Compound-specific Carbon Isotope Ratios Research Articles

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.

Botanical characterization and authentication of lavender essential oil using its volatile organic compounds and compound-specific carbon and hydrogen isotope ratio analysis

The determination of authenticity and provenance is one of the main issues in high-value natural products such as lavender (L. angustifolia) essential oil. Due to their high value, natural products are often totally or partially substituted with cheaper alternatives. Therefore, it is necessary to accurately characterize the composition of lavender essential oil and its related species, particularly lavandin (L. intermedia) essential oil, which is frequently used as an adulterant. In this study, we analyzed the most distinctive volatile organic compounds (VOCs) and their relative compound-specific stable carbon and hydrogen (δ13C and δ2H) isotope ratios in lavender, lavandin, and commercial lavender essential oil samples using fast GC-MS/MS and GC-IRMS methods and sparse Partial Least Square Discriminant Analysis (sPLS-DA) to classify and verify their botanical origin. For the first time, concentration ranges for 79 VOCs and the δ13C and δ2H values in 32 VOCs were used to characterize lavender essential oils. sPLS-DA models with either VOCs, δ13C and δ2H, or in combination successfully classify lavender and lavandin with 100% accuracy. VOCs such as camphor, borneol, eucalyptol, α-bisabolol, and α-pinene were found to be the most important variables for differentiating lavender oil from lavandin. Similarly, δ13C in camphor, eucalyptol, trans-β-ocimene and 3-octanone, and δ2H in α-terpineol and trans-β-ocimene and 3-octanone also differentiated lavender and lavandin oil. In addition, we demonstrated that compound-specific δ13C and δ2H detected the adulteration of natural lavender or lavandin oil if more than 15% of linalool, linalyl acetate, eucalyptol, and α-terpineol were of synthetic origin. These preliminary results with sPLS-DA models suggest that VOCs and compound-specific δ13C and δ2H can be a promising tool for the botanical classification of lavender essential oil and the detection of possible adulteration with synthetic compounds.

Compound-specific carbon isotope measurements of individual lipid biomarkers from immature Ediacaran rocks of Baltica

Compound-specific carbon isotope ratios (CSIA) were measured for a suite of lipid biomarker compounds extracted from immature, late Ediacaran sedimentary rocks from drill cores sampled across Baltica. Using a newly developed picomolar‐scale CSIA (pico‐CSIA) method, we measured carbon isotope compositions of the abundant n-alkanes and hopanes, as well as C29 sterane, pristane, and phytane. Total organic carbon (TOC) of the Kotlin Regional Horizon in Baltica (Saint Petersburg area, Utkina Zavod drill core), from a low-salinity coastal environment, is consistently enriched in 13C by up to 10‰, compared to that for Redkino and Kotlin marine rocks from other locations in Baltica. This 13C enrichment is also recorded by the n-alkanes, hopanes, phytane, and C29 sterane. In all locations, the δ13C values of the C29 sterane are within 2‰ of the bacterial hopane δ13C values and within 0.7‰ of δ13CTOC, suggesting that the abundant hopanes within these sediments could be derived from RuBisCO Calvin-Benson-Bassham pathway-utilizing organisms, as well as from bacterial heterotrophs. Since δ13Clipid signature tracks δ13CTOC values for the Kotlin Regional Horizon samples from Utkina Zavod location, the significant 13C enrichments in this interval reflect either the δ13C composition of DIC used for autotrophy or a muted magnitude of carbon isotope fractionation during lipid biosynthesis, but are not due to enhanced preservation of organic compounds and geopolymers derived from 13C-enriched biochemicals. Pico-CSIA and biomarker data provide evidence for both regional environmental heterogeneity and secular changes in carbon cycling during deposition of sediments of the Kotlin and Redkino Regional Horizon intervals.

Fate of free and bound phytol and tocopherols during fruit ripening of two Capsicum cultivars

Phytol and tocopherols and their fatty acid esters (PFAE and TFAE) are isoprenoid lipid components which can be found for instance in vegetables. Their behavior during maturation of fruits and vegetables could reveal valuable information on their biosynthetic formation and biological function. As pods of the genus Capsicum contain considerable amounts of both PFAE and TFAE, two cultivars (i.e. Capsicum annuum var. Forajido and Capsicum chinense var. Habanero) were grown in a greenhouse project. The date of flowering and fruit formation of each blossom was noted and fruits were harvested in four specific periods which corresponded with different stages of ripening, i.e. unripe, semi-ripe, ripe and overripe. Quantification by means of gas chromatography mass spectrometry and creation of development profiles strongly supported the suggestion that PFAE and TFAE were formed as storage molecules during fruit ripening and parallel degradation of chlorophyll. Additionally, compound-specific carbon isotope ratios (δ13C values (‰)) of originally in PFAE and chlorophyll bound phytol ultimately proved that PFAE, besides tocopherols, serve as sink for the cytotoxic phytol moiety released from chlorophyll degradation during fruit ripening. Furthermore, color measurements were successfully implemented to simplify the usually cumbersome separation of chili fruits into different ripening degrees.

Dried Blood Spot Sampling of Landlocked Arctic Char (Salvelinus alpinus) for Estimating Mercury Exposure and Stable Carbon Isotope Fingerprinting of Essential Amino Acids.

Dried blood spots (DBS), created by applying and drying a whole blood sample onto filter paper, provide a simple and minimally invasive procedure for collecting, transporting, and storing blood. Because DBS are ideal for use in field and resource-limited settings, we aimed to develop a simple and accurate DBS-based approach for assessing mercury (Hg) exposure and dietary carbon sources for landlocked Arctic char, a sentinel fish species in the Arctic. We collected liquid whole blood (from the caudal vein), muscle, liver, and brains of Arctic char (n = 36) from 8 lakes spanning a Hg gradient in the Canadian High Arctic. We measured total Hg concentrations ([THg]) of field-prepared DBS and Arctic char tissues. Across a considerable range, [THg] of DBS (0.04-3.38 μg/g wet wt) were highly correlated with [THg] of all tissues (r2 range = 0.928-0.996). We also analyzed the compound-specific carbon isotope ratios (expressed as δ13 C values) of essential amino acids (EAAs) isolated from DBS, liquid whole blood, and muscle. The δ13 C values of 5 EAAs (δ13 CEAAs ; isoleucine [Ile], leucine [Leu], phenylalanine [Phe], valine [Val], and threonine [Thr]) from DBS were highly correlated with δ13 CEAAs of liquid whole blood (r2 range = 0.693-0.895) and muscle (r2 range = 0.642-0.881). The patterns of δ13 CEAAs of landlocked Arctic char were remarkably consistent across sample types and indicate that EAAs are most likely of algal origin. Because a small volume of blood (~50 µL) dried on filter paper can be used to determine Hg exposure levels of various tissues and to fingerprint carbon sources, DBS sampling may decrease the burdens of research and may be developed as a nonlethal sampling technique. Environ Toxicol Chem 2020;39:893-903. © 2020 SETAC.

Assessment of hexachlorcyclohexane biodegradation in contaminated soil by compound-specific stable isotope analysis

Compound-specific isotope analysis (CSIA) was firstly applied to explore the biodegradation of hexachlorcyclohexane (HCH) isomers in contaminated soil. Concentrations and compound-specific carbon isotope ratio profiles of HCH in different specific ex-situ pilot-scale contaminated soil mesocosms were determined. The addition of nutrients and Sphingobium spp. significantly enhanced the degradation of HCH in contaminated soils within 90 days. Isomer specific biodegradation of HCHs was observed with α- and γ-HCH being more degradable than β and δ-HCH. Stable carbon isotope fractionation of HCH was observed and the δ13C values shifted from −28.8 ± 0.3‰ to −24.8 ± 0.7‰ upon 87.3% removal, −27.9 ± 0.2‰ to −25.9 ± 0.5‰ upon 72.8% removal, −29.4 ± 0.3‰ to −19.9 ± 0.6‰ upon 95.8% removal, and −27.8 ± 0.5‰ to −23.6 ± 0.7‰ after 96.9% removal for α, β, γ, and δ-HCH, respectively. Furthermore, the enrichment factor ε for α, β, γ, and δ-HCH biodegradation in soil was obtained for the first time as −2.0‰, −1.5‰, −3.2‰, and −1.4‰, which could play a critical role in assessing in situ biodegradation of HCH isomers in field site soil. Results from ex-situ pilot-scale experiments clearly demonstrated that CSIA could be a promising tool to qualitatively and quantitatively evaluate in situ biodegradation of HCH in contaminated field site.

New Concepts for the Determination of Oxidation Efficiencies in Liquid Chromatography-Isotope Ratio Mass Spectrometry.

In liquid chromatography coupled to isotope ratio mass spectrometry (LC-IRMS), analytes are separated on an LC system and consecutively oxidized to CO2, which is required for the determination of compound-specific carbon isotope ratios. Oxidation is performed in an online reactor by sulfate radicals. Reaction conditions in the interface depend on the flow conditions determined by the LC method and the flow rates and concentrations of oxidation agent and phosphoric acid added in the interface. To determine accurate isotope ratios, a quantitative conversion of the carbon contained in the analyte to the CO2 measurement gas is a prerequisite. Oxidation efficiencies are not commonly evaluated during method development, although certain analytes are known to be difficult to be oxidized by sulfate radicals. For the assessment of the oxidation efficiency of the LC-IRMS system, three different approaches were evaluated. (1) Residual organic carbon in the eluent stream of the interface was determined to calculate oxidation yields depending on the initial analyte concentration. (2) The IRMS response was calibrated to an inorganic carbon reference material to determine oxidation efficiencies with the help of the IRMS as a detector. (3) The oxidation temperature was deliberately reduced while monitoring the δ13C and signal intensity. The common assumption that a linear relation of IRMS signal to analyte concentration is an indicator for complete oxidation in LC-IRMS could be disproved. All three approaches can be applied for future method development in LC-IRMS, monitoring of existing flow injection applications, as well as for verification of complete oxidation in established LC-IRMS methods.

Impact of drill core contamination on compound-specific carbon and hydrogen isotopic signatures

Compound-specific carbon and hydrogen isotope ratios are routinely measured on extractable organic matter to decipher biogeochemical processes and events in Earth history. To deliver accurate interpretations, it is paramount that isotopic values are derived from indigenous compounds and are not the result of contamination. However, distinguishing between compounds from these different provenances can be difficult, especially if a degree of mixing occurred. In this study, we assess the impact of hydrocarbon contamination on the carbon and hydrogen isotopic composition of n-alkanes from ∼820 Ma Precambrian evaporitic drill core samples through exterior/interior (E/I) rock extraction experiments. In these experiments, exterior and interior portions of the same rock samples were separately crushed to powder, extracted and processed. Compound-specific isotope values of n-alkanes from the different rock portions were subsequently measured and compared. In most cases, n-alkanes from exterior rock portions had consistently more depleted δ13C and δ2H values than their interior counterparts with an E/I isotopic offset averaging 0.1–6.9‰ for δ13C and 2–33‰ for δ2H. These diverging isotope patterns tend to correspond to E/I concentration differences of n-alkanes and are the result of contaminants overprinting on indigenous isotopic signals. Through the application of E/I experiments, the degree of isotopic overprinting can be investigated and mixed indigenous/contaminant signals identified.

Characteristics and compound-specific carbon isotope compositions of sedimentary lipids in high arsenic aquifers in the Hetao basin, Inner Mongolia

Organic matter, as an electron donor, plays a vital role in As mobilization mediated by microorganisms during reductive dissolution of Fe/Mn oxides in shallow aquifers. However, the specific types and sources of organic matter involved in biogeochemical processes accelerating As mobilization are still controversial. Both sediment and groundwater samples were collected at different depths from aquifers of the Hetao Basin, a typical inland basin hosting high As groundwater. Sedimentary lipids and their compound-specific carbon isotope ratios were analyzed to evaluate characteristics and sources of organic matter. Results show that sedimentary As were well correlated with Fe and Mn oxides, suggesting that As exist as Fe/Mn oxide bound forms. Groundwater As far exceeded the drinking water guide value of 10 μg/L. Moreover, As concentrations in shallow groundwater were relatively higher. Lipids in clay were mainly originated from terrestrial higher plants, while that in fine sand samples were derived from terrestrial higher plants, microorganism and petroleum. Shallow fine sand samples were also characterized by evident in-situ biodegradation. Compound-specific carbon isotope compositions of sedimentary lipids showed that short-chain n-alkanes and n-alkanoic acids had more positive δ13C values compared to long-chain compounds, especially in shallow fine sand samples. δ13CTOC were also low in shallow fine sand samples. These results jointly indicate that these lipids in shallow fine sand samples acted as carbon source for indigenous microorganism and the short-chain components were particularly more vulnerable to biodegradation, which may contribute to high As concentrations in shallow groundwater. The new findings provide the first evidence that short chain length n-alkyl compounds afforded a source of potential electron donors for microbially mediated As mobilization process in the shallow aquifers.

Microbial production of long-chain n-alkanes: Implication for interpreting sedimentary leaf wax signals

Relative distributions as well as compound-specific carbon and hydrogen isotope ratios of long-chain C25 to C33n-alkanes in sediments provide important paleoclimate and paleoenvironmental information. These compounds in aquatic sediments are generally attributed to leaf waxes produced by higher plants. However, whether microbes, such as fungi and bacteria, can make a significant contribution to sedimentary long-chain n-alkanes is uncertain, with only scattered reports in the early 1960s to 1970s that microbes can produce long-chain n-alkanes. Given the rapidly expanding importance of leaf waxes in paleoclimate and paleoenvironmental studies, the impact of microbial contribution to long-chain n-alkanes in sediments must be fully addressed. In this study, we performed laboratory incubation of peatland soils under both anaerobic and aerobic conditions in the absence of light with deuterium-enriched water over 1.5 years and analyzed compound-specific hydrogen isotopic ratios of n-alkanes. Under aerobic conditions, we find n-alkanes of different chain length display variable degrees of hydrogen isotopic enrichments, with short-chain (C18–C21) n-alkanes showing the greatest enrichment, followed by long-chain “leaf wax” (C27–C31) n-alkanes, and minimal or no enrichment for mid-chain (C22–C25) n-alkanes. In contrast, only the shorter chain (C18 and C19) n-alkanes display appreciable isotopic enrichment under anaerobic conditions. The degrees of isotopic enrichment for individual n-alkanes allow for a quantitative assessment of microbial contributions to n-alkanes. Overall our results show the microbial contribution to long-chain n-alkanes can reach up to 0.1% per year in aerobic conditions. For shorter chain n-alkanes, up to 2.5% per year could be produced by microbes in aerobic and anaerobic conditions respectively. Our results indicate that prolonged exposure to aerobic conditions can lead to substantial accumulation of microbially derived long-chain n-alkanes in sediments while original n-alkanes of leaf wax origin are degraded; hence caution must be exercised when interpreting sedimentary records of long-chain n-alkanes, including chain length distributions and isotopic ratios.

Enrichment of 13C in diacids and related compounds during photochemical processing of aqueous aerosols: New proxy for organic aerosols aging.

To investigate the applicability of compound specific stable carbon isotope ratios (δ13C) of organics in assessment of their photochemical aging in the atmosphere, batch UV irradiation experiments were conducted on two ambient (anthropogenic and biogenic) aerosol samples in aqueous phase for 0.5–120 h. The irradiated samples were analyzed for δ13C of diacids, glyoxylic acid (ωC2) and glyoxal. δ13C of diacids and related compounds became larger with irradiation time (i.e., aging), except for few cases. In general, δ13C of C2-C4 diacids showed an increasing trend with decreasing chain length. Based on δ13C of diacids and related compounds and their relations to their concentrations, we found that C2 and C3 are enriched with 13C during the photochemical decomposition and production from their higher homologues and oxoacids. Photochemical breakdown of higher (≥C3) to lower diacids is also important in the enrichment of 13C in C3-C9 diacids whereas their production from primary precursors causes depletion of 13C. In case of ωC2 and glyoxal, their photochemical production and further oxidation to highly oxygenated compounds both cause the enrichment of 13C. This study reveals that δ13C of diacids and related compounds can be used as a proxy to trace the aging of organic aerosols during long-range atmospheric transport.

Terrestrial n-alkanes and their carbon isotope records from the Hanon paleo-maar sediment, Jeju Island, Korea: Implications for paleoclimate and paleovegetation over the last 35 kyrs

The carbon isotope of total carbon (δ13Corg), long-chain n-alkanes, and their compound-specific carbon isotope ratios (δ13CALK) were investigated in the Hanon paleo-maar sediment, Jeju Island of Korea to understand paleoclimate variabilities and their paleovegetation linkages. Based on the organic geochemical data (TOC (%), TN (%), and their δ13Corg and δ15N), the core column stratigraphy was divided into three units, namely from the bottom to 14.5 ka (Unit I), from 14.5 ka to 3.0 ka (Unit II), and from 3.0 ka to the core top (Unit III), respectively. In particular, δ13Corg showed marked fluctuation from −17.31‰ to −28.68‰, suggesting different organic carbon sources. A relatively narrow range of variation in δ13Corg was observed in Unit III, and drastic changes in δ13Corg were observed from Unit I to Unit II. This may indicate a predominance of C4 plants in Unit I, and drastic changes from terrestrial C4 to C3 in Unit II and predominance of C3 plants in Unit III. The distributions of n-alkane were characterized by a continuous predominance of odd-numbered n-alkanes, particularly nC29 and nC31, and by high fluctuation of the total n-alkanes concentration. The average chain length (ACL), carbon preferences index (CPI), and paleo-plant proxy (Paq) showed high fluctuation and glacial-interglacial variations with distinctive a high and low ratio at about 9.2 ka, corresponding to the switching points of δ13Corg and a high concentration of n-alkane distribution. Individual n-alkane odd-numbered isotopes of δ13CALK ranged between −11.80‰ in δ13nC21 and -34.93‰ in δ13nC31, suggesting different sources of n-alkanes. The distribution of n-alkanes and their individual δ13CALK, in particular δ13nC21, support paleovegetation changes, and their time-dependent variations matched well with glacial-interglacial paleoclimate variations. Therefore, organic geochemical proxies recorded in Hanon paleo-maar sediment reflects paleoclimate variabilities as well as paleovegetation changes for the last 35 kyr in Jeju Island, Korea.

The origin of amino acids in lunar regolith samples

We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7ppb in hot-water extracts and 14.5–651.1ppb in 6M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, d- and l-alanine, d- and l-aspartic acid, d- and l-glutamic acid, d- and l-serine, l-threonine, and l-valine, all of which had previously been detected in lunar samples, as well as several compounds not previously identified in lunar regoliths: α-aminoisobutyric acid (AIB), d- and l-β-amino-n-butyric acid (β-ABA), dl-α-amino-n-butyric acid, γ-amino-n-butyric acid, β-alanine, and ε-amino-n-caproic acid. We observed an excess of the l enantiomer in most of the detected proteinogenic amino acids, but racemic alanine and racemic β-ABA were present in some samples.We also examined seven samples from Apollo 15, 16, and 17 that had been previously allocated to a non-curation laboratory, as well as two samples of terrestrial dunite from studies of lunar module engine exhaust that had been stored in the same laboratory. The amino acid content of these samples suggested that contamination had occurred during non-curatorial storage.We measured the compound-specific carbon isotopic ratios of glycine, β-alanine, and l-alanine in Apollo regolith sample 70011 and found values of −21‰ to −33‰. These values are consistent with those seen in terrestrial biology and, together with the enantiomeric compositions of the proteinogenic amino acids, suggest that terrestrial biological contamination is a primary source of the amino acids in these samples. However, the presence of the non-proteinogenic amino acids such as AIB and β-ABA suggests the possibility of some contribution from exogenous sources.We did not observe a correlation of amino acid content with proximity to the Apollo 17 lunar module, implying that lunar module exhaust was not a primary source of amino acid precursors. Solar-wind-implanted precursors such as HCN also appear to be at most a minor contributor, given a lack of correlation between amino acid content and soil maturity (as measured by Is/FeO ratio) and the differences between the δ13C values of the amino acids and the solar wind.

Paleovegetation and paleoclimate changes based on terrestrial n-alkanes and their carbon isotopes in sediment from the Jeongok-ri Paleolithic Site, Korea

Carbon isotope of total organic carbon (δ13Corg) and long-chain n-alkanes, which are terrestrial plant biomarkers, and their compound-specific carbon isotope ratios (δ13CALK) were investigated in the sediment of the Jeongok-ri Paleolithic Site in central Korea to interpret changes in paleovegetation and paleoclimate. The δ13Corg ranged between approximately −24‰ and −27‰, suggesting different organic matter sources. Relatively lighter δ13Corg occurred in lower part and the occurrence of heavier δ13Corg in upper part may indicate terrestrial C3 plant dominance and/or a mixture of C3 and C4 plants, respectively. The patterns of n-alkane distribution were characterized by a continuous predominance of odd-numbered n-alkanes, particularly nC29 and nC31, and by variation in the distribution of even-numbered n-alkanes. Total concentration of n-alkanes and distributions of each number of n-alkanes are quite different over time, suggesting paleovegetation changes. The average chain length (ACL) and carbon preferences index (CPI) showed gradual variations with distinctive switching points at about 160 ka. This variation reflecting changes in paleovegetation type, is coincident with those of the δ13Corg. Individual n-alkane isotopes, δ13CALK, ranged between −18.64‰ and −38.09‰, suggesting different sources of n-alkanes. Although some petrogenic sources of n-alkanes were possible, the distribution of n-alkanes and their δ13CALK support paleovegetation and paleoclimatic variations in Jeongok-ri Paleolithic site, Korea for the last 300 ka.

Assessing the origins of aliphatic amines in the Murchison meteorite from their compound-specific carbon isotopic ratios and enantiomeric composition

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of l-enantiomeric excesses for α-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are structurally related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with δ13C values ranging from +21‰ to +129‰, showing a decrease in 13C with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an l-enantiomeric excess of 9.7%; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

Source characterization of sedimentary organic matter using molecular and stable carbon isotopic composition of n-alkanes and fatty acids in sediment core from Lake Dianchi, China

The distribution and compound-specific carbon isotope ratios of n-alkanes and fatty acids in a sediment core (63cm) collected from Lake Dianchi were examined to investigate organic matter sources in the eutrophic lake. Fatty acids included free and bound fatty acids. The carbon isotope compositions of individual n-alkanes and fatty acids from Lake Dianchi sediments were determined using gas chromatography/isotope ratio mass spectrometry (GC–IRMS). The δ13C values of individual n-alkanes (C16–C31) varied between −24.1‰ and −35.6‰, suggesting a dominance of 13C-depleted n-alkanes that originated from C3 plants and lacustrine algae. Fatty acids from the sediment extracts were analyzed for their abundances and carbon isotopic compositions. Molecular and isotopic evidence indicates that most of the short-chain fatty acids from Lake Dianchi sediment extracts are sourced from intense microbial recycling and resynthesis of organic matter. Long-chain free fatty acids are mainly derived from terrestrial sources. However, long-chain bound fatty acids are sourced from a combination of terrestrial organic matter, bacteria and algae, with the contribution from algal sources higher in the hypereutrophic stage.

Analysis of household ignitable liquids and their post-combustion weathered residues using compound-specific gas chromatography-combustion-isotope ratio mass spectrometry

The continuing rise in home and vehicular arson cases involving the use of ignitable liquids continues to be an area of concern for criminal and civil investigators. In this study, the compound-specific δ13C values of various components of four flammable household chemicals were measured using a single quadrupole mass spectrometer and an isotope ratio mass spectrometer as simultaneous detectors for a gas chromatograph. Whereas compound-specific carbon isotope ratios were able to discriminate between different sources of neat (pre-combustion) ignitable liquids, analyses of the post-combustion residues were problematic. Weathering caused by combustion resulted in a significant increase in the 13C content of specific peaks relative to the neat liquids (i.e. less negative delta values) such that the isotopic comparison of pre- and post-combustion residues resulted in fractionation ranging from 0 to +10‰. Because of the current lack of understanding of isotopic fractionation during combustion, and because of problems encountered with co-elution in the more complex samples, compound-specific IRMS does not appear to be suitable for fire debris analysis. The comparison of non-combusted or non-weathered ignitable liquids is much more reliable, especially for relatively simple mixtures, and is best suited for exclusionary purposes until such time as a comprehensive database of samples is developed. Without a measure of the population variance, one cannot presently predict the false positive identification rate for the comparison of two ignitable liquids; i.e. the probability that two random ignitable liquid samples have indistinguishable isotope ratios.

Inverse gradients in leaf wax δD and δ13C values along grass blades of Miscanthus sinensis: Implications for leaf wax reproduction and plant physiology

Compound specific hydrogen and carbon isotopic ratios of higher plant leaf waxes have been extensively used in paleoclimate and paleoenvironmental reconstructions. However, studies so far have focused on the comparison of leaf wax isotopic differences in bulk leaf samples between different plant species. We sampled three different varieties of tall grasses (Miscanthus sinensis) in six segments from base to tip and determined hydrogen and carbon isotopic ratios of leaf waxes, as well as hydrogen and oxygen isotopic ratios of leaf water samples. We found an increasing, base-to-tip hydrogen isotopic gradient along the grass blades that can probably be attributed to active leaf wax regeneration over the growth season. Carbon isotopic ratios, on the other hand, show opposite trends to hydrogen isotopic ratios along the grass blades, which may reflect different photosynthetic efficiencies at different blade locales.

Precise and accurate compound-specific carbon and nitrogen isotope analysis of RDX by GC-IRMS

A new analytical method is presented for the compound-specific carbon and nitrogen isotope ratio analysis of a thermo-labile nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by gas chromatograph coupled to an isotope ratio mass spectrometer (GC-IRMS). Two main approaches were used to minimise thermal decomposition of the compound during gas chromatographic separation: programmed temperature vaporisation (PTV) as an injection technique and a high-temperature ramp rate during the GC run. δ15N and δ13C values of RDX measured by GC-IRMS and elemental analyser (EA)-IRMS were in good agreement within a standard deviation of 0.3‰ and 0.4‰ for nitrogen and carbon, respectively. Application of the method for the isotope analysis of RDX during alkaline hydrolysis at 50°C revealed isotope fractionation factors ε carbon = −7.8‰ and ε nitrogen = −5.3‰.

Light hydrocarbons geochemistry of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh

A geochemical study of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh, India was carried out using light hydrocarbon compounds to assess the hydrocarbon potential of the basin. Suite of 80 soil samples were collected from the depth of 2.5 m and analyzed for adsorbed light gaseous hydrocarbons namely methane (CH4), ethane (C2H6) and propane (C3H8) in Gas chromatograph. Compound specific Carbon isotope ratios for CH4 and C2H6 were also determined using GC-C IRMS (Gas Chromatograph Combustion Isotope Mass Spectrometer). The presence of moderate to low concentrations of methane ( $C_{CH_4 } $ : 1 to 138 ppb), ethane ( ${H_4 }$ : 1 to 35 ppb) and propane ( $C_{C_3 H_8 } $ : 1 to 20 ppb) was measured in the soil samples. Carbon isotopic composition of $\delta ^{13} C_{CH_4 } $ ranges between −27.9 to −47.1 ‰ and $\delta ^{13} C_{C_2 H_6 } $ ranged between −36.9 to −37.2 ‰ (V-PDB) indicating that these gases are of thermogenic origin. Study of soil samples suggests the area has good potential for hydrocarbon.