Isotope Ratio Mass Spectrometer Research Articles

Altered Intramuscular Lipid Metabolism Relates to Diminished Insulin Action in Men, but Not Women, in Progression to Diabetes

Whether sex differences in intramuscular triglyceride (IMTG) metabolism underlie sex differences in the progression to diabetes are unknown. Therefore, the current study examined IMTG concentration and fractional synthesis rate (FSR) in obese men and women with normal glucose tolerance (NGT) vs. those with prediabetes (PD). PD (n = 13 men and 7 women) and NGT (n = 7 men and 12 women) groups were matched for age and anthropometry. Insulin action was quantified using a hyperinsulinemic-euglycemic clamp with infusion of [6,6-(2)H(2)]-glucose. IMTG concentration was measured by gas chromatography/mass spectrometry (GC/MS) and FSR by GC/combustion isotope ratio MS (C-IRMS), from muscle biopsies taken after infusion of [U-(13)C]palmitate during 4 h of rest. In PD men, the metabolic clearance rate (MCR) of glucose was lower during the clamp (4.71 ± 0.77 vs. 8.62 ± 1.26 ml/kg fat-free mass (FFM)/min, P = 0.04; with a trend for lower glucose rate of disappearance (Rd), P = 0.07), in addition to higher IMTG concentration (41.2 ± 5.0 vs. 21.2 ± 3.4 µg/mg dry weight, P ≤ 0.01), lower FSR (0.21 ± 0.03 vs. 0.42 ± 0.06 %/h, P ≤ 0.01), and lower oxidative capacity (P = 0.03) compared to NGT men. In contrast, no difference in Rd, IMTG concentration, or FSR was seen in PD vs. NGT women. Surprisingly, glucose Rd during the clamp was not different between NGT men and women (P = 0.25) despite IMTG concentration being higher (42.6 ± 6.1 vs. 21.2 ± 3.4 µg/mg dry weight, P = 0.03) and FSR being lower (0.23 ± 0.04 vs. 0.42 ± 0.06 %/h, P = 0.02) in women. Alterations in IMTG metabolism relate to diminished insulin action in men, but not women, in the progression toward diabetes.

Simultaneous Identification and δ13C Classification of Drugs Using GC with Concurrent Single Quadrupole and Isotope Ratio Mass Spectrometers*

In this study, δ¹³C values of six cocaine samples were identified and classified using a single quadrupole mass spectrometer and an isotope ratio mass spectrometry (IRMS) as simultaneous gas chromatography detectors. Our instrument modification is simple to use and is useful (i) when the sample is of limited size or can only be injected once, (ii) to help identify peaks in a complicated IRMS chromatogram, and (iii) to help differentiate very simple systems when impurity profiling is not possible. The EI-MS confirmed the identity of cocaine in each sample. The IRMS data distinguished 12 of the 15 possible pair-wise comparisons at the 95% CL. Three samples could not be differentiated by their δ¹³C ratios for cocaine. ANOVA demonstrated that the measurement variance was consistently larger than the sample variance. As the δ¹³C values clearly show, this technique enables the exclusion of a potential common source even when two samples have otherwise identical chemical and physical properties.

Elemental and isotopic characterization of cane and beet sugars

An interlaboratory program designed to assess the feasibility of using multi-element and isotopic measurements for determining the geographic origin of sugars permitted an intercomparison of the performance (in terms of limits of detection, reproducibility and bias) of various analytical techniques: inductively coupled plasma (ICP)-optical emission spectrometry (OES); different variations of ICP-mass spectrometry (MS): quadrupole (QMS), sector-field (SFMS) and multi-collector (MC-ICP-MS); thermal ionization MS (TIMS); and isotope ratio MS (IRMS). These various methods were applied to cane (raw and refined) and beet (refined) sugars from different origins. Concentrations of 63 elements and isotope ratios of Pb, Sr and C in sugar samples are reported. Determining the geographic origin of sugars appears feasible using elemental fingerprinting.

Geographic origin of southern Brazilian wines by carbon and oxygen isotope analyses

We present a method that can differentiate between the varieties of grapes and the vintages of wines and show the relationship between the grapes, the wine and the geographic location. The place of origin and its geographic and climatic characteristics were determined by the isotopic ratios, (13)C/(12)C of the ethanol and (18)O/(16)O of the water content of wine (wine water), for southern Brazil wines. The producing subregions of Pinto Bandeira, Vale dos Vinhedos and Nova Pádua showed differences in the temperature, rainfall and humidity conditions used for the production under microvinification conditions of Merlot and Cabernet Sauvignon varieties, in the harvests of 2005 and 2006. An isotope ratio mass spectrometer coupled to an elemental analyzer was used to measure the (13)C/(12)C of ethanol and the (18)O/(16)O of wine water. Regardless of the grape variety used, it was possible to determine the subregion through measurement of the δ(18)O values in both harvests. The altitudes of the different subregions led to statistical differences and demonstrated an influence mainly on the δ(18)O values of wine water. The δ(18)O value of wine water was determined to be more selective for the determination of the cultivation subregions than the δ(13)C value of the ethanol. The altitude and latitude influenced mainly the δ (18)O values of wine water and the ethanol. The climatic influences are more noteworthy in distinguishing the year of the harvest than the cultivation subregion.

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 CO(2) extraction yield, and (ii) the oxygen isotopic composition of CO(2). The CO(2) 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 CO(2) 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 CO(2) 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 CO(2). The measured δ(18)O 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 CO(2) is nearly constant and the reaction efficiency is relatively high. The determined difference between the δ(18)O value of oxygen in silver phosphate and that in CO(2) extracted from this phosphate is +0.70‰.

13C Discrimination: A Stable Isotope Method to Quantify Root Interactions between C3 Rice (Oryza sativa) and C4 Barnyardgrass (Echinochloa crus-galli) in Flooded Fields

Assessing belowground plant competition is complex because it is very difficult to separate weed and crop roots from each other by physical methods. Alternative techniques for separating crop and weed roots from each other are needed. This article introduces a stable isotope method that can quantify the amounts of roots of rice and barnyardgrass intermixed in flooded field soils. It relies on the biological principle that rice, a C3 (photosynthetic pathway) species, discriminates more effectively than barnyardgrass, a C4 species, against a relatively rare isotopic form (13C) of CO2. This results in different 13C: 12C isotope ratios (expressed as δ13C) in root tissues of the two species. δ13C values for monoculture barnyardgrass and rice grown in a standard flood-irrigated system were highly stable over 4 crop-years, averaging −13.12 ± 0.80 (SD) and −28.5 ± 0.11 (SD)‰, respectively, based on analysis by an isotope ratio mass spectrometer. Standard concentration curves relating measured δ13C values to set proportions of rice:barnyardgrass root biomass were described by linear regressions, typically with r2 values of 0.96 or greater. Quantities of intermixed rice and barnyardgrass roots sampled 0 to 5 cm deep from soil between rice rows were estimated by extrapolation from standard curves based on δ13C values. About 50% more barnyardgrass root tissue was detected in plots of Lemont long-grain rice than in weed-suppressive PI 312777 indica rice, demonstrating the feasibility of using this stable carbon isotope method in flooded rice systems.

Advances in natural stable isotope ratio analysis of human hair to determine nutritional and metabolic status

We review the literature on the use of stable isotope ratios at natural abundance to reveal information about dietary habits and specific nutrient intakes in human hair protein (keratin) and amino acids. In particular, we examine whether hair isotopic compositions can be used as unbiased biomarkers to provide information about nutritional status, metabolism, and diseases. Although the majority of research on the stable isotope ratio analysis of hair has focused on bulk protein, methods have been recently employed to examine amino acid-specific isotope ratios using gas chromatography or liquid chromatography coupled to an isotope ratio mass spectrometer. The isotopic measurement of amino acids has the potential to answer research questions on amino acid nutrition, metabolism, and disease processes and can contribute to a better understanding of the variations in bulk protein isotope ratio values. First results suggest that stable isotope ratios are promising as unbiased nutritional biomarkers in epidemiological research. However, variations in stable isotope ratios of human hair are also influenced by nutrition-dependent nitrogen balance, and more controlled clinical research is needed to examine these effects in human hair. Stable isotope ratio analysis at natural abundance in human hair protein offers a noninvasive method to reveal information about long-term nutritional exposure to specific nutrients, nutritional habits, and in the diagnostics of diseases leading to nutritional stress and impaired nitrogen balance.

Isotopic composition and concentration measurements of atmospheric CO2 with a diode laser making use of correlations between non-equivalent absorption cells

Correlations between a sample and a sealed reference cell of a tunable diode laser spectrometer for the measurement of the isotopic composition (δ13C) and the concentration of atmospheric carbon dioxide in air have been investigated. Likely due to fluctuations of the laser emission profile, these correlations have been used to improve the performance of the instrument. In a comparison with isotope ratio mass spectrometer and gas chromatographic measurements, an accuracy of 0.15‰ for δ13C and 0.05 ppmv for the CO2 concentration is demonstrated for 40 s integration time. Long-term stability and field deployment of the instrument have been investigated during a few days measurement campaign in Paris.

Error propagation in normalization of stable isotope data: a Monte Carlo analysis

A higher analytical precision of a stable isotope ratio mass spectrometer does not automatically guarantee accurate determination of the true isotope composition (delta-value) of samples, since estimates of true delta-values are obtained from the normalization of raw isotope data. We performed both Monte Carlo simulations and laboratory experiments to investigate aspects of error propagation during the normalization of carbon stable isotope data. We found that increasing both the number of different reference standards and the number of repetitions of each of these standards reduces the normalization error. A 50% reduction in the normalization error can be achieved over the two-point normalization by either analyzing two standards four times each, or four standards two times each. If the true delta-value of a sample is approximately known a priori, the normalization error may then be reduced through a targeted choice of locally optimal standards. However, the difference in improvement is minimal and, therefore, a more practical strategy is to use two or more standards covering the whole stable isotope scale. The selection of different sets of standards by different laboratories or for different batches of samples in the same laboratory may lead to significant differences in the normalized delta-values of the same samples, leading to inconsistent results. Hence, the same set of standards should always be used for a particular element and a particular stable isotope analytical technique.

Caution on the Use of Liquid Nitrogen Traps in Stable Hydrogen Isotope-Ratio Mass Spectrometry

An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN(2)) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ(2)H reproducibility (1σ standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN(2) is used as a moisture trap for gaseous hydrogen.

Inflexibility in Intramuscular Triglyceride Fractional Synthesis Distinguishes Prediabetes From Obesity in Humans

Whether intramuscular triglyceride (IMTG) concentration or flux is more important in the progression to type 2 diabetes is controversial. Therefore, this study examined IMTG concentration, as well as its fractional synthesis rate (FSR), in obese people with normal glucose tolerance (NGT; n = 20) vs. obese people with prediabetes (PD; n = 19), at rest and during exercise. Insulin action and secretion were assessed using an intravenous glucose tolerance test. [U-(13)C]palmitate was infused for 4 h before and throughout 1.5 h of treadmill walking at 50% VO(2(max)). IMTG concentration was measured by gas chromatograph/mass spectrometer, and FSR by gas chromatography-combustion isotope ratio mass spectrometer, from muscle biopsies taken immediately before and after exercise. Basal IMTG concentration was higher (43 +/- 5.7 vs. 27 +/- 3.9 mg/mg dry weight, P = 0.03) and FSR trended lower (0.23 +/- 0.04 vs. 0.32 +/- 0.05/h, P = 0.075), as did insulin action (S(i); 2.9 +/- 0.43 vs. 3.3 +/- 0.35 x 10(-4)/mU/ml, P = 0.07), in PD vs. NGT. IMTG concentration did not change significantly during exercise, but was no longer different in PD vs. NGT (45 +/- 7.7 vs. 37 +/- 5.8 mg/mg dry weight, P = 0.41). IMTG FSR suppressed during exercise in NGT (-81% to 0.06 +/- 0.13/h, P = 0.02), but not PD (+4% to 0.24 +/- 0.13%/h, P = 0.95). Palmitate oxidation was similar during rest (P = 0.92) and exercise (P = 0.94) between groups, but its source appeared different with more coming from muscle at rest and plasma during exercise in NGT, whereas the converse was true in PD. Altogether, higher basal IMTG concentration that is metabolically inflexible distinguishes obese people with PD from those with NGT.

δ13C Stable Isotope Analysis of Atmospheric Oxygenated Volatile Organic Compounds by Gas Chromatography-Isotope Ratio Mass Spectrometry

We present a new method for analyzing the delta(13)C isotopic composition of several oxygenated volatile organic compounds (OVOCs) from direct sources and ambient atmospheric samples. Guided by the requirements for analysis of trace components in air, a gas chromatograph isotope ratio mass spectrometer (GC-IRMS) system was developed with the goal of increasing sensitivity, reducing dead-volume and peak band broadening, optimizing combustion and water removal, and decreasing the split ratio to the isotope ratio mass spectrometer (IRMS). The technique relies on a two-stage preconcentration system, a low-volume capillary reactor and water trap, and a balanced reference gas delivery system. The instrument's measurement precision is 0.6 to 2.9 per thousand (1sigma), and results indicate that negligible sample fractionation occurs during gas sampling. Measured delta(13)C values have a minor dependence on sample size; linearity for acetone was 0.06 per thousand ng C(-1) and was best over 1-10 ng C. Sensitivity is approximately 10 times greater than similar instrumentation designs, incorporates the use of a diluted working reference gas (0.1% CO(2)), and requires collection of >0.7 ng C to produce accurate and precise results. With this detection limit, a 1.0 L sample of ambient air provides sufficient carbon for isotopic analysis. Emissions from vegetation and vehicle exhaust are compared and show clear differences in isotopic signatures. Ambient samples collected in metropolitan Miami and the Everglades National Park can be differentiated and reflect multiple sources and sinks affecting a single sampling location. Vehicle exhaust emissions of ethanol, and those collected in metropolitan Miami, have anomalously enriched delta(13)C values ranging from -5.0 to -17.2 per thousand; we attribute this result to ethanol's origin from corn and use as an additive in automotive fuels.

An automated method for ‘clumped‐isotope’ measurements on small carbonate samples

Clumped-isotope geochemistry deals with the state of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of earth sciences. Clumped-isotope thermometry allows reconstructing the temperature of formation of carbonate minerals without knowing the isotopic composition of the water from which they were formed. This feature enables new approaches in paleothermometry. The currently published method is, however, limited by sample weight requirements of 10-15 mg and because measurements are performed manually. In this paper we present a new method using an automated sample preparation device coupled to an isotope ratio mass spectrometer. The method is based on the repeated analysis (n = 6-8) of 200 microg aliquots of sample material and completely automated measurements. In addition, we propose to use precisely calibrated carbonates spanning a wide range in Delta(47) instead of heated gases to correct for isotope effects caused by the source of the mass spectrometer, following the principle of equal treatment of the samples and standards. We present data for international standards (NBS 19 and LSVEC) and different carbonates formed at temperatures exceeding 600 degrees C to show that precisions in the range of 10 to 15 ppm (1 SE) can be reached for repeated analyses of a single sample. Finally, we discuss and validate the correction procedure based on high-temperature carbonates instead of heated gases.

Correction for the 17O interference in δ(13C) measurements when analyzing CO2 with stable isotope mass spectrometry (IUPAC Technical Report)

Measurements of δ(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor λ, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [δ(13C) ≍ 45 δ VPDB-CO2 + 2 17 R/13 R (45 δ VPDB-CO2 – λ46 δ VPDB-CO2)] closely approximates δ(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for δ(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

Validez de los índices de masa corporal y de masa grasa como indicadores de sobrepeso en adolescentes españoles: estudio Esccola

To determine the accuracy of body mass index (BMI), fat mass index (FMI) and fat-free mass index (FFMI) to find cut-off points related to overweight in adolescents aged 12-18 years. 150 adolescents were assessed (75 boys aged 14.81+/-1.86yr, height 168.8+/-8.8cm, weight 65.84+/-16kg and BMI 22.89+/-4.4kg x m(2), and 75 girls aged 14.88+/-1.94yr, height 159.4+/-7.6cm, weight 54.77+/-9.54kg and BMI 21.48+/-3.1kg x m(2)). Body composition was measured by using the deuterium dilution technique with an isotope ratio mass spectrometer and fat free mass hydration constants were applied. Taylor's age-related overweight classification was applied and receiver operating characteristic (ROC) curves analyses were performed. Areas under curve were calculated for every index (BMI, FMI and FFMI). Sensitivity and specificity values of BMI and FMI to diagnose overweight were evaluated. Among boys, predictive positive values for BMI were 78.1% and 89.2% for FMI; predictive positive values in girls was 34.8% for BMI and 81.4% for FMI. Predictive negative values were 81.4% and 100% in boys and 98.1% and 100% in girls for BMI and FMI. Areas under curve of FMI for boys (0.988, 95%CI: 0.930-0.998) and girls (0.996, 95%CI: 0.943-1.000) showed high accuracy for overweight diagnose. Cutoff points of 4.58kg x m(2) in boys and 7.76kg x m(2) in girls for FMI and 23.07kg x m(2) in boys and 23.18kg x m(2) in girls for BMI had high sensitivity and specificity as indicators of overweight classification. FMI showed high accuracy for overweight screening. Thus, our cut-off points may be useful as a tool to surveillance children's overweight on clinical and epidemiologic settings.

Genuineness assessment of mandarin essential oils employing gas chromatography‐combustion‐isotope ratio MS (GC‐C‐IRMS)

Cold-pressed mandarin essential oils are products of great economic importance in many parts of the world and are used in perfumery, as well as in food products. Reconstituted mandarin oils are easy to find on the market; useful information on essential oil authenticity, quality, extraction technique, geographic origin and biogenesis can be attained through high-resolution GC of the volatile fraction, or enantioselective GC, using different chiral stationary phases. Stable isotope ratio analysis has gained considerable interest for the unveiling of citrus oil adulteration, detecting small differences in the isotopic carbon composition and providing plenty of information concerning the discrimination among products of different geographical origin and the adulteration of natural essential oils with synthetic or natural compounds. In the present research, the authenticity of several mandarin essential oils was assessed through the employment of GC hyphenated to isotope ratio MS, conventional GC flame ionization detector, enantioselective GC and HPLC. Commercial mandarin oils and industrial natural (declared as such) mandarin essential oils, characterized by different harvest periods and geographic origins, were subjected to analysis. The results attained were compared with those of genuine cold-pressed Italian mandarin oils, obtained during the 2008-2009 harvest season.

Fully automated system for stable isotopic analyses of dissolved nitrous oxide at natural abundance levels

Isotopic and isotopomeric analyses of dissolved nitrous oxide (N2O) can provide important information about the mechanisms of production and consumption of this climatically important trace gas. Increased spatial and temporal data coverage for N2O isotopic measurements are needed to improve our understanding of the production of N2O in a variety of aquatic environments, such as coastal and open ocean areas. A new method is presented for automated measurement of δ15Nbulk, δ18O, and site preference of dissolved nitrous oxide in natural waters using a GC‐Pal autosampler and a Finnigan DeltaPlus isotope ratio mass spectrometer and is capable of analyzing 30 samples in 22 h without user attention after the start of the run. The system was first tested with samples produced by injecting our N2O reference gas and/or N2O test mixtures, ranging in isotopic composition and concentration, into N2‐sparged seawater. The method was then applied to samples containing a large range of N2O concentrations, δ15Nbulk, δ18O, and site preference values from two high‐resolution depth profiles from the Arabian Sea. The results showed precise determination of isotopic values of N2O from 160 mL aqueous samples over the concentration range normally found in the oceans (5–80 nmol L−1). Sample standard deviation for triplicate 160 mL samples at 6 nmol L−1 N2O is better than 0.3‰ for δ15Nbulk, 0.5‰for δ18O, and 1.0‰ for 15N site preference. The automated technique described here requires relatively minor modifications of existing N2O purge and trap systems and can be implemented broadly for a variety of applications.

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 (13)C/(12)C 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 (13)C-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 CO(2). We therefore coupled a high-temperature combustion TOC analyzer with an isotope ratio mass spectrometer, by trapping and focusing the CO(2) 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) < or = 0.6 per thousand), acceptable accuracy, good linearity (overall SD = 1 per thousand) and without significant memory effects. In a (13)C-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 (13)C/(12)C ratio of DOC in soil solutions.

PRELIMINARY INVESTIGATION INTO THE GEOGRAPHICAL ORIGIN DIFFERENTIATION OF SAFFRON (CROCUS SATIVUS L.) BY MULTI-ELEMENT (HCN) STABLE ISOTOPE ANALYSIS

ISHS III International Symposium on Saffron: Forthcoming Challenges in Cultivation, Research and Economics PRELIMINARY INVESTIGATION INTO THE GEOGRAPHICAL ORIGIN DIFFERENTIATION OF SAFFRON (CROCUS SATIVUS L.) BY MULTI-ELEMENT (HCN) STABLE ISOTOPE ANALYSIS

13C/12C Analysis of Ultra-Trace Amounts of Volatile Organic Contaminants in Groundwater by Vacuum Extraction

We developed a method for the vacuum extraction (VacEx) of volatile organic compounds (VOCs) from water samples for ultratrace determinations of carbon isotopic signatures. Our method permits compound-specific stable carbon isotope analysis (CSIA) at VOC concentrations as low as 0.03-1.34 microg/L. VacEx was developed to extract and preconcentrate VOCs for subsequent carbon-CSIA by the standard technique purge-and-trap (P&T) coupled to an isotope-ratio mass spectrometer (IRMS). Even without complete extraction, the delta(13)C signatures of VOCs determined by VacEx-P&T-IRMS were in good agreement (deviation <1 per thousand) with signatures determined by P&T-IRMS. This indicates that VacEx does not cause isotopic discrimination. Limits of quantification (LOQs) for delta(13)C analysis were: 0.03-0.06 microg/L for benzene, toluene, o-xylene, m-p-xylene and ethylbenzene, 0.09 microg/L for methyl tert-butyl ether (MTBE), and 0.18-0.27 microg/L for trans-DCE, cis-DCE, TCE and PCE. These are the lowest LOQs reported to date for continuous-flow isotope-ratio determinations using a commercially available and automated system. To our knowledge, analytical protocols adopted from noble gas analysis in water were applied for the first time to determine the isotope composition of organic contaminants. We applied VacEx in a field study to illustrate how the determination of VOC isotopic signatures at very low concentrations opens new avenues in the in situ assessment of these priority groundwater pollutants.