ?2.02‰), and (3) a natural calcite with isotopic compositions closer to atmospheric values (‘OMC‐J1’, δ¹³C = ?4.24‰ and δ¹⁸O = ?8.71‰). To quantitatively control the extent of isotope‐scale contraction in the system during mass spectrometric measurement other available international and local carbonate reference materials (L‐SVEC, IAEA‐CO‐1, IAEA‐CO‐8, CAL‐1 and CAL‐2) were also processed. As a further control pure CO₂ reference gases (Narcis I and II, NIST‐RM 8563, GS19 and GS20) were mixed with CO₂‐free synthetic air. Independently, the pure CO₂ gases were measured on the dual inlet systems of the same mass spectrometers. The isotopic record of a large number of independent batches prepared over the course of several months is presented. In addition, the relationship with other implementations of the VPDB‐scale for CO₂‐in‐air (e.g. CG‐99, based on calibration of pure CO₂ gas) has been carefully established. The systematic high‐precision comparison of secondary carbonate and CO₂ reference materials covering a wide range in isotopic composition revealed that assigned δ‐values may be (slightly) in error. Measurements in this work deviate systematically from assigned values, roughly scaling with isotopic distance from NBS 19. This finding indicates that a scale contraction effect could have biased the consensus results. The observation also underlines the importance of cross‐contamination errors for high‐precision isotope ratio measurements. As a result of the experiments, a new standard reference material (SRM), which consists of two 5‐L glass flasks containing air at 1.6 bar and the CO₂ evolved from two different carbonate materials, is available for distribution. These ‘J‐RAS’ SRM flasks (‘Jena‐Reference Air Set’) are designed to serve as a high‐precision link to VPDB for improving inter‐laboratory comparability. a Copyright © 2005 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.     

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.     

Solvent-induced isotope effects in NMR spectroscopy. A study of hydrogen bonding between the carbonyl group in chalcone and trifluoracetic acid (TFA-d or TFA) in chloroform solution

Splittings, δ_i, were observed for each carbon atom, C_i, of chalcone in spectra obtained from coaxial 5 and 10 mm NMR sample tubes containing solutions equimolar in the concentration of the ketone and of TFA or TFA-d as hydrogen-bond donors, respectively. It was found that a linear expression, δ_i = (K–1)x_HΔ_i+x_Dδ_i(D, H) relates these splittings, δ_i, induced by the isotopic substitution in a hydrogen bond, to the parameter Δ_i, denoting the change in chemical shift for each carbon site in complexed and free ketone, and δ_i(D, H), the solvent-induced isotope effect in a complex. The origin of the phenomenon is briefly discussed. It is also shown that the secondary deuterium isotope effect can give the same information about the form of the potential energy well in the hydrogen-bond as the primary H/D isotopte shifts.     

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.     

A system for high‐quality CO2 isotope analyses of air samples collected by the CARIBIC Airbus A340‐600

In 2007, JRC‐IRMM began a series of atmospheric CO₂ isotope measurements, with the focus on understanding instrumental effects, corrections as well as metrological aspects. The calibration approach at JRC‐IRMM is based on use of a plain CO₂ sample (working reference CO₂) as a calibration carrier and CO₂‐air mixtures (in high‐pressure cylinders) to determine the method‐related correction under actual analytical conditions (another calibration carrier, in the same form as the samples). Although this approach differs from that in other laboratories, it does give a direct link to the primary reference NBS‐19‐CO₂. It also helps to investigate the magnitude and nature for each of the instrumental corrections and allows for the quantification of the uncertainty introduced. Critical tests were focused on the instrumental corrections. It was confirmed that the use of non‐symmetrical capillary crimping (an approach used here to deal with small samples) systematically modifies δ¹³C(CO₂) and δ¹⁸O(CO₂), with a clear dependence on the amount of extracted CO₂. However, the calibration of CO₂‐air mixtures required the use of the symmetrical dual‐inlet mode. As a proof of our approach, we found that δ¹³C(CO₂) on extracts from mixtures agreed (within 0.010‰) with values obtained from the ‘mother’ CO₂ used for the mixtures. It was further found that very low levels of hydrocarbons in the pumping systems and the isotope ratio mass spectrometry (IRMS) instrument itself were critical. The m/z 46 values (consequently the calculated δ¹⁸O(CO₂) values) are affected by several other effects with traces of air co‐trapped with frozen CO₂ being the most critical. A careful cryo‐distillation of the extracted CO₂ is recommended. After extensive testing, optimisation, and routine automated use, the system was found to give precise data on air samples that can be traced with confidence to the primary standards. The typical total combined uncertainty in δ¹³C(CO₂) and δ¹⁸O(CO₂) on the VPDB‐CO₂ scale, estimated on runs of CO₂‐air mixtures, is ±0.040‰ and 0.060‰ (2‐σ values). Inter‐comparison with MPI‐BGC resulted in a scale discrepancy of a similar magnitude. Although the reason(s) for this discrepancy still need to be understood, this basically confirms the approach of using specifically prepared CO₂‐air mixtures as a calibration carrier, in order to achieve scale unification among laboratories. As important practical application and as a critical test, JRC‐IRMM took part in the passenger aircraft‐based global monitoring project CARIBIC ( http://www.caribic‐atmospheric.com ). In this way, reliable CO₂ isotope data for the tropopause region and the free troposphere were obtained. From June 2007 to January 2009, approximately 500 CARIBIC air samples have been analysed. Some flights demonstrated a compact correlation of both δ¹³C(CO₂) and δ¹⁸O(CO₂) with respect to CO₂ concentration, demonstrating mixing of tropospheric and stratospheric air masses. These excellent correlations provide an independent, realistic data quality check. Copyright © 2009 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.     

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.     

Precise and accurate compound-specific carbon and nitrogen isotope analysis of RDX by GC-IRMS

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‰.     

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.