Compound-specific Isotope Analysis Research Articles

Holocene landscape evolution, palaeoclimate and human impact in the Fotsch Valley, Stubai Alps, Austria: Interrogating biomarkers, stable isotopes, macrofossils and palynological indicators from a subalpine mire archive

Peatlands are receiving increasing attention in palaeoenvironmental research and represent very useful terrestrial archives for reconstructing vegetation, climate and human history. Previous palaeoenvironmental studies in the Fotsch Valley, Stubai Alps, Austria, focused on geoarchaeological investigations on the Ullafelsen representing a very important prehistorical encampment site used by Mesolithic hunter-gatherers (10.9–9.5 cal. kyr BP). In order to contribute to a better understanding of the landscape evolution of the Fotsch Valley, we here studied the close-by subalpine ‘Potsdamer Hütte Mire’ by applying radiocarbon dating as well as elemental, biomarker, compound-specific stable isotope, palynological and macrofossil analyses on bulk peat samples. The calculated age-depth model using R Bacon indicates the beginning of peat formation during the Early Holocene and shows a strongly reduced peat accumulation rate (PAR) from 170 to 121 cm depth (8.5–2.1 cal. kyr BP) and/or a striking hiatus. Results of leaf wax-derived n-alkane biomarkers as well as macrofossils and palynological indicators reflect the local presence of coniferous trees and the synchronous expansion of deciduous trees during the Early Holocene. The above-mentioned strongly reduced PAR and/or hiatus coincides with the Neolithic, the Bronze and the Iron Age, and goes hand in hand with strong changes in vegetation and an increase of micro-charcoal and black carbon. Despite age uncertainties, these changes can be explained with strongly increasing human and livestock activities in form of deforestation, domestic fires and the beginning of Alpine pastoralism. The latter is confirmed by the finding of pasture and cultural indicator pollen (Cerealia-type, Rumex, Plantago lanceolata, Poaceae) occurring since the Middle to Late Bronze Age. The oxygen isotope composition of sugar biomarkers (δ18Osugars) likely reflects the dry versus humid climatic variability associated with the Holocene climatic optimum during the Mesolithic, the Roman Age, the Late Antique Little Ice Age, the Middle Ages and the Little Ice Age.

Uptake and Transformation of Hexachlorocyclohexane Isomers (HCHs) in Tree Growth Rings at a Contaminated Field Site.

The potential transformation of hexachlorocyclohexane isomers (HCHs) within tree trunks could have a significant impact on the use of phytoscreening. However, the transformation mechanisms of HCH in trunks particularly in growth rings are not yet well understood. Therefore, a field study on an HCH-contaminated field site was conducted to investigate the fate of HCH, particularly α-HCH in tree trunks using multielement compound-specific isotope analysis (ME-CSIA) and enantiomer fractionation. The results indicate that α-HCH was transformed, as evidenced by higher δ13C and δ37Cl values detected across different growth ring sections and in the bark compared to those in muck and soil. Remarkably, in the middle growth ring section, δ13C values of HCH were only marginally higher or comparable to those in muck, whereas δ37Cl values were higher than those of the muck, indicating a different transformation mechanism. Moreover, the δ37Cl values of β-HCH also increased in the tree trunks compared to those in soil and muck, implying a transformation of β-HCH. Additionally, dual-element isotope analysis revealed that there are different transformation mechanisms between the middle growth rings and other sections. Our findings suggest that the transformation of HCHs in trunks could bias quantitative phytoscreening approaches; however, ME-CISA offers an option to estimate the degradation extent.

Development and Application of a Purification Method for the Determination of Three EDCs Isotopes in Sediments and Water

Compound-specific stable isotope analysis (CSIA) is an efficient method for source apportionment and the identification of the transformation process in organic compounds. However, most studies of CSIA are still limited to laboratory experiments. Few studies used have CSIA in an in situ environment due to the complexity of environmental samples. Therefore, a purification method for analyzing the carbon isotope ratios of three phenolic endocrine disrupting compounds (EDCs) (nonylphenols (NPs), octylphenol (OP), and bisphenol A(BPA)) in sediment and water samples was developed in this study. The silica gel column was used to isolate EDCs from complex matrices with multiple organic solvents. Gas chromatography/mass spectrometry was used to quantify the targeted EDCs and analyze the purity of the extracts in full-scan mode. The interfering peaks disappeared, the baseline was sharply reduced, and all the target compounds appeared as single peaks in the chromatogram after purification. Analyzing the standard samples with known isotope ratios showed that the purification treatment did not cause isotope fractionation. The isotopic difference before and after purification was less than 0.04. The method was successfully used to analyze the isotope composition of BPA, OP, and NPs in river water and sediments in the Guangzhou River, Pearl River Delta, South China. Sewage discharge significantly affected the carbon isotope values of BPA, OP and NPs in Guangzhou rivers, suggesting that sewage discharge is the main source of EDCs in the Guangzhou rivers. There is a significant correlation between the isotopic values and concentrations of OP and NPs in sediments, indicating that they may undergo chemical transformation.

Movements and trophic ecology of dolphinfish (Coryphaena hippurus) in the Mexican Central Pacific inferred from stomach content, bulk, and compound-specific stable isotope analyses

Movements and trophic ecology of dolphinfish (Coryphaena hippurus) in the Mexican Central Pacific inferred from stomach content, bulk, and compound-specific stable isotope analyses

Avoiding Interferences in Advance: Cyclodextrin Polymers to Enhance Selectivity in Extraction of Organic Micropollutants for Carbon Isotope Analysis

Compound-specific isotope analysis (CSIA) of organic water contaminants can provide important information about their sources and fate in the environment. Analyte enrichment from water remains nonetheless a critical yet inevitable step before measurement. Commercially available solid-phase extraction (SPE) sorbents are inherently nonselective leading to co-extraction of concurrent dissolved organic matter (DOM) and in turn to analytical interferences, especially for low-occurring contaminants. Here, we (i) increased extraction selectivity by synthesizing cyclodextrin polymers (α-, β-, γ-CDP) as SPE sorbents, (ii) assessed their applicability to carbon isotope analysis for a selection of pesticides, and (iii) compared them with commonly used commercial sorbents. Extraction with β-CDP significantly reduced backgrounds in gas chromatography-isotope ratio mass spectrometry (GC-IRMS) and enhanced sensitivity by a factor of 7.5, which was further confirmed by lower carbon-normalized CDOM/Canalyte ratios in corresponding extracts as derived from dissolved organic carbon (DOC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Gibbs free energies of adsorption demonstrated weak competition between DOM and analyte on the three CDPs. No isotopic fractionation (Δδ13C within ± 0.3‰) was observed for the investigated pesticides after using β-CDP as an SPE sorbent covering a range of concentrations (5-500 μg L-1), flow velocities (5-40 cm min-1), and sorbent regeneration (up to six times). The present study highlights the benefit of selecting innovative extraction sorbents to avoid interferences in advance. This strategy in combination with existing cleanup approaches offers new prospects for CSIA at field concentrations of tens to hundreds of nanograms per liter.

Isotopic evidence (δ13C, δ37Cl, δ2H) for distinct transformation mechanisms of chloroform: Catalyzed H2-water system vs. zero-valent iron (ZVI)

Catalytic hydrodechlorination is an efficient technology for degrading organochlorinated compounds, such as chloroform (CF), into harmless products. Compound-specific stable isotope analysis (CSIA) of multiple elements is widely used for the investigation of degradation mechanisms. Yet, its application in the study of catalytic hydrodechlorination is still limited. We have applied CSIA to derive chlorine, carbon, and hydrogen isotope enrichment factors (ε) during the degradation of CF over Pd/Al2O3 and over Rh/Al2O3. In addition, the enrichment factors for the same isotopes were derived for the reaction of CF with zero-valent iron (ZVI) for comparison. For the reactions of CF over Pd/Al2O3 and Rh/Al2O3, εC values (−21.9 ± 0.25 ‰ and −23.4 ± 2.3 ‰) and εCl values (−12.1 ± 1.7 ‰ and −10.3 ± 0.6 ‰) were determined, respectively. The corresponding εC and εCl values, for the dechlorination of CF with ZVI were −22.2 ± 2.8 ‰ and −4.7 ± 0.45 ‰, respectively. The apparent kinetic isotope effects (AKIE) of Cl suggest that the transformation mechanism in the catalyzed hydrogen-water system is a non-concerted reaction, unlike the known reductive dechlorination of CF with ZVI. Moreover, dual-isotope slopes (ΛC/Cl) for both catalyzed reactions (ΛPd = 1.8 ± 0.13 and ΛRh = 2.1 ± 0.14) are markedly different than for the ZVI (ΛZVI = 5.8 ± 0.41), reflecting that the reactions proceed in different mechanisms. For hydrogen isotopes, while there was no clear trend for the catalyzed reactions, an inverse secondary hydrogen isotope effect was observed for the reaction of CF with ZVI.

Compound-Specific Carbon, Hydrogen, and Nitrogen Isotope Analysis of Nitro- and Amino-Substituted Chlorobenzenes in Complex Aqueous Matrices.

Compound-specific isotope analysis (CSIA) is an established tool to study the fate of legacy groundwater contaminants but is only emerging for nonconventional contaminants, e.g., nitro- and amino-substituted chlorobenzenes that are widely used as industrial feedstock and the target of this work. To date, CSIA of the target compound groups used special combustion interfaces and the potential matrix interferences in environmental samples has not been assessed. We validated CSIA methods for δ13C, δ2H, and δ15N of four analytes from each chemical group and developed a solid-phase extraction (SPE) method to minimize matrix interferences during preconcentration of complex aqueous samples. The SPE recovery was >80% and the method quantification limits of SPE-CSIA for δ13C, δ2H, and δ15N were 0.03-0.57, 1.3-2.7, and 3.4-10.2 μM aqueous-phase concentrations, respectively, using 2 L of spiked MQ water. The SPE-CSIA procedure showed negligible isotope fractionation for δ13C (≤0.5‰), δ15N (≤0.5‰), and δ2H (≤5‰ for nitroaromatics and ≤10‰ for aminoaromatics). In addition, solvent evaporation, water sample storage up to 7 months, and SPE extract storage for 1.5 years did not change analytes' δ13C signatures beyond ±0.5‰. However, to avoid significant δ2H and δ15N fractionation of aminoaromatics, cartridge breakthrough should be avoided and SPE preconcentration must be conducted at pH > pKa + 2. Application of the method at a contaminated site showed excellent precision, at ≤0.3‰ for C and N, and ≤1.5‰ for H. The methods validated here now allow the use of multielement CSIA to track the environmental fate of nitro- and amino-substituted chlorobenzenes in complex aqueous samples.

Effect of thermal maturation on the isotopic compositions of volatile organic sulfur compounds released from a kerogen by hydrous and anhydrous pyrolysis

Volatile organic sulfur compounds (VOSCs) may provide an alternative and improved approach in the evaluation of source and thermal maturity of natural gas. However, the role of water in the generation and decomposition of VOSCs is still ambiguous. Hydrous pyrolysis experiments were conducted on the isolated type Ⅱ-S kerogen of a source rock collected from the Ghareb Formation, Israel at 200–360 ℃ for 72 h (Easy%Ro = 0.32–1.20). The evolved gases were quantified for C1-C5 hydrocarbons, CO2, H2S and VOSCs. Compound specific isotope analysis were conducted both on the VOSCs and H2S (δ34S), and also on the C1-C5 hydrocarbons and CO2 (δ13C, δ2H). The results show that thiols concentration increased from 200 ℃ to 300 ℃ and then decreased from 300 ℃ to 360 ℃. The formed thiols isotopically co-vary with H2S from 200 ℃ to 340 ℃ and present the opposite trend with H2S from 340 ℃ to 360 ℃. The δ34S values of thiols are usually 3–7‰ lighter than the parent kerogen and 0.5–4‰ heavier than H2S. The concentrations of thiophenes generally increased with thermal stress with peak generation at 360 ℃, the δ34S values of thiophenes are mostly < 2–4‰ lighter than the parent kerogen and 2–8‰ heavier than H2S through the experiments. The δ13C and δ2H values of gaseous hydrocarbons are gradually enriched in heavy isotopes with increased thermal maturity. VOSCs dominated by thiols and thiophenes are generated by two ways: 1. the interactions between H2S and hydrocarbon molecules (synthetic pathway), 2. thermal cracking of OMs including kerogen and associated bitumen primary cracking and hydrocarbon secondary cracking (thermal cracking pathway). The synthetic pathway played the major role in the generation of thiols at the immature and early mature stages (200–300 ℃, Easy%Ro = 0.32–0.71), the cracking pathway has the dominant effect on the occurrence of thiols at higher thermal maturity levels (300–360 ℃, Easy%Ro = 0.71–1.20). The main pathway of thiophenes formation throughout the experiments is by the thermal cracking pathway. In the hydrous experiments, water promotes the synthetic pathway that generated thiols and retarded the thermal cracking pathway that forms thiophenes, but had no significant impact on δ34S values of individual VOSCs, δ13C and δ2H values of gaseous hydrocarbons. Therefore, combining with carbon and hydrogen isotopic compositions of gaseous hydrocarbons, molecular and sulfur isotopic compositions of individual VOSCs in the gas phase can provide valuable clues for petroleum systems in sedimentary basins including gas sources, generation pathways, thermal maturity levels and petroleum secondary transformations, such as thermochemical sulfate reduction in the subsurface reservoirs.

Aquatic methylmercury is a significant subsidy for terrestrial songbirds: Evidence from the odd mass-independent fractionation of mercury isotopes

In contrast to aquatic food chains, knowledge of the origins and transfer of mercury (Hg) and methylmercury (MeHg) in terrestrial food chains is relatively limited, especially in songbirds. We collected soil, rice plants, aquatic and terrestrial invertebrates, small wild fish, and resident songbird feathers from an Hg-contaminated rice paddy ecosystem for an analysis of stable Hg isotopes to clarify the sources of Hg and its transfer in songbirds and their prey. Significant mass-dependent fractionation (MDF, δ202Hg), but no mass-independent fractionation (MIF, ∆199Hg) occurred in the trophic transfers in terrestrial food chains. Piscivorous, granivorous, and frugivorous songbirds and aquatic invertebrates were all characterized by elevated Δ199Hg values. The estimated MeHg isotopic compositions obtained using linear fitting and a binary mixing model explained both the terrestrial and aquatic origins of MeHg in the terrestrial food chains. We found that MeHg from aquatic habitats is an important subsidy for terrestrial songbirds, even those that feed mainly on seeds, fruits, or cereals. The results show that MIF of the MeHg isotope is a reliable tool to reveal MeHg sources in songbirds. Because the MeHg isotopic compositions was calculated with a binary mixing model or directly estimated from the high proportions of MeHg, compound-specific isotope analysis of Hg would be more useful for the interpretation of the Hg sources, and is highly recommended for future studies.

Insight of microbial degradation of n-hexadecane and n-heneicosane in soil during natural attenuation and bioaugmentation by Compound-specific Stable Isotope Analysis (CSIA)

Microbial degradation of n-hexadecane (n-C16) and n-heneicosane (n-C21) in soil during natural attenuation (NA) and bioaugmentation (BA) were investigated by compound-specific stable isotope analysis (CSIA), microbial community and key enzyme genes analysis. In both NA and BA treatments, more than 95% of n-C16 and n-C21 were degraded within 3 and 6 days, respectively, with a slight faster degradation in BA than NA. According to CSIA, n-C16 showed a reverse hydrogen isotope fractionation effect, while n-C21 had a normal hydrogen isotope fractionation effect, and the degree of hydrogen isotope fractionation in BA were greater than NA. Isotope enrichment factors (εH) of n-C16 and n-C21were 3.50 ± 0.60‰ and − 2.11 ± 0.57‰ in NA, and 5.18 ± 0.46‰ and − 2.73 ± 0.39‰ in BA, respectively. The dominant genera in BA and NA were significantly different for n-C16 and n-C21 degradation and few strains added during BA remained active, such as Rhodococcus in both n-C16 and n-C21, and Brevundimonas only in n-C21, which showing high application potential in alkanes contamination remediation. Both alkB and almA genes played more key roles than Cytochromes P450 in n-C16 and n-C21 biodegradation, but alkB was much more promoted by n-C16 while almA was more motivated by n-C21. The different types of alkane-degrading bacteria with different enzyme reaction kinetics might be the reason of opposite hydrogen isotope fractionation of n-C16 and n-C21 during their biodegradation. Above all, CSIA can be a proper technology to quantitatively evaluate the biodegradation of different alkane during NA and BA bioremediation process in contamination sites.

Novel 13C enrichment technique reveals early turnover of DHA in peripheral tissues

The brain is rich in DHA, which plays important roles in regulating neuronal function. Recently, using compound-specific isotope analysis that takes advantage of natural differences in carbon-13 content (13C/12C ratio or δ13C) of the food supply, we determined the brain DHA half-life. However, because of methodological limitations, we were unable to capture DHA turnover rates in peripheral tissues. In the current study, we applied compound-specific isotope analysis via high-precision GC combustion isotope ratio mass spectrometry to determine half-lives of brain, liver, and plasma DHA in mice following a dietary switch experiment. To model DHA tissue turnover rates in peripheral tissues, we added earlier time points within the diet switch study and took advantage of natural variations in the δ13C-DHA of algal and fish DHA sources to maintain DHA pool sizes and used an enriched (uniformly labeled 13C) DHA treatment. Mice were fed a fish-DHA diet (control) for 3 months, then switched to an algal-DHA treatment diet, the 13C enriched-DHA treatment diet, or they stayed on the control diet for the remainder of the study time course. In mice fed the algal and 13C enriched-DHA diets, the brain DHA half-life was 47 and 46 days, the liver half-life was 5.6 and 7.2 days, and the plasma half-life was 4.7 and 6.4 days, respectively. By using improved methodologies, we calculated DHA turnover rates in the liver and plasma, and our study for the first time, by using an enriched DHA source (very high δ13C), validated its utility in diet switch studies.

Trace mercury migration and human exposure in typical mercury-emission areas by compound-specific stable isotope analysis

Anthropogenic mercury (Hg) emissions have increased significantly since the Industrial Revolution, resulting in severe health impacts to humans. The consumptions of fish and rice were primary human methylmercury (MeHg) exposure pathways in Asia. However, the lifecycle from anthropogenic Hg emissions to human MeHg exposure is not fully understood. In this study, a recently developed approach, termed MeHg Compound-Specific Isotope Analysis (CSIA), was employed to track lifecycle of Hg in four typical Hg-emission areas. Distinct Δ199Hg of MeHg and inorganic Hg (IHg) were observed among rice, fish and hair. The Δ199Hg of MeHg averaged at 0.07 ± 0.15 ‰, 0.80 ± 0.55 ‰ and 0.43 ± 0.29 ‰ in rice, fish and hair, respectively, while those of IHg averaged at − 0.08 ± 0.24 ‰, 0.85 ± 0.43 ‰ and − 0.28 ± 0.68 ‰. In paddy ecosystem, Δ199Hg of MeHg in rice showed slightly positive shifts (∼0.2 ‰) from those of IHg, and comparable Δ199Hg of IHg between rice grain and raw/processed materials (coal, Hg ore, gold ore and sphalerite) were observed. Simultaneously, it was proved that IHg in fish muscle was partially derived from in vivo demethylation of MeHg. By a binary model, we estimated the relative contributions of rice consumption to human MeHg exposure to be 84 ± 14 %, 58 ± 26 %, 52 ± 20 % and 34 ± 15 % on average in Hg mining area, gold mining area, zinc smelting area and coal-fired power plant area, respectively, and positive shifts of δ202HgMeHg from fish/rice to human hair occurred during human metabolic processes. Therefore, the CSIA approach can be an effective tool for tracking Hg biogeochemical cycle and human exposure, from which new scientific knowledge can be generated to support Hg pollution control policies and to protect human health.

Theoretical Kinetic Isotope Effects in Establishing the Precise Biodegradation Mechanisms of Organic Pollutants.

Compound-specific isotope analysis (CSIA) for natural isotope ratios has been recognized as a promising tool to elucidate biodegradation pathways of organic pollutants by microbial enzymes by relating reported kinetic isotope effects (KIEs) to apparent KIEs (AKIEs) derived from bulk isotope fractionations (εbulk). However, for many environmental reactions, neither are the reference KIE ranges sufficiently narrow nor are the mechanisms elucidated to the point that rate-determining steps have been identified unequivocally. In this work, besides providing reference KIEs and rationalizing AKIEs, good relationships have been explained by DFT computations for diverse biodegradation pathways with known enzymatic models between the theoretical isotope fractionations (εbulk') from intrinsic KIEs on the rate-determining steps and the observed εbulk. (1) To confirm the mechanistic details of previously reported pathway-dependent CSIA, it includes isotope changes in MTBE biodegradation between hydroxylation by CYP450 and SN2 reaction by cobalamin-dependent methyltransferase, the regioselectivity of toluene biodegradation by CYP450, and the rate-determining step in toluene biodegradation by benzylsuccinate synthase. (2) To yield new fundamental insights into some unclear biodegradation pathways, it consists of the oxidative function of toluene dioxygenase in biodegradation of TCE, the epoxidation mode in biodegradation of TCE by toluene 4-monooxygenase, and the weighted average mechanism in biodegradation of cDCE by CYP450.

Reconstructions of individual fish trophic geographies using isotopic analysis of eye-lens amino acids.

Fish eye lenses are a proteinaceous structure that grows by accumulating layers in a chronological manner. Each layer becomes metabolically inert, capturing the ratio of heavy/light carbon and nitrogen isotopes at time of formation. Therefore, eye lenses contain chronological isotopic records and can be used to create a temporal isotopic history throughout an individual's lifetime. We analyzed eye lens amino-acid δ15N to address spatio-temporal baseline variability and to reconstruct trophic histories of 10 individual Red Snapper. Proteins from sequential eye lens laminae were derivatized to measure 10 amino acids, from which glutamic acid (trophic) and phenylalanine (source) were used to estimate trophic positions at different points in life. Best-fitting regressions were generated to represent individual (R2 ≥ 0.89) and generalized (R2 = 0.77) trophic trajectory for Red Snapper. The resulting trophic trajectories indicated an increase in trophic position with increasing length. Until recently, there has not been a lifetime isotopic structure with enough organic nitrogen to recreate geographic histories using compound-specific stable isotope analysis of amino acids (CSIA-AA). This study confirms that eye-lens laminae can be used to reconstruct trophogeographic histories via CSIA-AA.

An Overview of Lipid Biomarkers in Terrestrial Extreme Environments with Relevance for Mars Exploration.

Lipid molecules are organic compounds, insoluble in water, and based on carbon-carbon chains that form an integral part of biological cell membranes. As such, lipids are ubiquitous in life on Earth, which is why they are considered useful biomarkers for life detection in terrestrial environments. These molecules display effective membrane-forming properties even under geochemically hostile conditions that challenge most of microbial life, which grants lipids a universal biomarker character suitable for life detection beyond Earth, where a putative biological membrane would also be required. What discriminates lipids from nucleic acids or proteins is their capacity to retain diagnostic information about their biological source in their recalcitrant hydrocarbon skeletons for thousands of millions of years, which is indispensable in the field of astrobiology given the time span that the geological ages of planetary bodies encompass. This work gathers studies that have employed lipid biomarker approaches for paleoenvironmental surveys and life detection purposes in terrestrial environments with extreme conditions: hydrothermal, hyperarid, hypersaline, and highly acidic, among others; all of which are analogous to current or past conditions on Mars. Although some of the compounds discussed in this review may be abiotically synthesized, we focus on those with a biological origin, namely lipid biomarkers. Therefore, along with appropriate complementary techniques such as bulk and compound-specific stable carbon isotope analysis, this work recapitulates and reevaluates the potential of lipid biomarkers as an additional, powerful tool to interrogate whether there is life on Mars, or if there ever was.

On the Chemical Purity and Oxygen Isotopic Composition of α-Cellulose Extractable from Higher Plants and the Implications for Climate, Metabolic, and Physiological Studies.

The 18O/16O ratio of α-cellulose in land plants has proved of interest for climate, environmental, physiological, and metabolic studies. Reliable application of such a ratio may be compromised by the presence of hemicellulose impurities in the α-cellulose product obtainable with current extraction methods, as the impurities are known to be isotopically different from that of the α-cellulose. We first compared the quality of hydrolysates of "α-cellulose products" obtained with four representative extraction methods (Jayme and Wise; Brendel; Zhou; Loader) and quantified the hemicellulose-derived non-glucose sugars in the α-cellulose products from 40 land grass species using gas chromatography-mass spectrometry (GC/MS). Second, we performed compound-specific isotope analysis of the hydrolysates using GC/Pyrolysis/IRMS. These results were then compared with the bulk isotope analysis using EA/Pyrolysis/IRMS of the α-cellulose products. We found that overall, the Zhou method afforded the highest purity α-cellulose as judged by the minimal presence of lignin and the second-lowest presence of non-glucose sugars. Isotopic analysis then showed that the O-2-O-6 of the α-cellulose glucosyl units were all depleted in 18O by 0.0-4.3 mUr (average, 1.9 mUr) in a species-dependent manner relative to the α-cellulose products. The positive isotopic bias of using the α-cellulose product instead of the glucosyl units stems mainly from the fact that the pentoses that dominate hemicellulose contamination in the α-cellulose product are relatively enriched in 18O (compared to hexoses) as they inherit only the relatively 18O-enriched O-2-O-5 moiety of sucrose, the common precursor of pentoses and hexoses in cellulose, and are further enriched in 18O by the (incomplete) hydrolysis.

Mechanistic characterization of anaerobic microbial degradation of BTBPE in coastal wetland soils: Implication by compound-specific stable isotope analysis

As a novel brominate flame retardants, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) has been extensively used in various consumer products, and frequently detected in various environmental matrices. However, the microbial degradation of BTBPE remains unclear in the environment. This study comprehensively investigated the anaerobic microbial degradation of BTBPE and therein stable carbon isotope effect in the wetland soils. BTBPE degradation followed the pseudo-first-order kinetic, with degradation rate of 0.0085 ± 0.0008 day−1. Based on identification of degradation products, stepwise reductive debromination was the main transformation pathway of BTBPE, and tended to keep the stable of 2,4,6-tribromophenoxy group during the microbial degradation. The pronounced carbon isotope fractionation was observed for BTBPE microbial degradation, and carbon isotope enrichment factor (εC) was determined to be −4.81 ± 0.37‰, indicating cleavage of C–Br bond as the rate-limiting step. Compared to previously reported isotope effects, carbon apparent kinetic isotope effect (AKIEC = 1.072 ± 0.004) suggested that the nucleophilic substitution (SN2 reaction) was the potential reaction mechanism for reductive debromination of BTBPE in the anaerobic microbial degradation. These findings demonstrated that BTBPE could be degraded by the anaerobic microbes in wetland soils, and the compound-specific stable isotope analysis was a robust method to discover the underlying reaction mechanisms.

Compound-specific carbon isotope evidence that the initial carbon isotope excursion in the end-Triassic strata in northwest Tethys is not the product of CAMP magmatism

Compound-specific carbon isotopic analysis of biomarkers and palynological studies from sections across the end-Triassic mass extinction in the northwestern Tethys provide constraints on the origin of the bulk organic carbon ‘initial’ isotope excursion. This excursion is commonly used to correlate among geographically disparate sections that span this pivotal event associated with the rise of modern fauna. Palynological analysis is used to identify intervals of Liassic-equivalent strata in south Wales and northeast England for isotopic study. Compound-specific carbon isotope analysis of n-alkanes and regular isoprenoids from these intervals reveals a trend different than that displayed by bulk organic matter, suggesting the latter signal is not derived from large perturbations in the global carbon cycle but from localized source changes. The most pronounced changes in compound-specific isotope profiles are negative excursions in pristane and phytane, which occur within the positive phase of the bulk carbon isotope excursion and correspond to shifts in total organic carbon and increased heterotrophy. These findings indicate that a re-evaluation of temporal relationships between positive climate feedbacks and their effects is necessary to more accurately understand the likely global nature of the end-Triassic extinction, and more generally, carbon cycle perturbations associated with other mass extinction events.

Early Holocene dietary patterns on the Neolithic Jeju Island, South Korea: Evidence from stone tools and stable carbon isotope analysis

This study investigates Neolithic subsistence on Jeju Island in Korea during the Early Holocene. Gosanri, our main site, provides evidence of the Early Holocene peopling to the Island by 10,000 cal. BP with pottery making tradition, while the Neolithic sites appeared in the Korean peninsula only 2000 years later. Gosanri and most of the Early Holocene sites, collectively called the Incipient Neolithic (10,000–8000 cal. BP), are located along the coastal lines of Jeju, and thus Incipient Neolithic people were assumed to conduct marine-based subsistence activities. This assumption has not been tested partly as most sites did not preserve any organic remains that can reflect diet. We examine this unanswered question by providing direct evidence on diet through the compound specific isotope analysis on pottery and by examining the stone tool compositions for procuring food. Our analyses suggest that Early Holocene islanders relied on terrestrial resource substantially. The proximity to the coast is not a self-sufficient evidence for the assumption of marine-oriented diet. Instead, the seasonality of food resources, the seasonal climate fluctuation, and the locational merit to a quarry, all equally affected Jeju islanders’ diet preference and subsistence practice. Overall Gosanri provides another convincing case of the broad-spectrum resource use to the transition to the Early Holocene.

Volatile organic compounds identification and specific stable isotopic analysis (δ13C) in microplastics by purge and trap gas chromatography coupled to mass spectrometry and combustion isotope ratio mass spectrometry (PT-GC-MS-C-IRMS).

Microplastics (MPs) have become one of the major global environmental issues in recent decades due to their ubiquity in the environment. Understanding MPs source origin and reactivity is urgently needed to better constrain their fate and budget. Despite improvements in analytical methods to characterize MPs, new tools are needed to help understand their sources and reactivity in a complex environment. In this work, we developed and applied an original Purge-&-Trap system coupled to a GC-MS-C-IRMS to explore the δ13C compound-specific stable isotope analysis (CSIA) of volatile organic compounds (VOC) embedded in MPs. The method consists of heating and purging MP samples, with VOCs being cryo-trapped on a Tenax sorbent, followed by GC-MS-C-IRMS analysis. The method was developed using a polystyrene plastic material showing that sample mass and heating temperature increased the sensitivity while not influencing VOC δ13C values. This robust, precise, and accurate methodology allows VOC identification and δ13C CSIA in plastic materials in the low nanogram concentration range. Results show that the monomer styrene displays a different δ13C value (- 22.2 ± 0.2‰), compared to the δ13C value of the bulk polymer sample (- 27.8 ± 0.2‰). This difference could be related to the synthesis procedure and/or diffusion processes. The analysis of complementary plastic materials such as polyethylene terephthalate, and polylactic acid displayed unique VOC δ13C patterns, with toluene showing specific δ13C values for polystyrene (- 25.9 ± 0.1‰), polyethylene terephthalate (- 28.4 ± 0.5‰), and polylactic acid (- 38.7 ± 0.5‰). These results illustrate the potential of VOC δ13C CSIA in MP research to fingerprint plastic materials, and to improve our understanding of their source cycle. Further studies in the laboratory are needed to determine the main mechanisms responsible for MPs VOC stable isotopic fractionation.