Isotope Ratio Mass Spectrometry

The doubly labelled water method is valuable for measuring energy expenditure in humans. It usually involves blood or urine sampling, which might be difficult in neonates and children with cerebral palsy or other disabilities. We therefore aimed to validate a method making use of saliva samples analyzed by automated thermal conversion elemental analyzer in combination with isotope ratio mass spectrometry (TC-EA/IRMS). The subjects received labelled water orally and urine and saliva samples were collected and analyzed. Deuterium as well as oxygen 18 was measured in one single run using a peak jump method. Excellent linearity was found for measurement of enrichments of deuterium (R 2 ¼ 0.9999) and oxygen 18 (R 2 ¼ 0.9999). The intra-assay precision and the inter-assay precision of the measurement of two standards were good for both deuterium and oxygen 18. The variation between urine and saliva samples was small (4.83% for deuterium and 2.33% for oxygen 18 n ¼ 40). Saliva sampling is to be preferred, therefore, as it can be easily collected and is non-invasive. Moreover, its time of production is almost exactly known. The TC-EA/IRMS method is a good alternative to the more laborious off-line IRMS measurements.

The aim of this study was to evaluate the accuracy of a new, continuous real time (13)C-urea breath test, BreathID, for the diagnosis of Helicobacter pylori in patients taking proton pump inhibitors (PPIs). Fifty-two consecutive patients, positive for H. pylori by BreathID, were prospectively evaluated. Patients were randomized to receive either omeprazole 20 mg/day or pantoprazole 40 mg/day for 14 days. A repeat breath test was performed on day 14 while patients received their last PPI pill. Patients were given a test drink containing 75 mg (13)C-urea and 4.0 g citric acid. Real time, continuously sampled expired (13)CO(2), obtained within 6-20 min, was compared with measurement of expired (13)CO(2) by isotope ratio mass spectrometry (IRMS). A full set of test data was available for 43 patients. After 14 days of treatment with PPIs, false negative detection of H. pylori occurred in only 1/43 (2.3%) patients examined by continuous real time (13)C-urea breath test compared with 2/43 ...

List of Figures xiii List of Tables xix Introduction: Stable Isotope 'Fingerprinting' or Chemical 'DNA': A New Dawn for Forensic Chemistry? xxi Table III.A.1 Athlete's versus reported δ 13 C values for pathway-linked testosterone metabolites

This review highlights the many roles mass spectrometry plays in the discovery and development of new therapeutics by both the pharmaceutical and the biotechnology industries. Innovations in mass spectrometer source design, improvements to mass accuracy, and implementation of computer-controlled automation have accelerated the purification and characterization of compounds derived from combinatorial libraries, as well as the throughput of pharmacokinetics studies. The use of accelerator mass spectrometry, chemical reaction interface-mass spectrometry and continuous flow-isotope ratio mass spectrometry are promising alternatives for conducting mass balance studies in man. To meet the technical challenges of proteomics, discovery groups in biotechnology companies have led the way to development of instruments with greater sensitivity and mass accuracy (e.g., MALDI-TOF, ESI-Q-TOF, Ion Trap), the miniaturization of separation techniques and ion sources (e.g., capillary HPLC and nanospray), and the utilization of bioinformatics. Affinity-based methods coupled to mass spectrometry are allowing rapid and selective identification of both synthetic and biological molecules. With decreasing instrument cost and size and increasing reliability, mass spectrometers are penetrating both the manufacturing and the quality control arenas. The next generation of technologies to simplify the investigation of the complex fate of novel pharmaceutical entities in vitro and in vivo will be chip-based approaches coupled with mass spectrometry.

Sub-basins within the New York/New Jersey (NY/NJ) Harbor host variable amounts and sources of polycyclic aromatic hydrocarbons (PAHs). Analyses of radionuclides 137Cs and 7Be were used to assign approximate dates to individual sections of sediment cores collected from four major sub-basins of the harbor complex. Sampling sites range from heavily contaminated Newark Bay and Passaic River to less contaminated Raritan Bay and Jamaica Bay. PAHs were identified with GC–MS and quantified by GC respectively. Gas chromatography–isotope ratio mass spectrometry (GC/IRMS) was applied to determine δ13C values of pyrene (δ13CPy), a principal 4 ring parent PAH. Two end-member PAH source components, petroleum-related PAHs (PRPAH) and combustion-related PAHs (CRPAH), were calculated from a carbon isotopic mass balance equation based on assumptions that petroleum-related δ13CPy is −29‰, and that combustion-derived δ13CPy is −24‰. Temporal trends of PRPAH in these cores are similar to those of the petroleum-derived unresolved complex mixture (UCM), whereas CRPAH resembled trends of “Total” PAH (TPAH). Three molecular ratios, fluoranthene to fluoranthene plus pyrene (Fl/(Fl + Py)), high molecular weight 4–6 ring PAH to total PAH (Ring456/TPAH) and parent to total (Par/(Par + Alkyl)), correlate strongly with each other, and show a moderate to strong positive correlation with δ13CPy. In contrast, the ratios of anthracene to phenanthrene plus anthracene (A/(Pa + A)), benzo[a]anthracene to benzo[a]anthracene plus chrysene (BaA/(BaA+Chy)), and indeno[1,2,3-cd]pyrene to indeno[1,2,3-cd]pyrene plus benzo[ghi]perylene (IP/(IP + Bghi)) show no, weak, or even negative correlation with the four well correlated ratios (δ13CPy, Par/(Par + Alkyl), Fl/(Fl + Py), and Ring456/TPAH). Combined application of the four well correlated molecular indicators suggests that PAH contribution from combustion became more important in most areas of the NY/NJ Harbor during the last three decades of the 20th century.

This review highlights the many roles mass spectrometry plays in the discovery and development of new therapeutics by both the pharmaceutical and the biotechnology industries. Innovations in mass spectrometer source design, improvements to mass accuracy, and implementation of computer-controlled automation have accelerated the purification and characterization of compounds derived from combinatorial libraries, as well as the throughput of pharmacokinetics studies. The use of accelerator mass spectrometry, chemical reaction interface-mass spectrometry and continuous flow-isotope ratio mass spectrometry are promising alternatives for conducting mass balance studies in man. To meet the technical challenges of proteomics, discovery groups in biotechnology companies have led the way to development of instruments with greater sensitivity and mass accuracy (e.g., MALDI-TOF, ESI-Q-TOF, Ion Trap), the miniaturization of separation techniques and ion sources (e.g., capillary HPLC and nanospra...

1] Abstract: Molybdenum isotopic compositions are precisely determined by MC-ICP-MS measurements using a Mo double spike. The double spike is added prior to chemical purification, so that laboratory and instrumental mass fractionations are separated from natural mass-dependent fractionation. Fractionation is determined on four Mo mass ratios, providing an internal consistency check. The external standard reproducibility is at 0.06 per mil on the 98 Mo/ 95 Mo ratio (2 standard deviation)). Using a normal microconcentric nebuliser with a cyclonic spray chamber, the minimum quantity of Mo is $1 mg for high-precision results. A hydrothermal molybdenite shows fractionation of À0.3 per mil on the 98 Mo/ 95 Mo ratio relative to our standard (Johnson Matthey, 1000 mg/mL (0.3%) ICP standard solution, lot 602332B). Fine-grained sediments show fractionation of 0.1 and À0.3 per mil on the 98 Mo/ 95 Mo ratio. The observed Mo isotope fractionation is small but resolvable with the presented high-resolution technique. , 2001. Determination of molybdenum isotope fractionation by doublespike multicollector inductively coupled plasma mass spectrometry,

The possibility of obtaining molecular information from lipid residues associated with archaeological pottery has dramatically increased the potential for deriving new information on the use of ancient vessels and the commodities processed therein. Motivated by the high proportion of the archaeological potsherds that have been shown to contain animal fats, a new approach invol- ving compound specific stable isotope analysis

A new method is described for distinguishing between animal fats preserved in ancient pottery. Analysis of lipid fractions from two morphologically distinct vessel types (lamps and ''dripping dishes'') using on-line gas chromatography-13 combustion-isotope ratio mass spectrometry (GC-C-IRMS) showed that they could be distinguished by plotting the d C 13 value for n-hexadecanoic acid against that for n-octadecanoic acid. The d C values obtained for modern reference fats from domesticated animals likely to have been important in antiquity showed the lamp extracts to correlate with ruminant animal 13 fat, such as sheep or cattle, whereas the ''dripping dishes'' had d C values similar to those of non-ruminant animal fat, such as pig. These findings were entirely consistent with distributional information obtained by GC and with positional isomer information gained from analysis of dimethyldisulphide derivatives of the monounsaturated fatty acids. The results indicate that GC-C-IRMS has considerable potential for the classification of animal fats absorbed in ancient pottery particularly where fatty acid distributions have been altered by degradation during vessel use or burial. d C values were also shown to be of value in detecting the use of vessels in the processing of animal products from more than one source.

The ratio of dibenzothiophene to phenanthrene and the ratio of pristane to phytane, when coupled together, provide a novel and convenient way to infer crude oil source rock depositional environments and lithologies. Such knowledge can significantly assist in identifying the source formation (s) in a basin thereby providing valuable guidance for further exploration. The ability to infer this information from analysis of a crude oil is especially valuable as frequently the earliest samples in a new area may be shows and/or drill stem test samples from exploratory wells which are characteristically drilled on structural highs stratigraphically remote from the source formation(s).

Since the introduction of isotope ratio mass spectro-meters (IRMS), on-line coupled to a gas chromatograph (GC) via a combustion interface (C), there has been increasing interest in its various analytical applica-tions.'-' The merits of this system, however, are some-what ...

We describe a new method of assessing, in a single run, 13 C isotopic enrichment of both Val and Thr by gas chromatography-combustion-isotope-ratio mass spectrometry (GC-C-IRMS). This method characterised by a rapid one-step derivatisation procedure performed at room temperature to form the N(O,S)-ethoxycarbonyl ethyl ester derivatives, and a polar column for GC. The suitability of this method for Val and Thr in in-vivo samples (mucosal hydrolysate) was demonstrated by studying protein metabolism with two tracers ( 13 C-valine or 13 C-threonine). The intra-day and inter-day repeatability were both assessed either with standards or with in-vivo samples at natural abundance and at low 13 C isotopic enrichment. For interday repeatability CVs were between 0.8 and 1.5% at natural abundance and lower than 5.5% at 0.112 and 0.190 atom% enrichment for Val and Thr, respectively. Overall isotopic precision was studied for eleven standard amino acid derivatives (those of Val, Ala, Leu, Iso, Gly, Pro, Asp, Thr, Ser, Met, and Phe) and was assessed at 0.32‰. The 13 C isotopic measurement was then extended to the other amino acids (Ala, Val, Leu, Iso, Gly, Pro, Thr, and Phe) at natural abundance for in-vivo samples. The isotopic precision was better than 0.002 atom% per amino acid (for n=4 rats). This analytical method was finally applied to an animal study to measure Thr utilization in protein synthesis.

Following previous studies on counterfeit of wines with synthetic ingredients, the possibility of frauds by natural external L-tartaric acid has also been investigated. The aim of this research was to map the stable isotope ratios of L-tartaric acid coming from botanical species containing large amounts of this compound: grape and tamarind. Samples of L-tartaric acid were extracted from the pulp of tamarind fruits originating from several countries and from grape must. δ13C and δ18O were measured for all samples. Additional δ2H measurements were performed as a complementary analysis to help discrimination of the botanical origin. Different isotopic patterns were observed for the different botanical origins. The multivariate statistical analysis of the data shows clear discrimination among the different botanical and synthetic sources. This approach could be a complementary tool for the control of L-tartaric acid used in oenology. Copyright © 2007 John Wiley & Sons, Ltd.

A geochemical study of crude oils and samples of various Permian, Triassic and Jurassic organic-rich rock units from the southern Taroom Trough was undertaken to test the prevailing Permian-source hypothesis for the petroleum reserves of the Bowen/Surat Basin. Seventy three core and cuttings samples were screened using organic petrography, total organic carbon analysis, Rock-Eval pyrolysis, and solvent extraction. Saturated and aromatic hydrocarbon fractions of selected source rocks, kerogen hydrous pyrolysates, and thirteen oils were then analysed by gas chromatography, gas chromatography mass spectrometry and isotope ratio mass spectrometry, for the purpose of oil-tosource correlation. On the basis of their bulk carbon isotopic compositions and terpane, sterane and aromatic biomarker signatures, two oil families were identified. Those oils sourced by the Snake Creek Mudstone and reservoired in the Showgrounds Sandstone (both of Middle Triassic age) at Roswin North and Rednook are assigned to the "Snake Creek-Showgrounds" petroleum system. The remaining oils belong to the "Blackwater-Precipice" system. These originated in the Late Permian coal measures of the Blackwater Group but are produced from the Precipice Sandstone and other reservoir rocks of Permian to Jurassic age along the southeastern and southwestern margins of the trough.

Isotope Ratio Mass Spectrometry (IRMS) is a specialized technique used to provide information about the geographic, chemical, and biological origins of substances. The ability to determine the source of an organic substance stems from the relative isotopic abundances of the elements which comprise the material. Because the isotope ratios of elements such as carbon, hydrogen, oxygen, sulfur, and nitrogen can become locally enriched or depleted through a variety of kinetic and thermodynamic factors, measurement of the isotope ratios can be used to differentiate between samples which otherwise share identical chemical compositions. Several sample introduction methods are now available for commercial isotope ratio mass spectrometers. Combustion is most commonly used for bulk isotopic analysis, whereas gas and liquid chromatography are predominately used for the real-time isotopic analysis of specific compounds within a mixture. Here, highlights of advances in instrumentation and applications within the last three years are provided to illustrate the impact of this rapidly growing area of research. Some prominent new applications include authenticating organic food produce, ascertaining whether or not African elephants are guilty of night-time raids on farmers' crops, and linking forensic drug and soil samples from a crime scene to a suspected point of origin. For the sake of brevity, we focus this Minireview on the isotope ratio measurements of lighter-elements common to organic sources; we do not cover the equally important field of inorganic isotope ratio mass spectrometry. His research interests include ion trap development, forensic applications of isotope ratio mass spectrometry and the construction of miniature, portable mass spectrometers. He also teaches workshops on Forensic Applications of Mass Spectrometry.

On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision 13C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure 13C isotopic enrichment of underivatised amino acids (Asp, Thr–Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(δ13C) reported with this method was found to be below 1‰ . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (δ13C = − 12.3 to 150.8‰), the calculated root-mean-square (rms) of SD was 0.38 and 0.46‰ and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (δ13C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound 13C–Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p > 0.05). The results of this work indicate that the LC-IRMS was successful for high-precision 13C isotopic measurements in tracer studies giving 13C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio. Copyright © 2008 John Wiley & Sons, Ltd.

AbstractmThe on-line coupling of gas chromatography and isotope ratio mass spectrometry via a pyrolysis interface (GC-pyrolysis-IRMS, GC-P-IRMS) allows the simultaneous determination of d 13 C and d 18 O values for organic compounds. On the basis of illustrative investigations of vanillin from different origins, the scope and limitations of the new method are discussed.

ABSTRACT:
There is a known bias in C/N, d13C and d15N values of organic matter (OM) due to pre-analysis acid treatment methods. We report here, for the first time, the results of a pre-analysis acid treatment method comparison of measured C/N, d13C and d15N values in bulk OM from a sedimentary sequence of samples to illustrate this bias. Here we show that acid treatment significantly reduces the accuracy (between method biases) and precision (within method bias) of C/N, d13C and d15N values of OM, suggesting a differential response of sample OM between methods and sample horizons, and in some cases inefficient removal of inorganic carbon. We show that different methods can significantly influence environmental interpretation in some of our sample horizons (i.e. interpretation of aquatic vs. terrestrial OM source; C3 vs. C4 vegetation). Specifically, there are unpredictable and non-linear differences between methods for C/N values in the range of ~ 1 – 100; d13C values in the range of 0.2 – 6.8 ‰ and; d15Nvalues in the range of 0.3 – 0.7 ‰. Importantly, these ranges are mostly much greater than the instrument precision (defined as the standard deviation of replicate analysis of standard reference materials; for this study, ± 0.5 for C/N values, ± 0.1 ‰ for d13C values and; ± 0.1 ‰ for d15N). The accuracy and precision of measured C/N, d13C and d15N values of bulk OM is not just dependent upon environmental variability, but on acid pre-treatment, residual inorganic carbon and organic matter state and composition. Collectively, this makes the correlation between samples prepared in different ways, including those from down core reconstructions, highly questionable.

Keywords: C/N ratios, δ13C, δ15N, organic matter; pre-analysis acid treatment methods, environmental interpretation, palaeoclimate.

Sub-basins within the New York/New Jersey (NY/NJ) Harbor host variable amounts and sources of polycyclic aromatic hydrocarbons (PAHs). Analyses of radionuclides 137 Cs and 7 Be were used to assign approximate dates to individual sections of sediment cores collected from four major sub-basins of the harbor complex. Sampling sites range from heavily contaminated Newark Bay and Passaic River to less contaminated Raritan Bay and Jamaica Bay. PAHs were identified with GC-MS and quantified by GC respectively. Gas chromatography-isotope ratio mass spectrometry (GC/IRMS) was applied to determine d 13 C values of pyrene (d 13 C Py ), a principal 4 ring parent PAH. Two end-member PAH source components, petroleum-related PAHs (PRPAH) and combustion-related PAHs (CRPAH), were calculated from a carbon isotopic mass balance equation based on assumptions that petroleum-related d 13 C Py is À29&, and that combustion-derived d 13 C Py is À24&. Temporal trends of PRPAH in these cores are similar to those of the petroleum-derived unresolved complex mixture (UCM), whereas CRPAH resembled trends of ''Total'' PAH (TPAH). Three molecular ratios, fluoranthene to fluoranthene plus pyrene (Fl/(Fl + Py)), high molecular weight 4-6 ring PAH to total PAH (Ring456/TPAH) and parent to total (Par/(Par + Alkyl)), correlate strongly with each other, and show a moderate to strong positive correlation with d 13 C Py . In contrast, the ratios of anthracene to phenanthrene plus anthracene (A/(Pa + A)), benzo[a]anthracene to benzo[a]anthracene plus chrysene (BaA/(BaA+Chy)), and indeno[1,2,3-cd]pyrene to indeno[1,2,3-cd]pyrene plus benzo[ghi]perylene (IP/(IP + Bghi)) show no, weak, or even negative correlation with the four well correlated ratios (d 13 C Py, Par/(Par + Alkyl), Fl/(Fl + Py), and Ring456/TPAH). Combined application of the four well correlated molecular indicators suggests that PAH contribution from combustion became more important in most areas of the NY/NJ Harbor during the last three decades of the 20th century.

Multi-isotope fingerprinting (sulphur, oxygen and strontium isotopes) has been tested to study the provenances of medieval and Renaissance French and Swedish alabaster artwork. Isotope signatures of historical English, French and Spanish alabaster source quarries or areas reveal highly specific, with a strong intra-group homogeneity and strong inter-group contrasts, especially for Sr and S isotopes. The chosen combination of isotope tracers is a good basis for forensic work on alabaster provenance allowing verification of hypotheses about historical trade routes as well as identification of fakes and their origin. The applied analytical techniques of continuous flow isotope ratio mass spectrometry (CF-IRMS) and thermal ionisation mass spectrometry (TIMS) only require micro-samples in the low mg range thus minimising the impact on artwork.

This paper discusses the advance of the speleothem luminescence
research.  Potential,  resolution  and  limitations  of  high  resolution  luminescence  speleothem  proxy  records  of
Paleotemperature, Solar Insolation, Solar Luminosity, Glaciations, Sea Level advances, Past Precipitation, Plants
Populations, Paleosoils, Past Karst Denudation, Chemical Pollution, Cosmic Rays Flux variations, Cosmogenic
Isotopes production and Supernova Eruptions in the Past, Advances of Hydrothermal Waters, and Techtonic Uplift are
discussed. It is demonstrated that speleothems allow extremely high resolution (higher than in any other paleoclimatic
terrestrial archives) and long duration of records. Some speleothems can be used as natural climatic stations for
obtaining of quantitative proxy records of Quaternary climates with annual resolution.

In May 2014, the Rosetta spacecraft is scheduled to rendezvous with the comet Churyumov-Gerasimenko ('67P'). One of the instruments on board the 'Lander' which will descend on to the surface of the comet is a miniaturised GC/MS system that incorporates an ion trap mass spectrometer, specially developed for isotope ratio analysis. This article describes the development and optimisation of the ion trap for this unique application, and presents a summary of the range of pre-programmed experiments that will contribute to the characterisation of the solid and volatile cometary materials.

Scorrer J, Faillace KE, Hildred A, Nederbragt AJ, Andersen MB, Millet M-A, Lamb AL, Madgwick R. 2021 Diversity aboard a Tudor warship: investigating the origins of the Mary Rose crew using multi-isotope analysis. R. Soc. Open Sci. 8: 202106. The great Tudor warship, the Mary Rose, which sank tragically in the Solent in 1545 AD, presents a rare archaeological opportunity to research individuals for whom the precise timing and nature of death are known. A long-standing question surrounds the composition of the Tudor navy and whether the crew were largely British or had more diverse origins. This study takes a multi-isotope approach, combining strontium (87Sr/86Sr), oxygen (
18O), sulfur (
34S), carbon (
13C) and nitrogen (
15N) isotope analysis of dental samples to reconstruct the childhood diet and origins of eight of the Mary Rose crew. Forensic ancestry estimation was also employed on a subsample. Provenancing isotope data tentatively suggests as many as three of the crew may have ...

Pregnenolone (PREG) can potentially be abused by athletes to maintain an equilibration of the steroidal environment after sex steroids administrations. Five men volunteers orally ingested 50 mg PREG to determine optimal urinary markers for detection of this steroid. Our findings show that ingestion of PREG has no significant effects on the testosterone/epitestosterone (T/E) and testosterone/luteinizing hormone (T/LH) ratios, whereas variable changes on the carbon isotopic values of three T metabolites: androsterone, etiocholanolone, 5␤-androstane-3␣,17␤-diol (5␤-androstanediol) together with 16(5␣)-androsten-3␣-ol (androstenol) and 5␤-pregnane-3␣,20␣-diol (pregnanediol) have been observed. The difference between the carbon isotopic values (δ 13 C-values) of androstenol and pregnanediol is potentially the most reliable marker of exogenous PREG administration in males. For all subjects, the differences differ by 3.0‰ or more over a period of about 10 h and for both of them the detection window for positivity is extended over 40 h.

An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures. The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid. Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed. The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material. Crown

Gas chromatographic (GC) determination of volatile constituents and isotope ratio mass spectrometry (IRMS) analysis of 13C/12C isotope ratios as well as SNIF-NMR analysis of (D/H)-ratios of ethanol in authentic (n=12) and commercial tequila samples (n=13) were used to differentiate analytically between tequila derived from 100% agave (Agave tequilana Weber var. Azul) and tequila produced with other fermentable sugars ('mixed' tequila). Evaluating the correlation of methanol and 2-/3-methyl-1-butanol concentrations, GC analysis was found to be a suitable method for the authenticity assessment of '100% agave' and 'mixed' tequilas. Additional determinations of δ13CVPDB and (D/H) ratios of ethanol were used to show the perspectives and limits of the methods.

We applied direct injections of headspace gas into a Gas Chromatography -Combustion -Isotope Ratio Mass Spectrometry (GC-C-IRMS) system to measure 13 C/ 12 C isotopic ratio of carbon dioxide from the headspace of several sparkling and soft-drinks. This straightforward technique, which consists in an automated analysis of the headspace sample with no prior purification steps, improves the determination of d 13 C values of CO 2 gas as a food probe authenticity. However, for an ultimate test, combination with other isotopic data is required.

Since considerable time, isotopic analysis of different elements present in a sample, material or object (such as the 'light' elements H, C, N, O and S and 'heavy' elements, such as Sr and Pb), has been used in provenancing studies, as several factorsdefined by "the environment" or origin of the samplecan lead to measurable differences in their isotopic composition. For the light elements, traditionally, (gas source) isotope ratio mass spectrometry (IR-MS) is used, while for a long period of time, thermal ionization mass spectrometry (TIMS) was considered as the only technique capable of detecting subtle variations in the isotopic composition of the 'heavier' elements. However, since the introduction of the first inductively coupled plasma mass spectrometers (ICP-MS), considerable attention has been devoted to the development of methodologies and strategies to perform isotopic analysis by means of ICP-MS. While the relatively modest isotope ratio precision offered by single-collector ICP-MS may already be fit-for-purpose under some circumstances, especially the introduction of multi-collector ICP-MS instruments, equipped with an array of Faraday detectors instead of a single electron multiplier, has lead to tremendous improvements in the field of isotopic analysis. As a result, MC-ICP-MS can be seen as a very strong competitor of TIMS nowadays, while it even provides information on the small isotopic variations shown by some elements, that are not or hardly accessible by means of TIMS (e.g., elements with a high ionization energy). Owing to these new instrumental developments, the application field of isotopic analysis by means of ICP-MS is continuously growing, also in the field of provenance determination. This paper is intended as a review of the developments in and the recent applications of isotopic analysis by means of ICP-MS in this specific research field.

Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseous samples. Nowadays, laser spectroscopy is clearly recognized as a valid alternative to isotope ratio mass spectrometry. Laser-based instruments are leaving the research laboratory stage and are being used by a growing number of isotope researchers for significant advances in their own field of research. In this review article, we discuss the current status and new frontiers of research on high-sensitivity and high-precision laser spectroscopy for isotope ratio analyses. Although many of our comments will be generally applicable to laser isotope ratio analyses in molecules of environmental importance, this paper concerns itself primarily with water and carbon dioxide, two molecules that were studied extensively in our respective laboratories. A complete coverage of the field is practically not feasible in the space constraints of this issue, and in any case doomed to fail, considering the large body of work that has appeared ever since the review by Kerstel in 2004 ( Handbook of Stable Isotope Analytical Techniques, Chapt. 34, pp. 759-787).

Since considerable time, isotopic analysis of different elements present in a sample, material or object (such as the 'light' elements H, C, N, O and S and 'heavy' elements, such as Sr and Pb), has been used in provenancing studies, as several factorsdefined by "the environment" or origin of the samplecan lead to measurable differences in their isotopic composition. For the light elements, traditionally, (gas source) isotope ratio mass spectrometry (IR-MS) is used, while for a long period of time, thermal ionization mass spectrometry (TIMS) was considered as the only technique capable of detecting subtle variations in the isotopic composition of the 'heavier' elements. However, since the introduction of the first inductively coupled plasma mass spectrometers (ICP-MS), considerable attention has been devoted to the development of methodologies and strategies to perform isotopic analysis by means of ICP-MS. While the relatively modest isotope ratio precision offered by single-collector ICP-MS may already be fit-for-purpose under some circumstances, especially the introduction of multi-collector ICP-MS instruments, equipped with an array of Faraday detectors instead of a single electron multiplier, has lead to tremendous improvements in the field of isotopic analysis. As a result, MC-ICP-MS can be seen as a very strong competitor of TIMS nowadays, while it even provides information on the small isotopic variations shown by some elements, that are not or hardly accessible by means of TIMS (e.g., elements with a high ionization energy). Owing to these new instrumental developments, the application field of isotopic analysis by means of ICP-MS is continuously growing, also in the field of provenance determination. This paper is intended as a review of the developments in and the recent applications of isotopic analysis by means of ICP-MS in this specific research field.

Total lipid extracts and insoluble organic matter, i.e. solvent insoluble matter and humic acids, were studied from soil samples taken from the three adjacent plots comprising the Broadbalk Wilderness at Rothamsted Experimental Station, Harpenden, Hertfordshire, U.K. Analyses involved high-temperature gas chromatography (HT-GC) and HT-GC-mass spectrometry (HT-GC-MS) to investigate trimethylsilylated total lipid extracts and Curie-point pyrolysis-GC (Py-GC) and Py-GC-MS to investigate solvent insoluble fractions. The plots were chosen specifically for their different types of vegetation cover. Samples of the vegetation were examined in parallel with the underlying soils in an effort to follow the fate of the major plant components in soil. The application of HT-GC and HT-GC-MS allowed changes in high molecular weight lipids, particularly intact acyl lipids, such as triacylglycerols, wax esters, steryl and triterpenyl esters, to be studied in leaf and soil extracts. The total lipid extracts of the soil samples from the wooded area were dominated by the input from leaf-derived lipids. The lipid extracts of soils from the grazed and stubbed areas were markedly different from those from the wooded area, and reflected the mixed vegetation cover dominated by grass species. In marked contrast, the pyrolysis data from the insoluble organic matter and humic fractions of the soils did not reflect the composition of the lignin comprising the overlying vegetation, but rather showed evidence of amino acid moieties probably present as polypeptides. The absence of the iignin signal is possibly due to rapid diagenetic changes presumed to be influenced by the slightly alkaline pH of the soil. The ability to recover recognizable chemical signals from soil lipids has important implications for archaeological investigations aimed at revealing temporal changes in vegetation cover and/or differences in land use at specific site locations. © 1997 Elsevier Science Ltd

This paper is a preliminary investigation into the use of a thermal desorption-gas chromatography-isotope ratio mass spectrometry (TD-GC-IR-MS) method to determine stable carbon isotopic compositions (d 13 C) of low molecular-weight volatile organic compounds (VOCs) in airborne samples (e.g. industrial and car exhaust emissions) as a means of differentiating their sources in the environment. A TD-GC-IR-MS method for obtaining d 13 C of VOCs (benzene, toluene, chlorobenzene, ethylbenzene, m-xylene and propylbenzene) in air samples has been optimised, and is proven to be both reproducible and linear. The d 13 C of the VOC standards was found to be comparable (within analytical error) to that obtained from direct GC-IR-MS analysis. This novel method of VOC analysis is valuable in environmental and forensic investigations.

Hadal trenches are isolated habitats that cover the greatest ocean depths (6,500–11,000 m) and are believed to host high levels of endemism across multiple taxa. A group of apparent hadal endemics is within the snailfishes (Liparidae), found in at least five geographically separated trenches. Little is known about their biology, let alone the reasons for their success at hadal depths around the world. This study investigated the life history of hadal liparids using sagittal otoliths of two species from the Kermadec (Notoliparis kermadecensis) and Mariana (Pseudoliparis swirei) trenches in comparison to successful abyssal macrourids found at the abyssal-hadal transition zone. Otoliths for each species revealed alternating opaque and translucent growth zones that could be quantified in medial sections. Assuming these annuli represent annual growth, ages were estimated for the two hadal liparid species to be from five to 16 years old. These estimates were compared to the shallower-living snailfish Careproctus melanurus, which were older than described in previous studies, expanding the potential maximum age for the liparid family to near 25 years. Age estimates for abyssal macrourids ranged from eight to 29 years for Coryphaenoides armatus and six to 16 years for C. yaquinae. In addition, 18 O/ 16 O ratios (δ 18 O) were measured across the otolith using secondary ion mass spectrometry (SIMS) to investigate the thermal history of the three liparids, and two macrourids. Changes in δ 18 O values were observed across the otoliths of C. melanurus, C. armatus, and both hadal liparids, the latter of which may represent a change of > 5 °C in habitat temperature through ontogeny. The results would indicate there is a pelagic larval stage for the hadal liparids that rises to a depth above 1000 m, followed by a return to the hadal environment as these liparids grow. This result was unexpected for the hadal liparids given their isolated environment and large eggs, and the biological implications and plausibility of interpretations of these data are discussed. This study presents a first look at the life history of some of the deepest-living fishes through otolith analyses.

Anecdotal evidence as well as observations made in our own stable isotope laboratory suggest for samples with either a high alkali and/or halogen content (such as marine samples or certain soil samples) or a high carbon and oxygen content (such as carbohydrates) to result in flash combustion temperatures exceeding temperature or burn time or both of flash combustion under typical conditions.  Whatever the exact circumstances during combustion of such samples, they compromise chemical and thus structural integrity and thus weaken the wall of the quartz glass reactors in the combustion zone and ultimately lead to pin-prick holes being formed through which carrier gas escapes thus resulting in a dramatic loss of carrier gas flow.  Occasionally these pin-prick holes get plugged or “sealed” by molten tin thus restoring carrier gas flow but at the other end of the spectrum these pin-prick holes can become so wide for molten tin being able to pass through and to run down the outside of the reactor tube.  In the latter event, a catastrophic failure of the reactor tube is inevitable with carrier gas flow downstream of the holes dropping to almost zero.
While pin-prick holes (going unnoticed during an autosampler run of a large batch of samples) typically result in the loss of 3 or 4 samples until the hole/s “self-sealed” with molten tin, in a worst case scenario a catastrophic failure of the reactor tube can result in the loss of 40 or more samples (depending on number of samples in a batch run and when the failure occurred).
Here we present examples of combustion reactor failure as well as observations made with crucibles made of quartz glass, stainless steel or inconel alloy during experiments to see if crucible design can mitigate against the effects of problematic samples.
Geophysical Research Abstracts, 15, EGU2013-13881.

The reputation of particular countries, and plantations within those countries, for the production of high quality tea means that these producers can ask a significantly higher price for their specific product than average. This leads to a temptation for unscrupulous producers to fraudulently label their product as coming from one of these areas to take advantage of this higher price. A simple method for the analysis and verification of the country and plantation of origin of tea would provide security to both tea growers and consumers and would largely stamp out this illegal activity. This paper details the use of complimentary organic and inorganic isotope techniques for the analysis of tea samples from Asia. The application of linear discriminant analysis of the isotope ratios and mineral concentrations permitted 97.6% correct classification of the tea samples using the following variables dD,

In this study we investigated the effects of experimental biomanipulation on community structure, ecosystem metabolism, carbon biogeochemistry and stable isotope composition of a shallow eutrophic lake in the Netherlands. Three different biomanipulation treatments were applied. In two parts of the lake, isolated from the rest, fish was removed and one part was used as a reference treatment in which no biomanipulation was applied. Stable isotopes have proved useful to trace trophic interactions at higher food web levels but until now methodological limitations have restricted species specific isotope analysis in the plankton community. We applied a new approach based on the combination of fluorescence activated cell sorting (FACS) and isotope ratio mass spectrometry (IRMS) to trace carbon flow through the planktonic food web. With this method we aimed at obtaining group specific δ 13 C signatures of phytoplankton and to trace possible shifts in δ 13 C resulting from fish removal.

Scorrer J, Faillace KE, Hildred A, Nederbragt AJ, Andersen MB, Millet M-A, Lamb AL, Madgwick R. 2021 Diversity aboard a Tudor warship: investigating the origins of the Mary Rose crew using multi-isotope analysis. R. Soc. Open Sci. 8: 202106.

The great Tudor warship, the Mary Rose, which sank tragically in the Solent in 1545 AD, presents a rare archaeological opportunity to research individuals for whom the precise timing and nature of death are known. A long-standing question surrounds the composition of the Tudor navy and whether the crew were largely British or had more
diverse origins. This study takes a multi-isotope approach, combining strontium (87Sr/86Sr), oxygen (
18O), sulfur (
34S), carbon (
13C) and nitrogen (
15N) isotope analysis of dental samples to reconstruct the childhood diet and origins of eight of the Mary Rose crew. Forensic ancestry estimation was also employed on a subsample. Provenancing isotope data tentatively suggests as many as three of the crew may have
originated from warmer, more southerly climates than Britain. Five have isotope values indicative of childhoods spent in western Britain, one of which had cranial morphology suggestive of African ancestry. The general trend of relatively high
15N and low
13C values suggests a broadly comparable diet to contemporaneous British and European communities. This multi-isotope approach and the nature of the
archaeological context has allowed the reconstruction of the
biographies of eight Tudor individuals to a higher resolution
than is usually possible.

Coarseware vessels from excavations at Isthmia, Greece, in contexts dating from the Hellenistic and Roman periods, resemble ceramic beehives used by the ancient Greeks and still in recent use on the Cycladic islands and Crete. Chemical investigations of absorbed residues were performed with the aim of obtaining direct evidence for the use of these vessels as beehives. High-temperature gas chromatography (HT-GC) and HT-GC/mass spectrometry (HT-GC/MS) were used to screen lipid extracts for the presence of compounds characteristic of beeswax. Samples of beeswax taken from a 19C ethnographic beehive was used as reference material. Potsherds from 10 pithoi recovered from the same Isthmia excavation served as controls. A significant proportion of the sherds from the putative beehive vessels contained compounds, i.e. n-alkanes, wax esters, fatty acids and long-chain alcohols congruent with those seen in the reference beeswax. 13 C values were determined for the individual components of the lipid extracts and reference beeswax by means of compound specific GC-combustion-isotope ratio mass spectrometry (GC-C-IRMS). On the basis of the molecular structures, carbon number distributions and 13 C values 16 of the 40 sherds studied were shown to contain residues of beeswax. None of the pithoi contained beeswax residues although two yielded residues consistent with degraded triacylglycerols.

Enantioselective capillary GC on a Supelco β-DEX 225 column (heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin SPB 20poly-20% diphenyl, 80% dimethylsiloxane) and isotope-ratio mass spectrometry, coupled online with capillary GC on an HP5 column have been used for origin-specific analysis and authenticity control of essential oils, for example lemon (Citrus limon), lemongrass (Cymbopogon citratus and Cymbopogon flexuosus), citronella (Cymbopogon nardus L.-Ceylon type and Cymbopogon winterianus-Java type), Litsea cubeba, Lippia citriodora, lemon myrtle (Backhousia citriodora), lemon gum (Eucalyptus citriodora), and, especially, precious lemon balm oil (Melissa officinalis L.). Isotope data (δ 13 C PDB and δ 2 H V-SMOW ) for citral (neral+geranial) and citronellal from on-line GC-C/Py-IRMS and chiral data for citronellal in these essential oils are reported. The possibility of using these data to determine the origin of these essential oils and to detect adulteration is discussed. Principal-components analysis (PCA) of specific compounds in two essential oils of lemongrass and Litsea cubeba was performed as a practical statistical method for distinguishing between these two types of oil.

Total lipid extracts and insoluble organic matter, i.e. solvent insoluble matter and humic acids, were studied from soil samples taken from the three adjacent plots comprising the Broadbalk Wilderness at Rothamsted Experimental Station, Harpenden, Hertfordshire, U.K. Analyses involved high-temperature gas chromatography (HT-GC) and HT-GC-mass spectrometry (HT-GC-MS) to investigate trimethylsilylated total lipid extracts and Curie-point pyrolysis-GC (Py-GC) and Py-GC-MS to investigate solvent insoluble fractions. The plots were chosen specifically for their different types of vegetation cover. Samples of the vegetation were examined in parallel with the underlying soils in an effort to follow the fate of the major plant components in soil. The application of HT-GC and HT-GC-MS allowed changes in high molecular weight lipids, particularly intact acyl lipids, such as triacylglycerols, wax esters, steryl and triterpenyl esters, to be studied in leaf and soil extracts. The total lipid extracts of the soil samples from the wooded area were dominated by the input from leaf-derived lipids. The lipid extracts of soils from the grazed and stubbed areas were markedly different from those from the wooded area, and reflected the mixed vegetation cover dominated by grass species. In marked contrast, the pyrolysis data from the insoluble organic matter and humic fractions of the soils did not reflect the composition of the lignin comprising the overlying vegetation, but rather showed evidence of amino acid moieties probably present as polypeptides. The absence of the iignin signal is possibly due to rapid diagenetic changes presumed to be influenced by the slightly alkaline pH of the soil. The ability to recover recognizable chemical signals from soil lipids has important implications for archaeological investigations aimed at revealing temporal changes in vegetation cover and/or differences in land use at specific site locations. © 1997 Elsevier Science Ltd