Gas Chromatography-isotope Ratio Mass Research Articles

The organic geochemistry of crude oil in the Saltpond Basin (Ghana): Organic source input, depositional environment, and thermal maturity

The Saltpond Basin, situated within the South Atlantic margin of Ghana, is a significant area for petroleum exploration but has received relatively limited research attention. Previous studies have examined source rock composition, but data on crude oil organic chemistry are lacking, hindering understanding of the basin’s petroleum system and evolution. To address this gap, we analyzed biomarkers and stable carbon-isotope ratios in Saltpond Basin crude oil using gas chromatography–mass spectrometry and gas chromatography–isotope ratio mass spectrometry to elucidate organic matter source, depositional environment, and thermal maturity. Findings were compared with oils from the West African segment of the South Atlantic margin, namely the Tano Basin and the Niger Delta Basin, to identify potential correlations and gain insights into regional variations. Molecular and isotopic results unveiled a significant prevalence of organic matter derived from lower marine organisms. Patterns of organic matter deposition and preservation in Saltpond oil samples suggested a suboxic marine transitional environment, contradicting conventional understanding of terrestrial dominance in such settings. Moreover, the potential for degradation processes to obscure differentiation between terrestrial and marine organic matter origins underscores the complex nature of organic matter dynamics in transitional marine environments. Analysis of molecular thermal maturity indices suggested Saltpond oils were expelled from source rocks exhibiting thermal maturity at the early maturity stage. Correlation analysis unveiled genetic disparities among crude oils sourced from the Saltpond Basin and those from the Tano and Niger Delta Basin, primarily due to variations in source input and depositional environment conditions. Saltpond oil exhibits lower terrestrial organic input than Tano Basin’s crude oils, which also have less terrestrial input than Niger Delta Basin crude oils. Additionally, its paleodepositional environment notably differs from oils in the Tano Basin (anoxic transitional marine-lacustrine settings) and the Niger Delta Basin (suboxic–oxic terrigenous deltaic or marine or lacustrine environments). Thermal maturity range of Saltpond oil is comparable to oils in the Tano Basin but lower than oils in the Niger Delta Basin. These findings provide valuable insights into petroleum generation history and unique organic geochemical characteristics within the Saltpond Basin, essential for exploration, production, and environmental management efforts in the region. Furthermore, correlation studies provide evidence that distinct biological, geological, and paleoenvironmental conditions shaped various oil types in the West African segment of the South Atlantic margin.

Single-species dinoflagellate cyst carbon isotope fractionation in core-top sediments: environmental controls, CO2 dependency and proxy potential

Abstract. Sedimentary bulk organic matter and various molecular organic components exhibit strong CO2-dependent carbon isotope fractionation relative to dissolved inorganic carbon sources. This fractionation (εp) has been employed as a proxy for paleo-pCO2. Yet, culture experiments indicate that CO2-dependent εp is highly specific at genus and even species level, potentially hampering the use of bulk organic matter and non-species-specific organic compounds. In recent years, significant progress has been made towards a CO2 proxy using controlled growth experiments with dinoflagellate species, also showing highly species-specific εp values. These values were, however, based on motile specimens, and it remains unknown whether these relations also hold for the organic-walled resting cysts (dinocysts) produced by these dinoflagellate species in their natural environment. We here analyze dinocysts isolated from core tops from the Atlantic Ocean and Mediterranean Sea, representing several species (Spiniferites elongatus, S. (cf.) ramosus, S. mirabilis, Operculodinium centrocarpum sensu Wall and Dale (1966) (hereafter referred to as O. centrocarpum) and Impagidinium aculeatum) using laser ablation–nano-combustion–gas-chromatography–isotope ratio mass spectrometry (LA/nC/GC-IRMS). We find that the dinocysts produced in the natural environment are all appreciably more 13C-depleted compared to the cultured motile dinoflagellate cells, implying higher overall εp values, and, moreover, exhibit large isotope variability. Where several species could be analyzed from a single location, we often record significant differences in isotopic variance and offsets in mean δ13C values between species, highlighting the importance of single-species carbon isotope analyses. The most geographically expanded dataset, based on O. centrocarpum, shows that εp correlates significantly with various environmental parameters. Importantly, O. centrocarpum shows a CO2-dependent εp above ∼ 240 µatm pCO2. Similar to other marine autotrophs, relative insensitivity at low pCO2 is in line with active carbon-concentrating mechanisms at low pCO2, although we here cannot fully exclude that we partly underestimated εp sensitivity at low pCO2 values due to the relatively sparse sampling in that range. Finally, we use the relation between εp and pCO2 in O. centrocarpum to propose a first pCO2 proxy based on a single dinocyst species.

Determination of intermolecular and intramolecular isotopic compositions of low-abundance gaseous hydrocarbons using an online hydrocarbon gas concentration method

The stable isotopic composition of natural gas can be used to identify its origin and source. However, low concentrations of gaseous hydrocarbons in high-mature natural and shale gases hinder accurate determination of their compound- and position-specific isotopic compositions. In this study, an online C2+ hydrocarbon gas concentration system combined with gas chromatography–isotope ratio mass spectrometry (GC–IRMS) or gas chromatography–pyrolysis–gas chromatography–isotope ratio mass spectrometry (GC–Py–GC–IRMS) was developed to determine compound- and position-specific isotopic compositions of low-abundance gaseous hydrocarbons. The lower limit of the gas concentration required for isotope ratio determination using the online concentration system is 0.001% (0.003%) for compound-specific carbon (hydrogen) isotopes and 0.005% for position-specific carbon isotopes and is thus applicable to most natural gas samples. The online concentration technique does not cause significant isotopic fractionation effects, and the combination with GC–IRMS and GC–Py–GC–IRMS can accurately and precisely determine the compound-specific δ13C and δD values of low-content C2+ gaseous hydrocarbons and the position-specific δ13C values (δ13Ca, δ13Cb, and SP values) of propane in low-content propane samples, respectively. The application of our method to two natural gas samples from the Ordos and Sichuan basins further confirms that the online concentration method allows simple and rapid determination of the compound- and position-specific isotopic compositions of low-abundance gaseous hydrocarbons.

Source apportionment and evolution of N-containing aerosols at a rural cloud forest in Taiwan by isotope analysis

Abstract. Ammonium and nitrate are major N-containing aerosol components. The deposition of N-containing aerosols has impacts on regional ecology and the biogeochemical cycle. In this study, aerosols in a rural cloud forest (Xitou in Taiwan) were studied using 15N and 18O isotope analysis to assess the sources and formation pathways of the local N-containing aerosols linking to a metropolitan. Aerosol samples of different size ranges were collected using a micro-orifice uniform deposit impactor (MOUDI) on a half-day basis in December 2018. The chemical functional groups were analyzed using a Fourier-transform infrared spectroscopy with attenuated total reflection (FTIR-ATR) technique, while the isotope analysis was performed using a gas chromatography–isotope ratio mass spectrometer (GC–IRMS). The average measured aerosol concentration (PM10) was 0.98 (ranging from 0.15 to 3.31) and 0.25 (ranging from 0.00 to 1.51) µg m−3 for NH4+ and NO3-, respectively. In general, a higher concentration than nighttime was observed during the daytime by a factor of 1.5–6, likely due to the transportation of pollutants from upper-stream urban and industrial regions through the local sea breeze combined with valley wind. The presence of fog can further elevate the concentration by a factor of 2–3, resulting from the stronger inversion and lower boundary layer height. The higher NH4+ concentration in fine particles under foggy conditions corresponds to submicron-sized NO3- formation via aqueous-phase dissolution with NH4+ neutralization. Furthermore, the higher RH during fog events shifted the mass distribution of aerosol functional groups to a larger mode size. By comparing the δ15N value directly or through the analysis using a statistical isotope mixing model, MixSIAR, NH4+ probably originated from the industries, coal-fired power plants (CFPPs), or fertilizer plants, while NO3- might be contributed from the CFPP, industrial or urban sources. The overall δ18O of NO3- is +72.66 ‰ ± 3.42 ‰, similar to that in other winter Asian studies, suggesting the major formation pathway via O3 oxidation (δ18O=+72.5 ‰ to 101.67 ‰). However, a lower δ18O (<+67 ‰) for particles less than 0.56 µm during foggy daytime suggests the local contribution via the peroxyl radical oxidation before partitioning into aerosol phase under foggy conditions. Overall, the δ15N and δ18O distribution profiles as a function of particle size in the studied rural forest site reveal the evolution of aerosol composition from remote coastal regions with chemical processes along the transport process, which can be further affected by weather conditions such as fog events.

State-of-the-Art Analytical Approaches for Illicit Drug Profiling in Forensic Investigations.

In forensic chemistry, when investigating seized illicit drugs, the profiling or chemical fingerprinting of drugs is considered fundamental. This involves the identification, quantitation and categorization of drug samples into groups, providing investigative leads such as a common or different origin of seized samples. Further goals of drug profiling include the elucidation of synthetic pathways, identification of adulterants and impurities, as well as identification of a drug’s geographic origin, specifically for plant-derived exhibits. The aim of this state-of-art-review is to present the traditional and advanced analytical approaches commonly followed by forensic chemists worldwide for illicit drug profiling. We discussed numerous methodologies for the physical and chemical profiling of organic and inorganic impurities found in illicit drug. Applications of powerful spectroscopic and chromatographic tools for illicit drug profiling including isotope-Ratio mass spectrometry (IRMS), gas chromatography–mass spectrometry (GC-MS), gas chromatography–isotope ratio mass spectrometry (GC-IRMS), ultra-high-performance liquid chromatography (UHPLC), thin layer chromatography (TLC), liquid chromatography–mass spectrometry (LC-MS) and inductively coupled plasma-mass spectrometry (ICP-MS) were discussed. Altogether, the techniques covered in this paper to profile seized illicit drugs could aid forensic chemists in selecting and applying a suitable method to extract valuable profiling data.

Use of the Lipolysis Inhibitor Acipimox Fails to Modulate Chronic Muscle Protein Synthesis Rates or Attenuate the Loss of Muscle Mass in a Rodent Model of Severe Burns

ObjectiveMassive burns result in chronic lipolysis of adipose stores resulting in ectopic lipid accumulation. Given reports that hyperlipidemia and/or increased intramyocellular lipid accumulation is associated with impaired synthesis of muscle proteins, we hypothesized that administering the lipolysis inhibitor acipimox could protect muscle protein synthesis capacity in a rodent model of burns, thereby blunting the loss of muscle mass.MethodsSprague Dawley rats (4 groups, 16 animals per group, n = 64) were randomized to receive a scald burn (~ 60 % total body surface area; n=32) or sham procedure. Animals in each group were assigned to receive either vehicle (saline) or acipimox (50 mg/kg/day) daily by i.p. injection for 7 days. All animals received a bolus of deuterated water (10 ml/kg, i.p.) followed by supplementation in drinking water (2 %) to monitor habitual muscle protein synthesis rates (MPS). On day 7, animals were sacrificed, and tissues collected. MPS was calculated by measuring intracellular and bound deuterium enrichment of alanine via Gas Chromatography Isotope Ratio Mass Spectrometry.ResultsSevere burns resulted in significant body weight loss compared to the sham injury group (7 % vs 10 %; p < 0.001). However, acipimox administration did not prevent the loss of body weight. There was a trend for gastrocnemius and tibialis anterior muscle weights to be lower in burn animals (P = 0.058 and P=0.057, respectively). However, acipimox did not prevent the loss of muscle weight with burn injury. Neither burn injury nor acipimox administration impacted habitual MPS rates.ConclusionIn sharp contrast to what is observed in patients, severe burns do not alter habitual MPS rates in rats. Given evidence that rats still experience a loss of muscle mass in response to thermal injury, it suggests that the dominant mechanism by which muscle protein content declines in these animals is via enhanced muscle proteolysis. Acipimox appears to exert no beneficial impact on muscle protein homeostasis in burn injured rodents.

Stable Carbon Isotope Analysis of Hexachlorocyclohexanes by Liquid-Liquid Extraction Gas Chromatography Isotope Ratio Mass Spectrometry: Method Evaluation and Applications.

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid–liquid extraction method of HCHs in water. The results showed that there were negligible changes in the δ13C of HCHs after extraction, indicating that liquid–liquid extraction can be used as a pre-concentration method for the determination of δ13C of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the α-HCH oxidation by CaO2/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched δ13C in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (εC) of −1.90 ± 0.10‰ were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.

Stable isotopic signatures of methane from waste sources through atmospheric measurements

This study aimed to characterize the carbon isotopic signatures (δ13C-CH4) of several methane waste sources, predominantly in the UK, and during field campaigns in the Netherlands and Turkey. CH4 plumes emitted from waste sources were detected during mobile surveys using a cavity ring-down spectroscopy (CRDS) analyser. Air samples were collected in the plumes for subsequent isotope analysis by gas chromatography isotope ratio mass spectrometry (GC-IRMS) to characterize δ13C-CH4. The isotopic signatures were determined through a Keeling plot approach and the bivariate correlated errors and intrinsic scatter (BCES) fitting method. The δ13C-CH4 and δ2H-CH4 signatures were identified from biogas plants (−54.6 ± 5.6‰, n = 34; −314.4 ± 23‰ n = 3), landfills (−56.8 ± 2.3‰, n = 43; −268.2 ± 2.1‰, n = 2), sewage treatment plants (−51.6 ± 2.2‰, n = 15; −303.9 ± 22‰, n = 6), composting facilities (−54.7 ± 3.9‰, n = 6), a landfill leachate treatment plant (−57.1 ± 1.8‰, n = 2), one water treatment plant (−53.7 ± 0.1‰) and a waste recycling facility (−53.2 ± 0.2‰). The overall signature of 71 waste sources ranged from −64.4 to −44.3‰, with an average of −55.1 ± 4.1‰ (n = 102) for δ13C, −341 to −267‰, with an average of −300.3 ± 25‰ (n = 11) for δ2H, which can be distinguished from other source types in the UK such as gas leaks and ruminants. The study also demonstrates that δ2H-CH4 signatures, in addition to δ13C-CH4, can aid in better waste source apportionment and increase the granularity of isotope data required to improve regional modelling.

Position-specific carbon isotopic composition of thermogenic propane: Insights from pyrolysis experiments

Position-specific isotope analysis (PSIA) of propane provides novel insights into formation mechanisms and thermal maturity of natural gas. The evolution of thermogenic propane in natural gas was simulated with pyrolysis experiments using types I, IIA, III kerogen and an oil. PSIA of propane involved on-line pyrolysis with gas chromatography–isotope ratio mass spectrometry to explore evolution characteristics and fractionation mechanisms of propane position-specific δ13C values. Results indicate the formation of propane can be considered in three stages. Stage I (<1.3% EasyRo) involves propane production mainly from primary kerogen cracking, with its precursors having homogeneous isotopic distributions and with position-specific 13C variation patterns depending on the kerogen molecular structure. In Stage II (1.3% EasyRo to maturity of peak propane yield), propane is derived mainly from secondary cracking of bitumen/oil, resulting in 13C enrichment of terminal (δ13Ca) and central (δ13Cb) C atoms with maturity and a strong linear relationship between δ13Ca and δ13Cb. A suggested new pattern is explained by a Rayleigh model for the evolution of propane position-specific δ13C values in this stage. In Stage III (maturity greater than the peak propane yield), propane destruction mainly controls its amount and isotopic signature. Propane site-preference (SP) value (δ13Ca–δ13Cb) can be used to determine its formation mechanism and maturity, with positive and negative values respectively indicating primary kerogen cracking and secondary oil/bitumen cracking. Increasing maturity causes decreasing values. The application of propane PSIA to the Tarim Basin gas samples demonstrates its potential for determining the mechanism of formation and maturity of natural gas.

Determination of carbon isotopic composition of crocetane in sediments by heart-cutting two-dimensional gas chromatography–isotope ratio mass spectrometry

Compound-specific isotope analysis of crocetane in sediments can be used to determine its origin. However, the co-elution of crocetane with phytane and complex substrates hinders the accurate determination of its isotopic composition. A heart-cutting two-dimensional gas chromatography–isotope ratio mass spectrometry (2D-GC–IRMS) method was developed to determine δ13C values of crocetane. Full chromatographic separation of crocetane was achieved with a 30 m CycloSil-B chiral capillary first column and a 60 m Chiraldex B-pH capillary second column (two series-connected 30 m Chiraldex B-pH capillary columns). Analyses of standard mixtures confirmed that the new method has satisfactory accuracy (deviations from the authentic values <0.5‰) and precision (RSDs <5%) for carbon isotope analyses of crocetane and phytane. The application of the method to two sediment samples indicates that baseline resolution is achieved (R >1.5) for crocetane and phytane, with 13C-depleted crocetane (δ13C values of −119.5‰ and −111.5‰ in the two natural samples, respectively) being an indicator of anaerobic oxidation of methane in cold seep areas. The new 2D-GC–IRMS method allows simple and efficient determination of the compound-specific carbon isotopic compositions of crocetane.

An Improved and Rapid Preparation Method for Gas Chromatography Isotope Ratio Mass Spectrometry of Hopanes

An Improved and Rapid Preparation Method for Gas Chromatography Isotope Ratio Mass Spectrometry of Hopanes

Analysis of Carbon and Hydrogen Stable Isotope Ratios of Phenolic Compounds: Method Development and Biodegradation Applications

Phenolic compounds are priority water pollutants of both natural and anthropogenic origins. Distinguishing the sources and degradation pathways of phenolic compounds in the environment is essential for sustainable water management. In this study, we have developed and validated methods based on gas chromatography–isotope ratio mass spectrometry for analysis of hydrogen and carbon isotope ratios of phenol and cresols. For carbon stable isotope analysis, solid-phase extraction was applied, whereas liquid–liquid extraction, followed by derivatization with trifluoroacetic anhydride, was used for hydrogen stable isotope analysis. The methods were verified in biodegradation experiments using p-cresol and phenol as substrates. Methyl group oxidation of p-cresol by Pseudomonas pseudoalcaligenes and Aromatoleum aromaticum resulted in the strong hydrogen (−76 ± 2 and −103 ± 2 mUr, respectively) and varying carbon isotopic fractionation (−2.1 ± 0.1 and −1.0 ± 0.1 mUr, respectively), leading to distinguishable two-dimensional plots for hydrogen versus carbon isotope ratios, indicating slightly different enzymatic reactions. For anaerobic phenol degradation by Desulfosarcina cetonica, the absence of hydrogen isotopic fractionation indicates adenosine triphosphate-dependent carboxylation as the initial step of the biodegradation pathway. The methods developed in this study are useful to detect biological degradation of phenolic compounds in highly contaminated aqueous environmental systems.

Dose–Response Oxidation of Ingested Phytoglycogen during Exercise in Endurance-Trained Men

BackgroundPhytoglycogen (PHY; PhytoSpherix; Mirexus Biotechnologies), a highly branched polysaccharide extracted from sweet corn, has considerable potential for exercise oxidation due to its low viscosity in water, high water retention, and exceptional stability. ObjectivesUsing gas chromatography–isotope ratio mass spectrometry, we investigated dose–response oxidation of ingested PHY during prolonged, moderate-intensity exercise. MethodsThirteen men (≥1 y endurance-training experience, ≥6 d·wk−1, ∼1–1.5 h·d−1; age, 25.7 ± 5.5 y; mass, 79.3 ± 10.0 kg; V̇O2max, 59.9 ± 5.5 mL·kg−1·min−1; means ± SDs) cycled for 150 min (50% maximal watt output) while ingesting PHY concentrations of 0.0% (0.0 g·min−1), 3.6% (0.5 g·min−1), 7.2% (1.0 g·min−1), 10.8% (1.5 g·min−1), or 14.4% (2 g·min−1) in water (2100 mL) (n = 7–10/dose). Substrate oxidation was determined using stable-isotope methods and indirect calorimetry. ResultsPHY oxidation plateaued between 60 and 150 min of exercise and increased (P < 0.001) from 0.49 to 0.72 g·min−1 with 0.5- and 1.0-g·min−1 doses without further increases (0.76 and 0.73 g·min−1; P > 0.05) with 1.5 or 2 g·min−1. Peak PHY oxidation (0.84 ± 0.04 g·min−1) occurred in the final 30 min of exercise with 2 g·min−1. Exercise blood glucose was greater (5.1 mmol·L−1) with 1.0-, 1.5-, and 2-g·min−1 doses compared with that of 0.5 (4.7 mmol·L−1) or 0.0 g·min−1 (4.2 mmol·L−1) (P < 0.0001). Gastrointestinal distress was minimal except with 2 g·min−1 (P < 0.001). ConclusionsIn male endurance athletes, PHY oxidation plateaued at 0.72–0.76 g·min−1 during 150 min of cycling at 50% Wmax (peak oxidation of 0.84 g·min−1 occurred during the final 30 min). This trial was registered at clinicaltrials.gov as NCT02909881.

Compound-specific carbon isotope analysis of volatile organic compounds in complex soil extracts using purge and trap concentration coupled to heart-cutting two-dimensional gas chromatography–isotope ratio mass spectrometry

Compound-specific carbon isotope analysis (CSIA) is a powerful tool to track the origin and fate of organic subsurface contaminants including petroleum and chlorinated hydrocarbons and is typically applied to water samples. However, soil can form a significant contaminant reservoir. In soil samples, it can be challenging to recover sufficient amounts of volatile organic compounds (VOC) to perform CSIA. Soil samples often contain complex contaminant mixtures and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) is highly dependent on good chromatographic separation due to the conversion to a single analyte. To extend the applicability of CSIA to complex volatile organic compound mixtures in soil samples, and to recover sufficient amounts of target compounds for carbon CSIA, we compared two soil extraction solvents, tetraglyme (TGDE) and methanol, and developed a heart-cutting two-dimensional GC-GC-C-IRMS method. We used purge & trap concentration of solvent-water mixtures to increase the amount of analyte delivered to the column and thus lower method detection limits. We optimized purge & trap and chromatographic parameters for twelve target compounds, including one suffering from poor purge efficiency. By using a 30 m thick-film non-polar column in the first and a 15 m polar column in the second dimension, we achieved good chromatographic separation for the target compounds in difficult matrices and high accuracy (trueness and precision) for carbon isotopic analysis. Tetraglyme extraction was shown to offer advantages over methanol for purge & trap concentration, leading to lower target compound method detection limits for CSIA of soil samples. The applicability of the developed method was demonstrated for a case study on soil extracts from a former manufacturing facility. Our approach extends the applicability of CSIA to an important matrix that often controls the long-term fate of contaminants in the subsurface.

Combining catalytic hydropyrolysis and GC–IRMS to reconstruct the geochemical characteristics of source rocks in the Baiyun deep-water area of the Pearl River Mouth Basin, China

Petroleum exploration has found that the Baiyun deep-water area of the Pearl River Mouth Basin (PRMB), China, holds abundant oil and gas resources with great prospects. However, conditions restricting offshore drilling in this area present significant challenges to the investigation of source rocks. Core samples are lacking, and any cuttings obtained are generally highly contaminated by drilling mud. As a result, the identification and evaluation of hydrocarbon sources in deep-water areas would be greatly aided by new techniques capable of reliably obtaining the geochemical characteristics of potential source rocks. This study combines catalytic hydropyrolysis (HyPy) and gas chromatography–isotope ratio mass spectrometry (GC–IRMS) to determine the carbon isotope composition of individual n-alkanes covalently bound in kerogen framework. Furthermore, it reconstructs the source and depositional environment of sedimentary organic matter in potential source rocks from the Baiyun deep-water area of the PRMB. The results indicate that the optimized degassing (i.e., degassing under high vacuum at 250 °C for 24 h) can effectively eliminate hydrocarbon contaminants in the kerogen. Determination by GC–IRMS of bound n-alkanes released from the degassed kerogen by HyPy can provide the molecular carbon isotope characteristics of the original organic matter in cuttings contaminated by drilling mud. The results improve the understanding of potential hydrocarbon source rocks in the Baiyun deep-water area of the PRMB.

Comprehensive Isotope Ratio Metabolomics: Gas chromatography Isotope Ratio Mass Spectrometry of urinary metabolites and exhaled breath

We have developed an analytical procedure to measure the carbon isotopic composition of multiple compounds even when there is a partial overlap in the chromatographic profiles and applied this procedure to measure the carbon isotopic composition of different metabolites in human urine and exhaled breath. Method development and validation was performed with CRM IAEA-600 caffeine after calibration of the reference CO2 gas using a mixture of certified undecane, pentadecane and eicosane δ(13C) standards. The alternative data treatment procedure included the correction of time-lag between Faraday cup amplifiers (44 ms at mass 45 and -160 ms at mass 46), the calculation and correction of chromatographic isotope effects on each peak (isotope shifts) and the calculation of the isotope ratio for each compound using the linear regression slope procedure with data only at the top of the chromatographic peak. In that way, partial chromatographic overlap between different metabolites can be tolerated (resolution equal or higher than 1). The reproducibility (SD) of the carbon isotope composition of 93 metabolites in human urine (n = 8) from one volunteer was typically better than 0.5 δ(13C) (range 0.1–2.0 δ(13C), median 0.4 δ(13C)). The method was applied to follow the carbon isotope composition of different metabolites in human urine and exhaled breath after the oral administration of 100 mg of universally labelled 13C-glucose to another human volunteer. It was demonstrated that isotopically labelled compounds could be detected in both samples even 2 h after administration. So, the developed methodology can be applied to multiple types of samples containing a large number of partially overlapping analytes including environmental applications, anti-doping control or metabolomics studies, including the use of enriched isotope tracers.

Compound specific isotope analysis (CSIA) of phthalates and non-targeted isotope analysis (NTIA) of SPE-extractable organic carbon in dilute aquatic environments

Isotope ratio analysis of total organic carbon (TOC) is well-established for the study of rivers, lakes, and oceans. Similarly, these aquatic systems are routinely surveyed to quantify natural and anthropogenic organic compounds and pollutants, including such things as pharmaceuticals, illicit drugs, and phthalates. We merged these two approaches to demonstrate compound specific isotope analysis (CSIA) on four phthalate esters and non-targeted isotope analysis (NTIA) on a gas chromatography isotope ratio mass spectrometry (GC-IRMS) platform. Water from the Rivers Foss and Trent and a waste-water treatment plant (WWTP) effluent was sampled, followed by solid phase extraction (SPE) and GC-IRMS. Di–ethyl hexyl phthalate (DEHP) concentration in the effluent was 0.20 µg/L while it was 0.22 µg/L and 0.14 µg/L in the Trent and Foss Rivers, respectively. CSIA δ 13C values for selected phthalates measured in river and effluent samples ranged from −24.3‰ to −28.8‰. NTIA returned over 100 compounds which in aggregate aligned well with published values for isotope analysis of TOC. NTIA demonstrated that the volatile SPE-extractable fraction of TOC has high heterogeneity with δ 13C from −26.8‰ to −44.3‰ for matched compounds in both rivers. GC-IRMS can be applied to dilute environmental systems using both compound specific and non-targeted strategies.

Developing an authentication approach using SPME-GC-IRMS based on compound-specific δ 13C analysis of six typical volatiles in wine

Abstract An analytical method using gas chromatography isotope ratio mass spectrometry (GC-IRMS) combined with solid phase micro-extraction (SPME) was developed to measure the δ 13C values of six typical volatiles commonly occurring in wine (isoamyl acetate, 2-octanone, limonene, 2-phenylethanol, ethyl octanoate and ethyl decanoate) for the first time. SPME selected with a divinylbenzene/carboxen/polydimethylsiloxane fiber was combined with the GC-IRMS for pretreatment optimization. The optimized SPME parameters of extraction time, extraction temperature and salt concentration were 40 min, 40 °C and 10%, respectively. The δ 13C values measured by SPME-GC-IRMS were in good agreement with those measured via elemental analyzer (EA)-IRMS and GC-IRMS. The differences range from 0.02 to 0.44‰ with EA-IRMS and from 0 to 0.28‰ with GC-IRMS, indicating the high accuracy of the method. This newly established method measured the precision within 0.30‰ and was successfully validated to discriminate imported real wine samples with identical label but amazing price differences from different importers.

A significant seawater sulfate reservoir at 2.0 Ga determined from multiple sulfur isotope analyses of the Paleoproterozoic Degrussa Cu-Au volcanogenic massive sulfide deposit, Western Australia

The Proterozoic rock record displays secular change from ferruginous to an oxic hydrosphere over the course of 2 billion years; however, debate continues on the periodicity, rate of change and steps in following atmospheric oxygenation that ultimately led to an oxygenated ocean. This is partly due to poor preservation of the Paleoproterozoic marine sedimentary record in the few hundred million years after the Great Oxidation Event. Whereas the 2.0 Ga rock record preserves only rare chemical sediments, it contains significant mafic igneous provinces, which are known to locally host volcanogenic massive sulfide (VMS) deposits. These hydrothermal environments fossilize the ancient interaction at the seafloor interface between volcanic rocks and seawater. In this context, the 2.01 Ga Degrussa VMS deposit of the Paleoproterozoic Capricorn Orogen, Western Australia offers an opportunity to probe the ancient ocean composition. The Degrussa VMS deposit preserves massive sulfide mineralisation (pyrite – chalcopyrite – pyrrhotite ± sphalerite ± galena) hosted in turbiditic sedimentary rocks interlayered with basaltic flows and cut by numerous gabbroic sills. Exhalite layers are composed of hematite and jasper associated with magnetite. This study documents the multiple sulfur isotope composition of the Degrussa VMS deposit through an integrated analytical approach, which comprises bulk fluorination gas chromatography isotope ratio mass spectrometry and in situ secondary ion mass spectrometry. By comparing the ultra-high precision bulk measurements (n = 21) with in situ measurements of variably-textured grains of pyrite, chalcopyrite and pyrrhotite (n = 252), we determine that VMS mineralisation yields δ34S between +2‰ and +5‰ with a peak at ∼+2.9‰, and negative Δ33S signal ranging from −0.08 to 0.00‰. A two component δ34S-Δ33S mixing model indicates 11% of H2S derived from thermochemically reduced seawater sulfate mixed with magmatic H2S. The most negative Δ33S values must be explained by interaction with sulfate in the near-surface, undergoing complex dissolution-reprecipitation reactions, necessitating a minimum seawater sulfate reservoir of ∼2 mmol/L, or 7% modern seawater at 2.01 Ga.

Isotope fractionation of micropollutants during large-volume extraction: heads-up from a critical method evaluation for atrazine, desethylatrazine and 2,6-dichlorobenzamide at low ng/L concentrations in groundwater

ABSTRACT Micropollutants are frequently detected in groundwater. Thus, the question arises whether they are eliminated by natural attenuation so that pesticide degradation would be observed with increasing residence time in groundwater. Conventional analytical approaches rely on parent compound/metabolite ratios. These are difficult to interpret if metabolites are sorbed or further transformed. Compound-specific stable isotope analysis (CSIA) presents an alternative for identifying degradation based on the analysis of natural isotope abundances in pesticides and their changes during degradation. However, CSIA by gas chromatography–isotope ratio mass spectrometry is challenged by the low concentrations (ng/L) of micropollutants in groundwater. Consequently, large amounts of water need to be sampled requiring enrichment and clean-up steps from interfering matrix effects that must not introduce artefacts in measured isotope values. The aim of this study was to evaluate the accuracy of isotope ratio measurements of the frequently detected micropollutants atrazine, desethylatrazine and 2,6-dichlorobenzamide after enrichment from large water volumes (up to 100 L) by solid-phase extraction with consecutive clean-up by HPLC. Associated artefacts of isotope discrimination were found to depend on numerous factors including organic matter content and extraction volume. This emphasizes the necessity to perform a careful method evaluation of sample preparation and sample pre-treatment prior reliable CSIA.