Gas Chromatography-isotope Ratio Mass Spectrometry Research Articles

The influence of sample matrix on the accuracy of nitrite N and O isotope ratio analyses with the azide method.

The isotope ratios of nitrogen (15 N/14 N) and oxygen (18 O/16 O) in nitrite (NO2 - ) can be measured by conversion of the nitrite into nitrous oxide (N2 O) with azide, followed by mass spectrometric analysis of N2 O by gas chromatography isotope ratio mass spectrometry (GC/IRMS). While applying this method to brackish samples, we noticed that the N and O isotope ratio measurements of NO2 - are highly sensitive to sample salinity and to the pH at which samples are preserved. We investigated the influence of sample salinity and sample preservation pH on the N and O isotope ratios of the N2 O produced from the reaction of NO2 - with azide. The N2 O isotope ratios were measured by GC/IRMS. Under the experimental reaction conditions, the conversion of NO2 - into N2 O was less complete in lower salinity solutions, resulting in respective N and O isotopic offsets of +2.5‰ and -14.0‰ compared with seawater solutions. Differences in salinity were also associated with differences in the fraction of O atoms exchanged between NO2 - and water during the reaction. Similarly, aqueous NO2 - samples preserved at elevated pH values resulted in the incomplete conversion of NO2 - into N2 O by azide, and consequent pH-dependent isotopic offsets, as well as differences in the fraction of O atoms exchanged with water. The addition of sodium chloride to the reaction matrix of samples and standards largely mitigated salinity-dependent isotopic offsets in the N2 O product, and nearly homogenized the fraction of O atom exchange among samples of different salinity. A test of the hypobromite-azide method to measure N isotope ratios of ammonium by conversion into NO2 - then N2 O revealed no influence of sample salinity on the N isotope ratios of the N2 O product. We outline recommendations to mitigate potential matrix effects among samples and standards, to improve the accuracy of N and O isotope ratios in NO2 - measured with the azide method.

Origin and depositional environments of source rocks and crude oils from Niger Delta Basin: Carbon isotopic evidence

ABSTRACT Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC12-nC33) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ13C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin.

An untargeted 13C isotopic evaluation approach for the discrimination of fermented food matrices at natural abundance: Application to vinegar

A non-destructive and comprehensive 13C isotopic evaluation approach based on 1H NMR spectroscopy was developed. The carbon isotope distribution (CID) of most of the components (S/N ≥ 1000) in food matrices were evaluated using frequency distribution of peak area ratios (PAR) of decoupling to non-13C-decoupling spectra at natural abundance. The approach was applied successfully to vinegar and it was found that the PAR of fermented vinegars is obviously narrower than that of the blended one and the one produced via chemically defined culture medium. Besides, the extra additives can also be evaluated by their characteristic PAR values. It was found that the sugars are the most commonly added components into the blended vinegars. The results obtained from the developed approach show good validity (baseline effect, RSD < 0.1%) and internal reproducibility (RSD < 0.1%). Practicability of the method is confirmed by gas chromatography-isotope ratio mass spectrometry (GC-IRMS) detection method. The results imply that the proposed approach could be used not only for the discrimination but also for the primary authentication of the blended components in the fermented food matrices.

Determination of δ13C of Trace Hydrocarbons in Natural Gas Using Syringe Solid Phase Extraction (SSPE) Coupled with Gas Chromatography/Isotope Ratio Mass Spectrometry (GC/IRMS)

Sample preparation technique, for the analysis of δ13C ratios in oil and gas samples, has gradually been recognized as one of the most crucial steps of the whole analytical process. In this study, a new convenient method, syringe solid phase extraction (SSPE), was proposed for measuring δ13C in natural gas samples. Based on conditional experiments of temperature and time, SSPE fitted with activated carbon adsorbent was applied with a gas chromatography/isotope ratio mass spectrometry (GC/IRMS) system for trace carbon isotope analysis. The results showed that isotopic fractionation was not clearly observed during the adsorption and desorption process, and the δ13C ratios measured by SSPE-GC/IRMS were in good agreement with the known δ13C ratios of CH4~C5H12 measured by GC/IRMS with the accuracy all within ±0.48‰. A natural gas sample was applied to verify the efficiency of this new method, and the obtained results confirmed that SSPE-GC/IRMS is a reliable technique characterized with simplicity, efficiency, and reliability.

Toward Improved Accuracy in Chlorine Isotope Analysis: Synthesis Routes for In-House Standards and Characterization via Complementary Mass Spectrometry Methods.

Increasing applications of compound-specific chlorine isotope analysis (CSIA) emphasize the need for chlorine isotope standards that bracket a wider range of isotope values in order to ensure accurate results. With one exception (USGS38), however, all international chlorine isotope reference materials (chloride and perchlorate salts) fall within the narrow range of one per mille. Furthermore, compound-specific working standards are required for chlorine CSIA but are not available for most organic substances. We took advantage of isotope effects in chemical dehalogenation reactions to generate (i) silver chloride (CT16) depleted in 37Cl/35Cl and (ii) compound-specific standards of the herbicides acetochlor and S-metolachlor (Aceto2, Metola2) enriched in 37Cl/35Cl. Calibration against the international reference standards USGS38 (-87.90 ‰) and ISL-354 (+0.05 ‰) by complementary methods (gas chromatography-isotope ratio mass spectrometry, GC-IRMS, versus gas chromatography-multicollector inductively coupled plasma mass spectrometry, GC-MC-ICPMS) gave a consensus value of δ37ClCT16 = -26.82 ± 0.18 ‰. Preliminary GC-MC-ICPMS characterization of commercial Aceto1 and Metola1 versus Aceto2 and Metola2 resulted in tentative values of δ37ClAceto1 = 0.29 ± 0.29 ‰, δ37ClAceto2 = 18.54 ± 0.20 ‰, δ37ClMetola1 = -4.28 ± 0.17 ‰ and δ37ClMetola2 = 5.12 ± 0.27 ‰. The possibility to generate chlorine isotope in-house standards with pronounced shifts in isotope values offers a much-needed basis for accurate chlorine CSIA.

Molecular and isotopic analyses on prehistoric pottery from the Virués-Martínez cave (Granada, Spain)

The analysis of the organic residues in archaeological pottery usually involves the use chromatography and mass spectrometry techniques. The identification of organic compounds processed in archaeological vessels, which generally degrade over archaeological timescales, provides insights about their origin and uses of the vessels. This paper provides an advance of archaeometric characterization of the organic residues in seventeen pottery vessels from the end of the 4th millennium BCE found in the Virués-Martínez cave (Granada, Spain), using gas chromatography–mass spectrometry (GC–MS), gas chromatography-isotope ratio mass spectrometry (GC-C-IRMS), and ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). To our knowledge this is the first study on the use of UPLC-HRMS on archaeological residues. Despite the fact that the identification of plant remains continues to be elusive, this study demonstrates the potential usefulness of UPLC-HRMS technique to study the polar fraction of plant residues, thus allowing us to formulate more specific hypotheses about the vegetal compounds that have survived in association with the pottery vessels (erucamide, matricarin, piptamine, piceatannol). Our results indicate that the occupants of the cave used the vessels to process plant materials and also degraded animal fats (ruminant fat) and it is very likely that the vessels were used for a variety of purposes, with accumulation of by-products over time, and were not made exclusively for funerary practices. The δ13C values C16:0 and C18:0 fatty acids obtained open a debate on the consumption of dairy compounds in the Iberian Peninsula during the end of the Neolithic and beginning of the Copper Age.

Compound‐specific stable carbon isotope analysis of hexabromocyclododecane diastereoisomers using gas chromatography/isotope ratio mass spectrometry

Compound-specific stable isotope analysis (CSIA) is a powerful tool for the source apportionment and characterization of environmental transformation processes, especially for new emerging contaminants. In this study, we have developed an effective method for determination of the stable carbon isotope ratios of hexabromocyclododecane diastereoisomers. Three diastereoisomers of hexabromocyclododecane (HBCD), α-, β-, and γ-HBCD, were separated on a preparative high-performance liquid chromatography (HPLC) system. Their carbon isotope ratios were determined using gas chromatography/isotope ratio mass spectrometry (GC/IRMS), and compared with data obtained by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS). α-, β-, and γ-HBCD were well separated by the preparative HPLC system. Method validation results indicated excellent precision and reproducibility. For a series of injection volumes (0.5 to 3 μL), the average carbon isotope ratios for α-HBCD, β-HBCD, and γ-HBCD were -26.42‰, -26.88‰, and -26.43‰, respectively, and their deviations from those of the HBCD standard (-26.52‰) were all lower than the analytical uncertainty of 0.5‰. Relative standard deviations of intra-day and inter-day injections of HBCD were in the ranges 0.35-0.64% and 0.37-0.76%, respectively. Comparison with EA/IRMS further verified the accuracy of the HBCD stable carbon isotope ratio measured by GC/IRMS. This work offers a novel approach to separate and concentrate the three major isomers of HBCD and to determine their stable carbon isotope ratios. This permits analysis of their carbon isotope ratios in environmental samples in order to elucidate the sources and abiotic or biological transformation processes of HBCD in the environment.

Biodegradation and photooxidation of phenolic compounds in soil—A compound-specific stable isotope approach

Phenolic compounds occur in a variety of plants and can be used as model compounds for investigating the fate of organic wastewater, lignin, or soil organic matter in the environment. The aim of this study was to better understand and differentiate mechanisms associated with photo- and biodegradation of tyrosol, vanillin, vanillic acid, and coumaric acid in soil. In a 29 d incubation experiment, soil spiked with these phenolic compounds was either subjected to UV irradiation under sterile conditions or to the native soil microbial community in the dark. Changes in the isotopic composition (δ13C) of phenolic compounds were determined by gas chromatography–isotope ratio mass spectrometry and complemented by concentration measurements. Phospholipid-derived fatty acid and ergosterol biomarkers together with soil water repellency measurements provided information on soil microbial and physical properties. Biodegradation followed pseudo-first-order dissipation kinetics, enriched remaining phenolic compounds in 13C, and was associated with increased fungal rather than bacterial biomarkers. Growing mycelia rendered the soil slightly water repellent. High sample variation limited the reliable estimation of apparent kinetic isotope effects (AKIEs) to tyrosol. The AKIE of tyrosol biodegradation was 1.007 ± 0.002. Photooxidation kinetics were of pseudo-zero- or first-order with an AKIE of 1.02 ± 0.01 for tyrosol, suggesting a hydroxyl-radical mediated degradation process. Further research needs to address δ13C variation among sample replicates potentially originating from heterogeneous reaction spaces in soil. Here, nuclear magnetic resonance or nanoscopic imaging could help to better understand the distribution of organic compounds and their transformation in the soil matrix.

Characterization of a novel marine origin aerobic nitrifying–denitrifying bacterium isolated from shrimp culture ponds

A novel marine origin Bacillus subtilis strain H1 isolated from a shrimp culture pond effectively removed NH₄⁺‐N, NO2-‐N and NO3-‐N, with a maximum ammonium, nitrite and nitrate removal rate of 2.35 mg NH₄⁺‐N L⁻¹ hr⁻¹ per OD, 9.64 mg NO2-‐N L⁻¹ hr⁻¹ per OD and 0.75 mg NO3-‐N L⁻¹ hr⁻¹ respectively. The gas chromatography–isotope ratio mass spectrometry results indicated that N₂O was emitted when ¹⁵NH₄Cl, Na¹⁵NO₂ or Na¹⁵NO₃ was used. Additionally, N₂ was also produced when Na¹⁵NO₂ was used. Single‐factor experiments suggested that the optimal conditions for NH₄⁺‐N and NO2-‐N removal were glucose as a carbon source, C/N 15, initial pH 7.5, 30 g/L NaCl, 28°C and a shaking speed of 160 rpm. Orthogonal tests showed that the optimal conditions for NH₄⁺‐N removal were C/N 15, pH 9, 10 g/L NaCl and shaking speed 160 rpm when ammonium chloride was used as the substrate. The optimal conditions for NO2-‐N removal were C/N 10, pH 6, 10 g/L NaCl and a shaking speed of 160 rpm when sodium nitrite was used as the substrate. In summary, B. subtilis strain H1 had highly efficient aerobic nitrifying–denitrifying ability and high adaptability, suggesting that it is potentially valuable to marine aquaculture.

Effects of chemical preservation on bulk and amino acid isotope ratios of zooplankton, fish, and squid tissues

It is imperative to understand how chemical preservation alters tissue isotopic compositions before using historical samples in ecological studies. Specifically, although compound-specific isotope analysis of amino acids (CSIA-AA) is becoming a widely used tool, there is little information on how preservation techniques affect amino acid δ15 N values. We evaluated the effects of chemical preservatives on bulk tissue δ13 C and δ15 N and amino acid δ15 N values, measured by gas chromatography/isotope ratio mass spectrometry (GC/IRMS), of (a) tuna (Thunnus albacares) and squid (Dosidicus gigas) muscle tissues that were fixed in formaldehyde and stored in ethanol for 2 years and (b) two copepod species, Calanus pacificus and Eucalanus californicus, which were preserved in formaldehyde for 24-25 years. Tissues in formaldehyde-ethanol had higher bulk δ15 N values (+1.4, D. gigas; +1.6‰, T. albacares), higher δ13 C values for D. gigas (+0.5‰), and lower δ13 C values for T. albacares (-0.8‰) than frozen samples. The bulk δ15 N values from copepods were not different those from frozen samples, although the δ13 C values from both species were lower (-1.0‰ for E. californicus and -2.2‰ for C. pacificus) than those from frozen samples. The mean amino acid δ15 N values from chemically preserved tissues were largely within 1‰ of those of frozen tissues, but the phenylalanine δ15 N values were altered to a larger extent (range: 0.5-4.5‰). The effects of preservation on bulk δ13 C values were variable, where the direction and magnitude of change varied among taxa. The changes in bulk δ15 N values associated with chemical preservation were mostly minimal, suggesting that storage in formaldehyde or ethanol will not affect the interpretation of δ15 N values used in ecological studies. The preservation effects on amino acid δ15 N values were also mostly minimal, mirroring bulk δ15 N trends, which is promising for future CSIA-AA studies of archived specimens. However, there were substantial differences in phenylalanine and valine δ15 N values, which we speculate resulted from interference in the chromatographic resolution of unknown compounds rather than alteration of tissue isotopic composition due to chemical preservation.

Microbial degradation of four dispersed crude oils by Rhodococcus sp. evaluated using carbon stable isotope analysis

AbstractBACKGROUNDThe high frequency and wide distribution of oil spills pose serious threats to the marine environmental ecosystem and human health. Microbial degradation is considered to be the most applicable means to process oil spills. Carbon isotope fractionation was employed as a crucial tool for evaluating the biodegradation of four crude oils by Rhodococcus sp. with Corexit 9500A as oil dispersant.RESULTSFollowing biodegradation, carbon isotope fractionation of n‐alkanes in four dispersed crude oil samples was measured by gas chromatography–isotope ratio mass spectrometry. A relationship between the carbon isotope ratios and residual concentrations of n‐alkanes was established based upon the Rayleigh equation, with a correlation coefficient, R2, ranging from 0.67 to 0.83. The carbon isotope enrichment factors for n‐alkanes of the four crude oil samples tended to be 0.04–0.25‰ in the residuals. The biodegradation level of n‐alkanes calculated from the Rayleigh equation agreed with the biodegradation results analyzed by gas chromatography–mass spectrometry.CONCLUSIONSThe degree of microbial degradation was positively correlated to the carbon isotope fractionation in n‐alkanes. Compound‐specific stable isotope analysis is capable of quantifying the biodegradation level of crude oil or oil spills. © 2019 Society of Chemical Industry

C and H stable isotope ratio analysis using solid-phase microextraction and gas chromatography-isotope ratio mass spectrometry for vanillin authentication

It is possible to distinguish precious vanillin from Vanilla species (planifolia or tahitensis) from much less expensive synthetic and nature-identical vanillin on the basis of the stable isotope ratios of H and C (2H/1H, 13C/12C). Analysis is usually performed using GC-IRMS (Gas Chromatography - Isotope Ratio Mass Spectrometry) after solvent extraction of vanillin from the sample. Recently, head-space solid-phase microextraction (HS-SPME) has been proposed as an alternative for determining 13C/12C.The aim of this study was to develop a method to analyse 2H/1H in vanillin using SPME-GC-IRMS for the first time, by testing different operating conditions and comparing the results with those obtained after solvent extraction. The ultimate scope was to develop a quick, robust and effective method to measure 2H/1H and 13C/12C in vanillin to assess the authenticity of labelling.Almost 50 authentic samples from vanilla pods, nature-identical (ex) and synthetic vanillin and 4 commercial food products were taken into account. All the samples were subjected to HS-SPME-GC-IRMS analysis and most of them to GC-IRMS analysis after solvent extraction of vanillin.The SPME method developed for 2H/1H analysis guarantees the absence of isotopic fractionation, repeatability and reproducibility standard deviation of below 7‰ and savings in terms of time (from 30 to 5 min) and solvent.HS-SPME GC-IRMS analysis of δ2H and δ13C can be proposed as a rapid and robust method to discriminate different types of vanillin and assess the authenticity of natural vanillin, also contained in food matrices.

Methyl sulfates as methoxy isotopic reference materials for δ13 C and δ2 H measurements.

Stable hydrogen and carbon isotope ratios of methoxy groups (OCH3 ) of plant organic matter have many potential applications in biogeochemical, atmospheric and food research. So far, most of the analyses of plant methoxy groups by isotope ratio mass spectrometry have employed liquid iodomethane (CH3 I) as the reference material to normalise stable isotope measurements of these moieties to isotope-δ scales. However, comparisons of measurements of stable hydrogen and carbon isotopes of plant methoxy groups are still hindered by the lack of suitable reference materials. We have investigated two methyl sulfate salts (HUBG1 and HUBG2), which exclusively contain carbon and hydrogen from one methoxy group, for their suitability as methoxy reference materials. Firstly, the stable hydrogen and carbon isotope values of the bulk compounds were calibrated against international reference substances by high-temperature conversion- and elemental analyser isotope ratio mass spectrometry (HTC- and EA-IRMS). In a second step these values were compared with values obtained by measurements using gas chromatography/isotope ratio mass spectrometry (GC/IRMS) where prior to analysis the methoxy groups were converted into gaseous iodomethane. The 2 H- and 13 C isotopic abundances of HUBG1 measured by HTC- and EA-IRMS and expressed as δ-values on the usual international scales are -144.5 ± 1.2 mUr (n = 30) and -50.31 ± 0.16 mUr (n = 14), respectively. For HUBG2 we obtained -102.0 ± 1.3 mUr (n = 32) and +1.60 ± 0.12 mUr (n = 16). Furthermore, the values obtained by GC/IRMS were in good agreement with the HTC- and EA-IRMS values. We suggest that both methyl sulfates are suitable reference materials for normalisation of isotope measurements of carbon of plant methoxy groups to isotope-δ scales and for inter-laboratory calibration. For stable hydrogen isotope measurements, we suggest that in addition to HUBG1 and HUBG2 additional reference materials are required to cover the full range of plant methoxy groups reported so far.

13C- and 15N-Isotope Analysis of Desphenylchloridazon by Liquid Chromatography-Isotope-Ratio Mass Spectrometry and Derivatization Gas Chromatography-Isotope-Ratio Mass Spectrometry.

The widespread application of herbicides impacts surface water and groundwater. Metabolites (e.g., desphenylchloridazon from chloridazon) may be persistent and even more polar than the parent herbicide, which increases the risk of groundwater contamination. When parent herbicides are still applied, metabolites are constantly formed and may also be degraded. Evaluating their degradation on the basis of concentration measurements is, therefore, difficult. This study presents compound-specific stable-isotope analysis (CSIA) of nitrogen- and carbon-isotope ratios at natural abundances as an alternative analytical approach to track the origin, formation, and degradation of desphenylchloridazon (DPC), the major degradation product of the herbicide chloridazon. Methods were developed and validated for carbon- and nitrogen-isotope analysis (δ13C and δ15N) of DPC by liquid chromatography-isotope-ratio mass spectrometry (LC-IRMS) and derivatization gas chromatography-IRMS (GC-IRMS), respectively. Injecting standards directly onto an Atlantis LC-column resulted in reproducible δ13C-isotope analysis (standard deviation <0.5‰) by LC-IRMS with a limit of precise analysis of 996 ng of DPC on-column. Accurate and reproducible δ15N analysis with a standard deviation of <0.4‰ was achieved by GC-IRMS after derivatization of >100 ng of DPC with 160-fold excess of (trimethylsilyl)diazomethane. Application of the method to environmental-seepage water indicated that newly formed DPC could be distinguished from "old" DPC by the different isotopic signatures of the two DPC sources.

Solid-phase extraction method for stable isotope analysis of pesticides from large volume environmental water samples.

Compound-specific isotope analysis (CSIA) is a valuable tool for assessing the fate of organic pollutants in the environment. However, the requirement of sufficient analyte mass for precise isotope ratio mass spectrometry combined with prevailing low environmental concentrations currently limits comprehensive applications to many micropollutants. Here, we evaluate the upscaling of solid-phase extraction (SPE) approaches for routine CSIA of herbicides. To cover a wide range of polarity, a SPE method with two sorbents (a hydrophobic hypercrosslinked sorbent and a hydrophilic sorbent) was developed. Extraction conditions, including the nature and volume of the elution solvent, the amount of sorbent and the solution pH, were optimized. Extractions of up to 10 L of agricultural drainage water (corresponding to up to 200 000-fold pre-concentration) were successfully performed for precise and sensitive carbon and nitrogen CSIA of the target herbicides atrazine, acetochlor, metolachlor and chloridazon, and metabolites desethylatrazine, desphenylchloridazon and 2,6-dichlorobenzamide in the sub-μg L-1-range. 13C/12C and 15N/14N ratios were measured by gas chromatography-isotope ratio mass spectrometry (GC/IRMS), except for desphenylchloridazon, for which liquid chromatography (LC/IRMS) and derivatization-GC/IRMS were used, respectively. The method validated in this study is an important step towards analyzing isotope ratios of pesticide mixtures in aquatic systems and holds great potential for multi-element CSIA applications to trace pesticide degradation in complex environments.

Method for Analyzing the Molecular and Carbon Isotope Composition of Volatile Hydrocarbons (C1-C9) in Natural Gas.

Solid-phase microextraction (SPME) coupled with gas chromatography-isotope ratio mass spectrometry (GC-IRMS) has already been applied to collect and identify volatile light hydrocarbons in oil and source rocks. However, this technology has not yet been used to analyze volatile light hydrocarbons in dry gas (natural gas with C1/C2+ > 95%). In this study, we developed a method to measure the molecular and carbon isotope composition of natural gas using divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber. This fiber proved to be suitable for extracting C1–C9 hydrocarbons from natural gas without inducing carbon isotopic fractionation. Notably, the extraction coefficients of the analytes were not the same but rather increased with the increasing carbon number of the hydrocarbons. Nevertheless, we successfully identified 24 hydrocarbons from the in-lab standard natural gas, while also obtaining the carbon isotope composition of C1 to C9 hydrocarbons with satisfying repeatability. The relative standard deviation (RSD) of the molecular composition data was in the range of 0.06–0.74%, with the RSDs of the carbon isotope composition data not exceeding 1‰. Finally, seven natural gas samples, collected from different sedimentary basins, were successfully analyzed and the stable carbon isotope compositions of C1–C9 hydrocarbons present in these were determined through this method. Overall, the new approach provides a simple but useful technique to obtain more geochemical information about the source and evolution of natural gas.

A novel method to measure the 13C composition of intact bacteriohopanepolyols

We present a novel method to measure the 13C/12C isotope ratio (reported as δ13C) of individual, intact bacteriohopanepolyols (BHPs) using semi-preparative ultrahigh pressure liquid chromatography (UPLC) followed by high temperature gas chromatography–isotope ratio mass spectrometry (HT-GC–IRMS). The method is reproducible, as indicated by the precision of δ13C values for bacteriohopanetetrol (BHT) extracted from R. palustris biomass and analyzed across an order-of-magnitude range of IRMS peak areas (δ13C = −33.4 ± 0.6‰ VPDB, n = 94, ±1σ). To show that this method successfully separates individual BHPs from complex environmental matrices, we report δ13C values for BHT and the BHT stereoisomer (BHT-II) from a ca. 2.9 Ma, organic-rich Mediterranean Sea sediment sample. These analyses suggest that intact BHP δ13C measurements can greatly improve the interpretation of environmental signals by alleviating the need for side-chain cleavage which reduces BHP source-specificity.

Alcohol consumption or contamination: A preliminary study on the determination of the ethanol origin by stable carbon isotope analysis

The origin of ethanol detected in bio-samples whether it be from the consumption of alcoholic beverages or contamination with disinfectants has been questioned in court cases in China recently. The stable carbon isotope naturally occurs in carbon-containing compounds and can help determine the origin of the compound in question. In total, 42 types of beers and 11 types of disinfectants were analyzed by gas chromatography-isotope ratio mass spectrometry. Consumption and contamination experiments were carried out with 6 volunteers. The δ13C values of ethanol ranged from −29.51‰ to −18.36‰ for the beer samples, which reflected the botanical features of C3 plants or mixtures of C3 and C4 plants. The δ13C values of ethanol ranged from −17.7‰ to −14.4‰ for disinfectants, which reflected the different origins of ethanol in disinfectants from those in beer. The δ13C value did not change in vivo after being consumed within the time limit used in this study. These characteristics of the δ13C values will facilitate to interpret whether the ethanol detected in bio-samples originated from consumption or contamination.

Molecularly Imprinted Polymers for Compound-Specific Isotope Analysis of Polar Organic Micropollutants in Aquatic Environments.

Compound-specific isotope analysis (CSIA) of polar organic micropollutants in environmental waters requires a processing of large sample volumes to obtain the required analyte masses for analysis by gas chromatography/isotope-ratio mass spectrometry (GC/IRMS). However, the accumulation of organic matter of unknown isotopic composition in standard enrichment procedures currently compromises the accurate determination of isotope ratios. We explored the use of molecularly imprinted polymers (MIPs) for selective analyte enrichment for 13C/12C and 15N/14N ratio measurements by GC/IRMS using 1 H-benzotriazole, a typical corrosion inhibitor in dishwashing detergents, as example of a widely detected polar organic micropollutant. We developed procedures for the treatment of >10 L of water samples, in which custom-made MIPs enabled the selective cleanup of enriched analytes in organic solvents obtained through conventional solid-phase extractions. Hydrogen bonding interactions between the triazole moiety of 1 H-benzotriazole, and the MIP were responsible for selective interactions through an assessment of interaction enthalpies and 15N isotope effects. The procedure was applied successfully without causing isotope fractionation to river water samples, as well as in- and effluents of wastewater treatment plants containing μg/L concentrations of 1 H-benzotriazole and dissolved organic carbon (DOC) loads of up to 28 mg C/L. MIP-based treatments offer new perspectives for CSIA of organic micropollutants through the reduction of the DOC-to-micropollutant ratios.

Determination of the Origin of 19-Norandrosterone in Urine by Gas Chromatography–Isotope-Ratio Mass Spectrometry for Doping Control

The most difficult task in antidoping control is the identification of compounds whose origin can be either endogenous or exogenous. This paper presents a procedure for determining the origin of 19-norandrosterone based on the extraction of target components from urine, their multistage purification by semipreparative HPLC, acetylation, and quantification by gas chromatography–isotope-ratio mass spectrometry and gas chromatography–mass spectrometry. Effects of isotope fractionation were not observed in sample preparation. The degree of extraction of the target analytes was 80 ± 5%.