Ratio Mass Spectrometry Method Research Articles

Two-Dimensional Liquid Chromatography Purified GC/C/IRMS Doping Control Method: Analysis of Endogenous and Exogenous Sources in Urine Samples from Asian Subjects Administered a Low Dose of AICAR

AICAR (5-amino-4-imidazolecarboxyamide ribonucleoside), as a metabolic modulator, is classified in the S4 category by the World Anti-Doping Agency (WADA). Carbon Isotope Ratio Mass Spectrometry (CIR) is the mainstream method for distinguishing the endogenous and exogenous sources of AICAR in urine due to the significant individual difference in the concentration. The purpose of this study is to establish a gas chromatography combustion Isotope Ratio Mass Spectrometry (GC/C/IRMS) method for AICAR based on efficient two-dimensional liquid chromatography (2D-HPLC) separation. MethodIn this study, an automated 2D-HPLC separation technique was used to separate and purify AICAR and endogenous reference substances in urine samples. Then, AICAR was derivatized with 3-TMS as the main derivative product, while the endogenous reference compounds remained in their original form. Subsequently, the developed GC/C/IRMS method was utilized for the detection of the target and reference substances. Followed, we evaluated the applicability of this method using urine samples from two Asian males administered a low dose of AICAR (3 grams). ResultsThe advantages of this study include: 1) reduced sample pretreatment time: the established 2D-HPLC separation method can separate the target and endogenous reference substances in one step; 2) low interference: the isotope chromatograms have low background interference, and the separation of endogenous reference substances is purer; 3) more accurate result calculations: this method only requires derivatization and result correction for AICAR, with the endogenous reference substances measured in their original form, reducing biases from corrections of multiple substances. The detection method performed well, with a concentriton limit of 2500 ng/mL, meeting the needs of routine detection concentrations. The CIR results from volunteer samples indicated that samples collected within 16 hours post-administration exceeded the threshold set in the literature. ConclusionThis study successfully established a 2D-HPLC-GC/IRMS method that integrates CIR as the most stable indicator for distinguishing the internal and external sources of AICAR. After administering a low dose of AICAR to the Asian population, exogenous drug characteristics were manifested within 16 hours. This observation, when compared to the 40-hour detection window cited in the literature, suggests that the length of the detection window is positively correlated with the dosage of the test drug.

Procedures from samples to sulfur isotopic data: A review.

Sulfur isotopes have been widely used to solve some key scientific questions, especially in the last two decades with advanced instruments and analytical schemes. Different sulfur speciation and multiple isotopes analyzed in laboratories worldwide and in situ microanalysis have also been reported in many articles. However, methods of sampling to measurements are multifarious, and occasionally some inaccuracies are present in published papers. Vague methods may mislead newcomers to the field, puzzle readers, or lead to incorrect data-based correlations. We have reviewed multiple methods on sulfur isotopic analyses from the perspectives of sampling, laboratory work, and instrumental analysis in order to help reduce operational inhomogeneity and ensure the fidelity of sulfur isotopic data. We do not deem our proposed solutions as the ultimate standard methods but as a lead-in to the overall introduction and summary of the current methods used. It has been shown that external contamination and transformation of different sulfur species should be avoided during the sampling, pretreatment, storage, and chemical treatment processes. Conversion rates and sulfur isotopic fractionations during sulfur extraction, purification, and conversion processes must be verified by researchers using standard or known samples. The unification of absence of isotopic fractionation is needed during all steps, and long-term monitoring of standard samples is recommended. This review compiles more details on different methods in sampling, laboratory operation, and measurement of sulfur isotopes, which is beneficial for researchers' better practice in laboratories. Microanalyses and molecular studies are the frontier techniques that compare the bulk sample with the elemental analysis/continuous flow-gas source stable isotope ratio mass spectrometry method, but the latter is widely used. The development of sulfur isotopic measurements will lead to the innovation in scientific issues with sulfur proxies.

Purity Assessment of Honey Based on Compound Specific Stable Carbon Isotope Ratios Obtained by LC-IRMS.

The use of stable carbon isotope ratios (δ13C) of sugar fractions of honey is a powerful tool to detect adulteration with sugar syrups. This is accomplished by calculating differences of the δ13C values between individual honey saccharides and comparing them to published purity criteria. A liquid chromatography-isotope ratio mass spectrometry (LC-IRMS) method for the determination of δ13C values of sugars in honey was previously validated by an interlaboratory comparison, but no further guidance was given how to include the obtained precision figures of the compound-specific δ13C values in the purity assessment of honey. To use existing data to estimate the standard deviation of the repeatability (sr) and reproducibility (sR) of differences (Δ δ13C) between the δ13C values of individual honey saccharides. Previously published δ13C values were used to calculate differences (Δ δ13C values) between δ13C fructose-δ13C glucose, δ13C glucose-δ13C disaccharides, etc. in a honey sample; sr and sR of Δ δ13C values were calculated according to ISO 5725-2:2019. The Δ δ13C sr and sR values were essentially of the same magnitude as the sr and sR values of δ13C values of the sugar fractions. The precision of the Δ δ13C values was used to estimate the critical difference for comparing a test result with a reference value according to ISO 5725-6:1994. This varied between 0.26 and 1.10‰. The estimated critical differences can be used to determine whether a honey test result complies with published Δ δ13C purity criteria. The proposed procedure will increase confidence in decisions based on compound-specific δ13C values regarding the conformity of honey with published purity criteria.

A modified laser ablation-isotope ratio mass spectrometry method for in situ analysis of sulfur isotope composition of sulfides.

A novel laser ablation-isotope ratio mass spectrometry (LA-IRMS) method for in situ analysis of sulfur isotopes in sulfides has been developed. Instead of the in situ reaction applied by the traditional laser microprobe, the analyte gas preparation in this method is separated temporally and spatially from the LA, resulting in improved precision and accuracy. Our LA-IRMS system combines an ultraviolet LA system, an elemental analyzer (EA), a custom-built cryogenic concentration system, a continuous-flow interface, and an IRMS. The sulfide aerosol particles generated from LA were transferred by a helium carrier gas from the ablation cell into the reaction tube and were then converted into SO2 . Subsequently, SO2 was enriched in two cold traps and was finally introduced into the ion source of the IRMS through the continuous-flow interface. We measured three synthetic and four natural sulfide reference materials to test the performance of this method. Precisions of ±0.25‰-±0.48‰ and ±0.32‰-±0.64‰ (1SD, n = 5) for δ34 S values of synthetic and natural sulfide standards can be obtained for spot sizes ranging from 64 to 80 μm. Measured values and their recommended values showed a good linear relationship (R2 within 0.998 and 0.9995) with the slope of approaching unity (within 1.0509 and 1.1313). Data from the measurement of reference materials showed that the precision and accuracy of our method were satisfactory. This method is a powerful tool for in situ sulfur isotope measurement of sulfides and can be further applied to in situ carbon and oxygen isotope analyses.

Exploring δ13 C data compatibility in a broad δ13 C range: Reassembling δ13 C values obtained for NIST CO2 RMs 8562-8564 at different laboratories.

Stable isotope datasets obtained in different laboratories over years must be compared and combined. The strict compatibility in δ13 C at ±0.01‰ and ±0.02‰, k= 1, respectively, is required for observations of greenhouse gases CO2 and methane. That implies the long-term compatibility of calibrations realized at different laboratories. Thus far, this level of compatibility has not been demonstrated for pure CO2 in a broad δ13 C range and over years. We reassemble the δ13 C obtained in different laboratories for NIST CO2 RMs 8562-8564, which are pure CO2 gases. If the measurements are based on independent calibrations and reported on the same 17 O correction framework, δ13 C of all three RMs can be used to estimate the long-term δ13 C data compatibility. δ13 C values obtained in different laboratories for NIST CO2 RMs 8562-8564 (a range of δ13 C from ~ -3.7‰ to ~ -41.6‰) from 1998 to 2020 agree within their uncertainties. Two NIST studies (1999 and 2004) have combined data from several laboratories using different Isotope ratio mass spectrometry (IRMS) methods and somewhat different approaches. Three single-laboratory studies (2003, 2008, and 2020) have used the same type of IRMS and similar approaches. The δ13 C values from these laboratories agree within ±0.01‰, k= 1, over the entire δ13 C range and have uncertainties about two times lower than those obtained at NIST by combining data from several laboratories. The δ13 C values for NIST CO2 RMs 8562-8564 obtained in three laboratories using the same IRMS (2003, 2008, and 2020) agree within ±0.01‰, k= 1. First, this confirms the long-term stability in δ13 C of RMs 8562-8564. Second, this example of compatibility in δ13 C calibrations on pure CO2 , from -3.7‰ to -41.6‰, is relevant to stable isotope measurements of greenhouse gases CO2 and methane. Third, this confirms the high accuracy of the δ13 C(air-CO2 ) calibrations performed in 2003 and 2008 for the project Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrumented Container (CARIBIC).

Isotopic (δ13C, δ18O) Analysis of Small Amounts of Carbonate in Silicate Rocks by the Continuous Flow Isotope Ratio Mass Spectrometry Method

An experimental study of the main factors affecting the accuracy of oxygen and carbon isotopic analysis in carbonates dispersed in silicate matrix is carried out. Artificial 1, 2, 5, and 10% mixtures of quartz with carbonates with different isotopic parameters (KH-2, Ko, MCA-8) were analyzed by continuous flow isotope ratio mass spectrometry (CF IRMS). It is established that, in addition to the influence of the instrumental nonlinearity, the results are affected by two factors: trace amounts of CO2, constantly present in the system (the blank effect) and the presence of chemically neutral silicate particles (the matrix effect). The blank effect depends on the isotopic parameters of the sample and has very little influence on the estimated carbonate content in the rock. The matrix effect, on the contrary, strongly affects the estimated carbonate content, and produces the isotopic shift towards underestimated contents of heavy 13C and 18O isotopes. It is shown that this effect is related to the processes occurring near the CO2–acid–quartz interface, which are accompanied by kinetic fractionation of carbon and oxygen isotopes. Both effects are dependent on the amount of silicate matrix in the system and most clearly manifested during analysis of carbonate-poor rocks. When the carbonate content in the rock is about 1–2%, deviations from the true δ13C and δ18O values can reach the first ppm, while carbonate content obtained by chromatographic peak calibration can be underestimated by 20–40%.

Isotopic (δ13C, δ18O) Analysis of Small Amounts of Carbonate in Silicate Rocks by the Continuous Flow Isotope Ratio Mass Spectrometry Method

An experimental study of the main factors affecting the accuracy of oxygen and carbon isotopic analysis in carbonates dispersed in silicate matrix is carried out. Artificial 1, 2, 5, and 10% mixtures of quartz with carbonates with different isotopic parameters (KH-2, Ko, MCA-8) were analyzed by continuous flow isotope ratio mass spectrometry (CF IRMS). It is established that, in addition to the influence of the instrumental nonlinearity, the results are affected by two factors: trace amounts of CO2, constantly present in the system (the blank effect) and the presence of chemically neutral silicate particles (the matrix effect). The blank effect depends on the isotopic parameters of the sample and has very little influence on the estimated carbonate content in the rock. The matrix effect, on the contrary, strongly affects the estimated carbonate content, and produces the isotopic shift towards underestimated contents of heavy 13C and 18O isotopes. It is shown that this effect is related to the processes occurring near the CO2–acid–quartz interface, which are accompanied by kinetic fractionation of carbon and oxygen isotopes. Both effects are dependent on the amount of silicate matrix in the system and most clearly manifested during analysis of carbonate-poor rocks. When the carbonate content in the rock is about 1–2%, deviations from the true δ13C and δ18O values can reach the first ppm, while carbonate content obtained by chromatographic peak calibration can be underestimated by 20–40%.

Using Liquid Chromatography-Isotope Ratio Mass Spectrometry for Detection of Economically Motivated Adulteration of Maple Syrup.

Maple syrup is a sought-after commodity, and used as a condiment and a sweetener. Also, it is an active target of economically motivated adulteration (EMA), similar to other foods such as lemon juice and honey. This study is aimed to detect low cost sugar adulteration in maple syrup via an internal standard method using malic acid through solid-phase extraction (SPE) and LC with isotope ratio mass spectrometric detection (LC-IRMS). In this work, an optimized SPE sample preparation procedure was used for the isolation of organic acids from maple syrup. Using LC-IRMS, malic acid was separated from other organic acids and the δ13C value of malic acid was determined. Eleven maple syrup samples, domestic or imported from Canada, were evaluated for 13C/12C ratios (δ13C values) using combustion module-cavity ring down spectrometry (CM-CRDS) and compared to the δ13C values obtained from well-established elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) methods. The δ13C values of isolated malic acid analyzed by SPE-LC-IRMS were used as internal standards and compared to the δ13C values of bulk maple syrup; difference (δ13Csugars - δ13Cmalic acid) values greater than 3.6‰ are indicative of low-cost sugar adulteration. Overall, the results obtained from SPE-LC-IRMS provided a faster, novel analysis approach for determining low-cost sugar adulteration in maple syrup for regulatory purposes. This method also provided lower detectable limits of adulteration versus current literature reports using bulk analysis and comparable detection limits to Tremblay and co-workers who utilized an internal standard method. SPE-LC-IRMS is a robust method that can be used for detecting adulteration in maple syrup samples for regulatory purposes. SPE-LC-IRMS is a faster, novel analysis approach for determining C4 adulteration in maple syrup with lower detection limits.

Intramolecular carbon isotope geochemistry of butane isomers from laboratory maturation and Monte-Carlo simulations of kerogen types I, II, and III

Position-specific (PS) carbon isotope compositions of light hydrocarbons such as propane and butane isomers (n-butane and i-butane) can provide a wealth of information on the history of natural gases in the subsurface reservoirs and other environments. For PS carbon isotope analysis of butane isomers, we have established a GC-pyrolysis-GC-isotope ratio mass spectrometry method with demonstrated accuracy. With this method, we analyzed PS δ13C values of butane isomers generated from the systematic laboratory pyrolysis experiments of three different kerogen types (I, II, and III) at temperatures of 310–430 °C with corresponding thermal maturity (Easy %Ro) ranging from 0.7 to 3.3. The observed evolution in the abundances of butane isomers can be interpreted and semi-quantitatively modeled based on the abundances of different CC bonds within the kerogens at low maturity and thermal degradation of butane isomers at high maturity. The δ13C values at the central sites of both nC4 and iC4 were heavier than those at the terminal positions, similar to our previous observations of propane. Their isotopic evolution with the maturity were controlled largely by kinetic isotope effects associated with breaking of different CC bonds during the generation and degradation of butane isomers. Kinetic Monte Carlo (kMC) simulations of n-butane generated from thermal cracking of model kerogens (I, II, and III) and an oil with a series of reactions (homolytic cleavage, β-scission, radical isomerization, H-abstraction, and termination by radical recombination) provided generally consistent results with the experimental observations, although the difference in PS δ13C values between the central and terminal positions are somewhat overestimated. On the other hand, the kMC simulation with homolytic cleavage and capping reactions alone produced significant deviations from the experimental results. Re-assessment of very limited data of PS δ13C values of natural butanes with our experimental and simulation results show that biodegradation significantly increased δ13C values at the central positions, not only of propane, but also of both butane isomers. This study lays a foundation and demonstrates the potential of PS isotope geochemistry of butane isomers to further improve our understanding of the sources, and geochemical and microbial processes of light hydrocarbons in the subsurface and other natural environments.

The intra-laboratory study of EIM-IRMS® (Ethanol Isotope Measurement–Isotope Ratio Mass Spectrometry) method performance with CS-qNMR (Cumulative Screening–quantitative NMR)

In our earlier publications we proposed the possibility of using new EIM–IRMS® instrumental technique and analytical parameter δDn wine ethanol, which represents δ2H value of non-exchangeable hydrogen stable isotope ratio in ethanol, to improve detection of illegal wine production practices such as addition of sugar and/or water to grape must prior to alcoholic fermentation. This article shows a comparative performance study between EIM-IRMS® and CS-qNMR methods in order to evaluate potential and demonstrate the precision of two isotopic concepts and their degree of detection of illegal wine production practices. Three batches of laboratory wine samples were prepared from three different types of grapes (N=24 samples). Sample results obtained from both methods are compared and a statistical data processing was carried out. Based on the results obtained using the EIM-IRMS® method we detected 11 out of 21 of previously adulterated wine samples which represents a success rate of 52.4% detection of illegal practices (beet sugar, water or beet sugar syrup additions). In addition, wines from the Republic of Serbia (90 samples) were examined as well using the EIM-IRMS® method and appropriate equipment to confirm their authenticity.

Validation of gas chromatographic methods for lavender essential oil authentication based on volatile organic compounds and stable isotope ratios

A combination of Gas Chromatography-tandem Mass Spectrometry (GC-MS/MS) and Gas Chromatography-Isotope Ratio Mass Spectrometry (GC-IRMS) methods is a powerful tool to control false declaration of various food matrices including lavender essential oil. However, the methods need to be validated to demonstrate data reliability.In the present study, we developed a GC-MS/MS method for determining volatile organic compounds in lavender essential oil. For this, a single chromatographic run was optimised to separate thirty-eight pure reference standards in<17 min using a suitable capillary column, a faster injection system, temperature ramp gradient, and acquiring mass spectra through dynamic monitoring reaction and full scan mode. The GC-MS/MS method was validated according to the “Harmonised guidelines of IUPAC” considering parameters such as linearity range, limit of detection, limit of quantification, regression coefficient, repeatability and reproducibility. The validation parameters suggested that the method was sufficiently sensitive, precise and accurate for the determination of VOCs.Moreover, we developed a GC-IRMS method to characterize the isotope ratios of carbon (δ13C) and hydrogen (δ2H) of a large selection of the VOCs present in the lavender oil. For this, different matrices of various essential oil compounds of known δ13C and δ2H values (obtained from bulk isotope ratio analysis) were analysed in the GC-IRMS. Similarly to the GC-MS/MS method, the GC-IRMS method was validated according to the recommendation by the Forensic Isotope Ratio Mass Spectrometry Network (FIRMS). In particular, the linearity test suggested that concentrations of at least 25 mg L−1 and 200 mg L−1 were required to produce reliable δ13C and δ2H values, respectively. Both δ13C and δ2H values were satisfactorily repeatable, reproducible and accurate. As expected, precision and accuracy of the δ2H were lower than those of the δ13C.Finally, the practical applicability of the methods was confirmed by the analysis of 3 lavender and 3 lavandin essential oil samples. We quantified the concentrations of 71 VOCs and the δ13C value of 32 and δ2H value of 30 compounds in real essential oil samples. These preliminary results showed that the combination of GC-MS/MS and GC-IRMS is potentially useful for botanical classification between lavender and lavandin essential oils thus representing an additional powerful tool for assessing the authenticity of commercial essential oils.

Removal of contamination in helium for precise SF6‐based Δ36S measurements

Quantifications of quadruple sulfur isotopic compositions (δ34 S, Δ33 S, and Δ36 S) of sulfur-bearing compounds in nature are valuable for providing new insights into the Earth's evolution such as the crust-mantle cycle, oxygenation of atmosphere and oceans, and the origin and evolution of early life. SF6 -based isotope ratio mass spectrometry is the most widely used method of quantification, but Δ36 S measurements at high precision and accuracy have always been technically difficult due to the low abundance of 36 S (~0.01%). In this paper, we identify a major source of isobaric interferences (i.e., contamination in helium carrier gas in the gas chromatography purification step) and propose a simple strategy to solve this problem. An SF6 fluorination and purification system was built. Laboratory SF6 reference gas and international Ag2 S standard (IAEA-S1) were used as reference materials to test our method. Contamination from helium carrier gas (99.999%) was purified by a simple two-step cryogenic method to allow for accurate and precise measurements of Δ36 S using the SF6 -based isotope ratio mass spectrometry method. Without proper purification of helium carrier gas, large errors in Δ36 S measurements were found. Measured Δ36 S values of SF6 with trace contamination from helium were >10‰ higher than expected values. Using a newly developed purification strategy, the difference in Δ36 S values of SF6 before and after passing through the gas chromatography is less than instrumental errors (<0.2‰). Our improved method yielded an overall Δ36 S precision for IAEA-S1 of 0.12‰ (n = 6). This precision is comparable to that found by other laboratories around the world. Our simple two-step cryogenic method significantly improved the accuracy and precision of Δ36 S measurements and is therefore recommended for future determination of quadruple sulfur isotopic compositions in natural samples.

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.

Development and Validation of Gas Chromatography – Tandem Mass Spectrometry and Gas Chromatography – Isotope Ratio Mass Spectrometry Methods for Determining Volatile Organic Compounds and Isotope Ratio Analysis of Carbon and Hydrogen in Lavender Essential Oil

Development and Validation of Gas Chromatography – Tandem Mass Spectrometry and Gas Chromatography – Isotope Ratio Mass Spectrometry Methods for Determining Volatile Organic Compounds and Isotope Ratio Analysis of Carbon and Hydrogen in Lavender Essential Oil

Results of an Interlaboratory Comparison of a Liquid Chromatography-Isotope Ratio Mass Spectrometry Method for the Determination of 13C/12C Ratios of Saccharides in Honey.

BackgroundStable carbon isotope analysis of sugars in honey by LC–isotope ratio mass spectrometry (IRMS) is a useful tool for detecting adulteration of honey with extraneous sugar. Purity criteria based on 13C/12C ratios of saccharides in honey, determined by LC–IRMS of a large number of authentic honey samples, have been elaborated. However, no interlaboratory comparison (ILC) has yet been performed to estimate the precision of the method under reproducibility conditions.ObjectiveTo address this knowledge gap an ILC involving 14 laboratories and using six honey samples was conducted.MethodsThe participants were allowed to use their LC–IRMS-based method of choice for sample preparation and compound separation.ResultsThe precision figures were estimated according to ISO 5725:1994. The repeatability relative standard deviation (RSDr) for the determination of δ13C values of fructose and glucose varied between 0.3 and 0.5%, with 0.3 and 1.0% for disaccharides, and 0.7 and 2.8% for trisaccharides. The RSDR varied between 0.8 and 1.8% for the monosaccharides, 1.0 and 1.5% for disaccharides, and 1.4 and 2.8% for trisaccharides.ConclusionBased on the obtained precision data the LC–IRMS method for the determination of 13C/12C ratios of saccharides in honey was considered fit for the conformity assessment of honey with established purity criteria.HighlightsPrecision estimates for a LC–IRMS method to determine 13C/12C ratios of saccharides in honey were obtained through an ILC. The data created can form the basis for the standardization of the method by interested standards-developing organizations for use in official control.

A GC-IRMS method for measuring sulfur isotope ratios of carbonyl sulfide from small air samples

A new system was developed for measuring sulfur isotopes δ33S and δ34S from atmospheric carbonyl sulfide (COS or OCS) on small air samples of several liters, using a pre-concentration and gas chromatography – isotope ratio mass spectrometry (GC-IRMS) method. Measurements of COS isotopes provide a tool for quantifying the COS budget, which will help towards better understanding climate feedback mechanisms. For a 4 liter sample at ambient COS mixing ratio, ~500 parts per trillion (ppt), we obtain a reproducibility error of 2.1 ‰ for δ33S and 0.4 ‰ for δ34S. After applying corrections, the uncertainty for an individual ambient air sample measurement is 3.3 ‰ for δ33S and 0.9 ‰ for δ34S. The ability to measure small samples allows application to a global-scale sampling program with limited logistical effort. To illustrate the application of this newly developed system, we present a timeseries of ambient air measurements, during the fall and winter of 2020 and 2021 in Utrecht, the Netherlands. The observed background values were δ33S = 1.0 ± 3.4 ‰ and δ34S = 15.5 ± 0.8 ‰ (VCDT). The maximum observed COS mixing ratios was 620 ppt, suggesting that the Netherlands receives little COS-containing anthropogenic emissions. We observed a change in COS mixing ratio and sometimes also δ34S with different air mass origin, as modelled with the Hybrid Single-Particle Lagrangian Integrated Trajectory model (HYSPLIT) backward trajectory analyses. An increasing trend of 40 ppt was observed in the COS mixing ratio between fall and winter, which is consistent with the expected seasonal cycle in the Netherlands. Additionally, we present the results from samples taken inside a highway tunnel in Utrecht to characterize vehicle COS emissions and isotopic composition. The vehicle emissions were small, with a COS/CO2 ratio of 0.4 ppt/ppm; the isotopic signatures are depleted relatively to background atmospheric COS.

Simultaneous measurement of &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;13&amp;lt;/sup&amp;gt;C, &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O and &amp;lt;i&amp;gt;δ&amp;lt;/i&amp;gt;&amp;lt;sup&amp;gt;17&amp;lt;/sup&amp;gt;O of atmospheric CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; – performance assessment of a dual-laser absorption spectrometer

Abstract. Using laser absorption spectrometry for the measurement of stable isotopes of atmospheric CO2 instead of the traditional isotope ratio mass spectrometry method decreases sample preparation time significantly, and uncertainties in the measurement accuracy due to CO2 extraction and isobaric interferences are avoided. In this study we present the measurement performance of a new dual-laser instrument developed for the simultaneous measurement of the δ13C, δ18O and δ17O of atmospheric CO2 in discrete air samples, referred to as the Stable Isotopes of CO2 Absorption Spectrometer (SICAS). We compare two different calibration methods: the ratio method, based on the measured isotope ratio and a CO2 mole fraction dependency correction, and the isotopologue method, based on measured isotopologue abundances. Calibration with the ratio method and isotopologue method is based on three different assigned whole-air references calibrated on the VPDB (Vienna Pee Dee Belemnite) and the WMO 2007 (World Meteorological Organization) scale for their stable isotope compositions and their CO2 mole fractions, respectively. An additional quality control tank is included in both methods to follow long-term instrument performance. Measurements of the quality control tank show that the measurement precision and accuracy of both calibration methods is of similar quality for δ13C and δ18O measurements. During one specific measurement period the precision and accuracy of the quality control tank reach WMO compatibility requirements, being 0.01 ‰ for δ13C and 0.05 ‰ for δ18O. Uncertainty contributions of the scale uncertainties of the reference gases add another 0.03 ‰ and 0.05 ‰ to the combined uncertainty of the sample measurements. Hence, reaching WMO compatibility for sample measurements on the SICAS requires reduction of the scale uncertainty of the reference gases used for calibration. An intercomparison of flask samples over a wide range of CO2 mole fractions has been conducted with the Max Planck Institute for Biogeochemistry, resulting in a mean residual of 0.01 ‰ and −0.01 ‰ and a standard deviation of 0.05 ‰ and 0.07 ‰ for the δ13C measurements calibrated using the ratio method and the isotopologue method, respectively. The δ18O could not be compared due to depletion of the δ18O signal in our sample flasks because of storage times being too long. Finally, we evaluate the potential of our Δ17O measurements as a tracer for gross primary production by vegetation through photosynthesis. Here, a measurement precision of &lt;0.01 ‰ would be a prerequisite for capturing seasonal variations in the Δ17O signal. Lowest standard errors for the δ17O and Δ17O of the ratio method and the isotopologue method are 0.02 ‰ and 0.02 ‰ and 0.01 ‰ and 0.02 ‰, respectively. The accuracy results show consequently results that are too enriched for both the δ17O and Δ17O measurements for both methods. This is probably due to the fact that two of our reference gases were not measured directly but were determined indirectly. The ratio method shows residuals ranging from 0.06 ‰ to 0.08 ‰ and from 0.06 ‰ to 0.1 ‰ for the δ17O and Δ17O results, respectively. The isotopologue method shows residuals ranging from 0.04 ‰ to 0.1 ‰ and from 0.05 ‰ to 0.13 ‰ for the δ17O and Δ17O results, respectively. Direct determination of the δ17O of all reference gases would improve the accuracy of the δ17O and thereby of the Δ17O measurements.

Carbonaceous Fractions Contents and Carbon Stable Isotope Compositions of Aerosols Collected in the Atmosphere of Montreal (Canada): Seasonality, Sources, and Implications

With the objective of better understanding the sources and dynamics of carbonaceous fractions of the aerosols present in the atmosphere of Montreal, we implemented here an online wet oxidation/isotope ratio mass spectrometry (IRMS) method to simultaneously measure both water-soluble organic carbon (WSOC) content and the corresponding δ13C of aerosol samples collected at four monitoring stations over a 1-year period representing distinct types of environmental conditions (i.e., background, road traffic, industrial, and downtown). We coupled these data with the corresponding concentrations of other carbon fractions: total carbon (TC), elemental carbon plus organic carbon (EC + OC), and carbonates. Results show that TC (6.64 ± 2.88 μg m–3), EC + OC (4.98 ± 2.23 μg m–3), and carbonates (1.71 ± 1.09 μg m–3) were characterized by lower concentrations in winter and higher ones between spring and early autumn, with all fractions expectedly showing significantly lower concentrations for aerosols collected at the background station. We observed a seasonal dependence of the δ13CEC+OC (−25.31 ± 0.94‰) with the EC + OC/total suspended particles (TSP) ratio: (i) an increase of the ratio during late spring, summer and early autumn associated to road traffic emissions characterized by a δ13C of ∼−25‰ and (ii) lower ratios during the winter months indicating the influence of two distinct emission sources, a first one with a δ13C ∼−27‰, suggesting the local influence of combined biomass burning from residential heating and of fossil fuel combustion, and a second one with a δ13C ∼−21‰, likely related to more regional emissions. WSOC (1.14 ± 0.67 μg m–3) presented a similar seasonal pattern for all monitoring stations, with low concentrations in winter, early spring and late autumn that rapidly increased until summer. Our results indicate that this seasonality is controlled by higher anthropogenic contributions from southern Canada and northeastern United States regions and probably from biogenic emissions during the warm months. Moreover, δ13CWSOC (−25.08 ± 1.47‰) showed a 13C-depletion in summer, indicating higher fossil fuel and biogenic contributions, whereas the higher isotope compositions observed in winter may result from the photochemical aging of regional aerosols. Ultimately, we identified the influence of local industrial emissions late in 2013 as well as the impact of aerosol emissions associated to the Lac-Mégantic rail disaster that occurred on July 6, ∼200 km east of Montreal.

Characterization of Algae Dietary Supplements Using Antioxidative Potential, Elemental Composition, and Stable Isotopes Approach.

Dietary supplements based on algae, known for their nutritional value and bioactive properties, are popular products among consumers today. While commercial algal products are regarded safe by numerous studies, information about the production and origin of such products is scarce. In addition, dietary supplements are not as strictly regulated as food and medicinal drugs. We characterized different algal products (kelps: Laminariales, Spirulina spp., Chlorella spp., and Aphanizomenon flos-aquae), obtained on Slovenian market, based on their elemental composition (X-ray fluorescence, inductively coupled plasma–mass spectrometry), antioxidative potential [DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, total phenolic content], and stable isotope values [carbon (C), nitrogen (N), and sulfur (S); elemental analyzer isotope ratio mass spectrometry (EA-IRMS) method]. Antioxidative potential is consistent among products of the same type, with A. flos-aquae samples having 4.4 times higher antioxidative potential compared to Chlorella spp. and 2.7 times higher compared to Spirulina spp. Levels of toxic trace elements (arsenic, cadmium, mercury, and lead) are below the maximum allowed values and as such do not pose risk to consumers' health. Samples of Spirulina spp. have relatively high δ15N (7.4 ‰ ± 4.4‰) values, which indicate use of organic nitrogen sources in certain samples. Likewise, different elemental composition and isotopic ratios of stable elements (C, N, and S) for the samples with Spirulina spp. or Chlorella spp. are the consequence of using different nutrient sources and algae-growing techniques. Statistical analysis (principal component analysis) has confirmed that all tested A. flos-aquae samples originate from the same source, supposedly Klamath Lake (Oregon, USA). Hawaiian Spirulina pacifica can also be differentiated from all the other samples because of its characteristically high metal content (iron, manganese, zinc, cobalt, nickel, vanadium). Chlorella spp. and Spirulina spp. require further analyses with larger number of samples, as differentiation is not possible based on results of this study.

Detecting the abuse of 19-norsteroids in doping controls: A new gas chromatography coupled to isotope ratio mass spectrometry method for the analysis of 19-norandrosterone and 19-noretiocholanolone.

The detection of 19-norsteroids abuse in doping controls currently relies on the determination of 19-norandrosterone (19-NA) by gas chromatography-tandem mass spectrometry (GC-MS/MS). An additional confirmatory analysis by gas chromatography coupled to isotope ratio mass spectrometry (GC-C-IRMS) is performed on samples showing 19-NA concentrations between 2.5 and 15 ng/ml and not originated from pregnant female athletes or female treated with 19-norethisterone. 19-Noretiocholanolone (19-NE) is typically produced to a lesser extent as a secondary metabolite. The aim of this work was to improve the GC-C-IRMS confirmation procedure for the detection of 19-norsteroids misuse. Both 19-NA and 19-NE were analyzed as target compounds (TCs), whereas androsterone (A), pregnanediol (PD), and pregnanetriol (PT) were selected as endogenous reference compounds (ERCs). The method was validated and applied to urine samples collected by three male volunteers after the administration of nandrolone-based formulations. Before the instrumental analysis, urine samples (<25 ml) were hydrolyzed with β-glucuronidase from Escherichia coli and extracted with n-pentane. Compounds of interest were purified through a single (for PT) or double (for 19-NE, 19-NA, A, and PD) liquid chromatographic step, to reduce the background noise and eliminate interferences that could have affect the accuracy of δ13 C values. The limit of quantification (LOQ) of 2 ng/ml was ensured for both 19-NA and 19-NE. The 19-NE determination could be helpful in case of "unstable" urine samples, in late excretion phases or when coadministration with 5α-reductase inhibitors occur.