Determination of Hg isotopic compositions in certified reference material NIES No. 13 Human Hair by cold vapor generation multi-collector inductively coupled plasma mass spectrometry

Hg isotopic ratios of NIES CRM No. 13 Human Hair were analyzed using cold vapor generation coupled to multi-collector inductively coupled plasma mass spectrometer to meet the growing demand for better understanding of Hg exposure routes by using Hg isotopic compositions in human hair samples. To validate and assure the accuracy of our analytical method, (1) the reproducibility of the Hg isotopic measurement was monitored and (2) the Hg isotopic compositions of four secondary reference materials—IAEA-085, IAEA-086, and CRPG-RL24H—were measured. Our results for NIES CRM No. 13 show the mass-dependent fractionation values of δ ¹⁹⁹Hg = (2.13 ± 0.07) ‰, δ ²⁰⁰Hg = (0.98 ± 0.08) ‰, δ ²⁰¹Hg = (2.77 ± 0.10) ‰, δ ²⁰²Hg = (1.89 ± 0.10) ‰, and δ ²⁰⁴Hg = (2.76 ± 0.16) ‰ (2SD, n = 11) and the mass-independent fractionation values of Δ ¹⁹⁹Hg = (1.65 ± 0.06) ‰, Δ ²⁰⁰Hg = (0.04 ± 0.04) ‰, Δ ²⁰¹Hg = (1.36 ± 0.07) ‰, and Δ ²⁰⁴Hg = (?0.04 ± 0.11) ‰ (2SD, n = 11). Interlaboratory comparison of the CRM performed at the University of Pau showed good agreement with the values obtained at NIES.     

A new method for the determination of low-level actinium-227 in geological samples

We developed a new method for the determination of ²²⁷Ac in geological samples. The method uses extraction chromatographic techniques and alpha-spectrometry and is applicable for a range of natural matrices. Here we report on the procedure and results of the analysis of water (fresh and seawater) and rock samples. Water samples were acidified and rock samples underwent total dissolution via acid leaching. A DGA (N,N,N′,N′-tetra-n-octyldiglycolamide) extraction chromatographic column was used for the separation of actinium. The actinium fraction was prepared for alpha spectrometric measurement via cerium fluoride micro-precipitation. Recoveries of actinium in water samples were 80 ± 8 % (number of analyses n = 14) and in rock samples 70 ± 12 % (n = 30). The minimum detectable activities (MDA) were 0.017–0.5 Bq kg^?1 for both matrices. Rock sample ²²⁷Ac activities ranged from 0.17 to 8.3 Bq kg^?1 and water sample activities ranged from below MDA values to 14 Bq kg^?1of ²²⁷Ac. From the analysis of several standard rock and water samples with the method we found very good agreement between our results and certified values.     

A new Chinese national reference material (GBW04481) for calcite oxygen and carbon isotopic microanalysis

Carbonate oxygen (O) and carbon (C) isotopes are widely used as proxies for tracing the processes and physicochemical conditions of many geological events and environmental changes in Earth Science. In particular, O and C isotopic variations at micrometer scales revealed by modern microbeam analytical techniques such as SIMS and NanoSIMS are robust archives for reconstructing palaeoenvironment and paleoclimate changes at annual and seasonal resolution or even higher temporal resolution. Widespread application of carbonate O and C isotopic microanalysis in Earth Sciences, however, has been restricted due to limitation of high-quality carbonate reference materials for O and C isotopic microanalysis. We introduce in this paper a new calcite reference material for calcite O and C isotopic microanalysis. This calcite is collected from a drill-core of the Oka carbonatite complex (Quebec, Canada). We demonstrated that the Oka calcite is fairly homogeneous in O and C isotopic compositions at micrometer scales based on homogeneity test by hundreds of SIMS O and C isotopic analyses. Precise determinations by using conventional gas-source IRMS yield the recommended value of δ¹⁸O_VPDB = −23.12 ± 0.15‰ (1SD) and δ¹³C_VPDB = −5.23 ± 0.06‰ (1SD) for the Oka calcite, which has been certified as the first class of Chinese national certified reference material (GBW04481) for O and C isotopic microanalysis.     

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.     

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.     

Oxygen isotope homogeneity assessment for apatite U-Th-Pb geochronology reference materials

Secondary ion mass spectrometry (SIMS) measurement of oxygen isotopes in apatite has been employed more and more in petrogenetic, metallogenic, and climate change studies. Well-characterised reference materials are needed due to the matrix effect, but they are yet to be well established. In this study, we conducted in-situ oxygen isotopic and chemical analyses on six commonly used apatite reference materials (ie, Emerald, Kovdor, McClure, Mud Tank, Otter Lake, and Slyudyanka) and two in-house apatite references (Qinghu and GEMS 203) to assess their oxygen isotope homogeneity and applicability for microbeam analyses. Our results show that all these apatite references are in general chemically homogeneous. In terms of oxygen isotopes, GEMS 203 (δ¹⁸O = 9.85 ± 0.40‰ [2SD], corrected by Durango 3), Kovdor (δ¹⁸O = 6.55 ± 0.38‰, 2SD), and McClure (δ¹⁸O = 5.94 ± 0.42‰, 2SD) are fairly homogeneous, whereas Emerald (δ¹⁸O = 10.37 ± 0.45‰, 2SD), Mud Tank (δ¹⁸O = 6.35 ± 0.46‰, 2SD), Otter Lake (δ¹⁸O = 9.71 ± 0.47‰, 2SD), Qinghu (δ¹⁸O = 5.44 ± 0.49‰, 2SD), and Slyudyanka (δ¹⁸O = 17.49 ± 0.43‰, 2SD) are less homogenous. This indicates that the former group represents better reference materials for in-situ oxygen isotopic analyses, whilst the latter group can be used as secondary reference material for analytical quality control.     

Extraction of lithium from GSJ rock reference samples and determination of their lithium isotopic compositions

Li was extracted completely from the Geological Survey of Japan (GSJ) rock reference samples by HF-HC1 decomposition and separated from other alkali metal ions by cation exchange chromatography. The degree of Li isotope fractionation during the preparations of samples for mass spectrometry for Li isotopic ratio measurements was, therefore, negligible. The isotopic compositions of Li extracted from the GSJ samples were measured by double-filament surface ionization mass spectrometry. The permil (%.) deviation, δ⁷Li, of the ⁷Li-to-⁶Li ratio of one of the GSJ samples (JR-1) from that of the Li isotope standard, IRM-016, was +3.9%., with a 95% confidence limit of 0.7%. The δ⁷Li values of the 16 GSJ samples varied in the range −2.5 to +6.4%.. These data are probably the first such data obtained for the GSJ rock samples. No clear dependence of the δ⁷Li value on the kind of rock was observed.     

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.     

High‐precision determination of lithium and magnesium isotopes utilising single column separation and multi‐collector inductively coupled plasma mass spectrometry

Rationale

Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single‐step cation‐exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices.

Methods

The column method utilises the macro‐porous AGMP‐50 resin and a high‐aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High‐precision isotope determination was conducted by multi‐collector inductively coupled plasma mass spectrometry (MC‐ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 10¹³ Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V.

Results

Sub‐nanogram Li samples (0.3–0.5 ng) were regularly separated (yielding Mg masses of 1–70 μg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long‐term external 2σ precisions of ±0.39‰ for δ⁷Li and ±0.07‰ for δ²⁶Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption.

Conclusions

The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters.

     

A novel approach to measure isotope ratios via multi-collector—inductively coupled plasma—mass spectrometry based on sample mixing with a non-enriched standard

In this work, a novel approach to measure isotope ratios via multi-collector—inductively coupled plasma—mass spectrometry (MC-ICP-MS) for low amounts of target element is proposed. The methodology is based on mixing of the sample (target element isolate) with a non-enriched in-house standard, previously characterized for its isotopic composition. This methodology has been applied to isotopic analysis of Cu and of Fe in whole blood samples. For this purpose, different mixtures of sample + in-house standard were prepared and adjusted to a final concentration of 500 μg/L of the target elements for isotopic analysis. δ⁶⁵Cu, δ⁵⁶Fe, and δ⁵⁷Fe varied linearly as a function of the amount of in-house standard (or of sample) present in the mixture. The isotopic composition of the sample was calculated considering the isotope ratios measured for (i) the mixture and (ii) the in-house standard and (iii) the relative concentrations of target element contributed by the sample and the standard to the mixture, respectively. For validation purposes, the isotopic analysis of whole blood Cu was carried out using both the conventional (using 2 mL of whole blood) and the newly developed approach (using 500 μL of whole blood). The δ⁶⁵Cu values obtained using mixtures containing 40 % (200 μg/L) of Cu from the blood samples and 60 % (300 μg/L) of Cu from the in-house standard were in good agreement with the δ⁶⁵Cu value obtained using the conventional approach (bias ≤0.15?‰).     

Use of [13C]/[12C] ratios as an indicator of the role of microorganisms in protection of plants from the phytotoxic action of naphthalene

Using molecular and isotopic mass spectrometry, we investigated the toxic effect of naphthalene as a representative of polycyclic aromatic hydrocarbons (PAHs) on plants growing under sterile conditions and plants inoculated with microorganisms capable and incapable of naphthalene degradation. Tobacco plants of the Samsun variety were grown in a closed gas-nutrient system on a mineral medium with sucrose as a carbon source. Naphthalene used as a toxicant at a concentration of 5.2 × 10^?4% contained ¹³C isotope whose amount was characterized by the value δ¹³C = +281.4 ± 0.6‰ relative to the PDB standard and differed from that of sucrose, the main source of carbon (δ¹³C = ?12.0 ± 0.1‰). Degradation of naphthalene was determined by the inclusion of its carbon in metabolic CO₂ and plant tissues (the root, stem, leaves). The effect of naphthalene on plants was indicated by the rates of O₂ production and CO₂ uptake during the light period as compared with the dark period of exposure. A decrease of the toxic effect of naphthalene on plants was observed only at the inoculation of plants with Pseudomonas aureofaciens BS1393 rhizosphere bacteria bearing plasmid pBS216, which controls the naphthalene biodegradation ability. The occurrence of other heterotrophic microorganisms incapable of naphthalene degradation had no similar protective effect.     

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.     

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.     

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.     

Accurate and precise lithium isotopic determinations of igneous rock samples using multi-collector inductively coupled plasma mass spectrometry

A second-generation multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) was applied to lithium isotopic measurements. The high sensitivity of the ICP-MS enabled high precision (±0.82‰, 2σ) analyses with small amount of Li (∼45 ng Li). A single-step column separation protocol was established with which rapid purification of lithium from rock solutions can be carried out with reduced blank (<10 pg). The influence of potential sources of error for acquisition of lithium isotopic data introduced during the separation, such as matrix effects and isotopic fractionation due to incomplete recovery, were examined with an artificially mixed solution of a composition similar to that of basalt, which was doped with Li isotopic standard reagent. The examinations demonstrated that our protocol suffered from negligible isotopic fractionation.The Li isotopic ratios obtained by our method for seawater and standard rocks (JA-1, JB-2, and JB-3) agree well with those of previously reported data by Moriguti and Nakamura [1] and [2], which were determined using a four-step column separation method and thermal ionisation mass spectrometry (TIMS). Our separation protocol combined with a sensitive MC-ICP-MS will enable Li isotopic analyses on silicate rock with low Li contents, such as meteorite and peridotites with increased sample throughput.     

In vacuo reduction of silver orthophosphate with graphite for high‐precision oxygen isotope analysis

The reduction of silver phosphate with graphite under vacuum conditions was studied at final reaction temperatures varying from 430 to 915°C to determine: (i) the CO₂ extraction yield, and (ii) the oxygen isotopic composition of CO₂. The CO₂ yield and oxygen isotopic composition were determined on a calibrated dual inlet and triple collector isotope ratio mass spectrometer. We observed the following three stages of the reduction process. (1) At temperatures below 590°C only CO₂ is formed, while silver orthophosphate decays to pyrophosphate. (2) At higher temperatures, 590–830°C, predominantly CO is formed from silver pyrophosphate which decays to metaphosphate; this CO was always converted into CO₂ by the glow discharge method. (3) At temperatures above 830°C the noticeable sublimation of silver orthophosphate occurs. This observation was accompanied by the oxygen isotope analysis of the obtained CO₂. The measured δ¹⁸O value varied from ?11.93‰ (at the lowest temperature) to ?20.32‰ (at the highest temperature). The optimum reduction temperature range was found to be 780–830°C. In this temperature range the oxygen isotopic composition of CO₂ is nearly constant and the reaction efficiency is relatively high. The determined difference between the δ¹⁸O value of oxygen in silver phosphate and that in CO₂ extracted from this phosphate is +0.70‰. Copyright © 2010 John Wiley & Sons, Ltd.     

δ34S for tracing the origin of cheese and detecting its authenticity

Casein δ³⁴S of 725 samples of cheese from all over the world were measured using IRMS. δ³⁴S alone made it possible to establish characteristic ranges of values for two types of Italian cheese (Grana Padano PDO and Parmigiano Reggiano PDO) and for the different regions and provinces of both the Grana Padano PDO and the Parmigiano Reggiano PDO zones. Moreover, δ³⁴S of PDO Italian samples were compared to both Italian (not PDO) and foreign competitive cheese samples. In all the cases, sulfur isotopic ratio analysis was a powerful tool to fix characteristic ranges of values for cheeses coming from different countries and to improve the information given by other isotopic parameters.     

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.     

Preparation and characterisation of synthetic mixtures of lithium isotopes

Re-certification of the absolute isotopic composition of the natural lithium isotopic reference material (IRM), IRMM-016, requires measurements calibrated by means of synthetic mixtures of highly enriched lithium isotopes. Ten such mixtures were prepared by weighing and mixing of two well characterised, isotopically enriched, Li₂CO₃ compounds. The starting materials, 99.9981% enriched ⁶Li, and 99.9937% enriched ⁷Li, were purified by ion exchange, and the purified materials converted from LiOH to Li₂CO₃ by reaction with CO₂. Ten new mixtures were prepared by mixing different weighed amounts of these dissolved Li₂CO₃ carrier compounds. The compounds had an estimated level of impurities of 100 ± 100 μg · g^–1 (expanded uncertainty with a coverage factor of 2). In the ten mixtures, the n(⁶Li)/n(⁷Li) ratio varies from 0.025 to 14 and the achieved expanded relative uncertainty on the amount ratio prepared is typically 2 · 10^–4. These mixtures were then used to determine the correction factor, K, for mass discrimination of the measurement procedure and instrument concerned.     

Deuterium-depleted water: A new tracer to label pulmonary surfactant lipids in adult rabbits

Stable isotope tracing can be safely used for metabolic studies in animals and humans. The endogenous biosynthesis of lipids (lipogenesis) is a key process throughout the entire life but especially during brain and lung growth. Adequate synthesis of pulmonary surfactant lipids is indispensable for life. With this study, we report the use of deuterium-depleted water (DDW), suitable for human consumption, as metabolic precursor for lipogenesis. We studied 13 adult rabbits for 5 days. Four rabbits drank tap water (TW) and served as controls; in four animals, DDW was substituted to drinking water, whereas five drank deuterium-enriched water (DEW). After 5 days, a blood sample and a bronchoalveolar lavage (BAL) sample were collected. The ²H/¹H (δ²H) of BAL palmitic acid (PA) desaturated phosphatidylcholine (DSPC), the major phospholipid of pulmonary surfactant, and of plasma water was determined by high-resolution mass spectrometry. We found that the δ²H values of DDW, DEW and TW were −984 ± 2‰, +757 ± 2‰ and −58 ± 1‰, respectively. After 5 days, plasma water values were −467 ± 87‰, +377 ± 56‰ and −53 ± 6‰, and BAL DSPC-PA was −401 ± 27‰, −96 ± 38‰ and −249 ± 9‰ in the DDW, DEW and TW, respectively. With this preliminary study, we demonstrated the feasibility of using DDW to label pulmonary surfactant lipids. This novel approach can be used in animals and in humans, and we speculate that it could be associated with more favourable study compliance than DEW in human studies.