Compound-specific Isotope Analysis Research Articles

Salps in the NW Atlantic Slope Water: metabarcoding and compound-specific stable isotope analysis of diet diversity and trophic interactions

Salps in the NW Atlantic Slope Water: metabarcoding and compound-specific stable isotope analysis of diet diversity and trophic interactions

Insight into Imidacloprid Degradation through Compound Specific Carbon Isotope Analysis and High-Resolution Mass Spectrometry

Insight into Imidacloprid Degradation through Compound Specific Carbon Isotope Analysis and High-Resolution Mass Spectrometry

Degradation study of δ-hexachlorocyclohexane by iron sulfide nanoparticles: elucidation of reaction pathway using compound specific isotope analysis and pH variation

pH influences the reactivity of iron (II) minerals towards halogenated pollutants like hexachlorocyclohexanes (HCHs). To explore these incompletely understood interactions, we investigated the carbon isotope fractionation of the δ-HCH isomer during dehalogenation by iron sulfide at pHs spanning a pH range across slightly acidic to alkaline domains (5.8 to 9.6). The δ-1,3,4,5,6-pentachlorocyclohex-1-ene (δ-PCCH) was the intermediate degradation product, while benzene, monochlorobenzene (MCB), but especially 1,2-dichlorobenzene (1,2-DCB), and 1,2,4-trichlorobenzene (1,2,4-TCB), were the main degradation products of δ-HCH. These degradation products suggested dehydrochlorination as the main degradation pathway of δ-HCH by iron sulfide. Different kinetic experiments indicate that the rate constants (ka) during dechlorination of δ-HCH by iron sulfide rose with pH: 0.003 d-1 (pH 5.8) < 0.034 d-1 (pH 8) < 0.085 (pH 9.3) < 0.286 d-1 (pH 9.6). Upon Rayleigh model calculations, an enrichment factor (εC) of -7.8 ± 1.0 ‰ was calculated for δ-HCH dehalogenation by FeS at pH 8.0. This suggests an apparent kinetic isotope effect (AKIEC) value of 1.049 ± 0.006 for dehydrohalogenation. The magnitude of the isotope effect from this paper furthermore supports dehydrohalogenation and opens the possibility to study the degradation of HCHs by iron (II) minerals containing FeS as mackinawite in oxygen-deprived environments.

Exploring hydrogen isotope fractionation in lipid biomolecules of freshwater algae: implications for ecological and paleoenvironmental studies

ABSTRACT Understanding the stable hydrogen isotope (δ 2H) composition and fractionation in lipid biomolecules of primary producers, such as terrestrial and aquatic plants, is crucial for deciphering past environmental conditions, as well as applying compound-specific stable isotope analysis for the study of metabolic and ecological processes. We conducted a new tracer experiment to explore the δ 2H composition of algal fatty acid biomarkers, focusing on freshwater algae, which form the base of aquatic food webs. We selected a range of algal species widely found in freshwater ecosystems and cultivated them under controlled conditions. First, we added 2H2O to ambient water as a tracer to investigate the net hydrogen isotope fractionation during algal lipid synthesis at isotopic equilibrium, which is particularly informative for paleo-geochemical studies. Then, we conducted kinetic experiments to quantify the time needed for algal fatty acids to achieve isotopic steady-state conditions in response to the change in ambient water δ 2H values. Our findings revealed substantial variability in hydrogen isotope fractionation among different algal taxa and various fatty acids. Based on taxa, different fatty acids exhibited faster integration of water hydrogen than others, but they were not necessarily in the order of the biosynthetic pathway. This experiment underscores the complexity of hydrogen isotope fractionation and the requirement for controlled laboratory studies to properly apply compound-specific stable H isotope analysis techniques in ecological and paleo-environmental studies.

Organic geochemical and compound specific stable carbon isotope analyses of n-alkanes and saturated carboxylic acids extracted from late Paleozoic coals

AbstractIsotopic studies of coal organic matter are often conducted to gain information about past ecosystems and plant communities e.g. under changing climate conditions. While many studies focused on isotope analysis of bulk coal organic matter or extractable aliphatic hydrocarbons, the polar fraction and compounds that are bound to kerogen and not freely extractable have received less attention. The aim of this study was to provide a systematic comparison and evaluation of information gained from different molecular compounds (n-alkanes, n-carboxylic acids) extracted from Paleozoic coals before and after alkaline hydrolysis. Stable carbon isotope analysis of these compounds were used to evaluate a possible application of extractable and ‘bound’ lipids for paleoenvironmental analyses. Coal samples of different stratigraphic age, low thermal maturity (VRr &lt; 1.02%, mostly VRr &lt; 0.8%) and from different paleogeographic locations were selected to investigate organic matter deposited under different paleoenvironmental and paleoclimatic conditions. Molecular distributions show prominent carbon preference suggesting preservation of biologic signatures in coal organic matter. Permian Gondwana coals show similar n-alkane and n-carboxylic acid distribution which may be related to Glossopteris flora. Molecular distributions of Carboniferous coal from Europe are more variable with unimodal or bimodal patterns and maxima in the short- or long-chain range, reflecting higher diversity of paleovegetation and different contribution from algae or bacteria in limnic and paralic environments. The isotope signals of free as well as bound fatty acids show closer response for different depositional environments, whereas signals of paraffins and bulk organic matter are less variable. However, averaged fatty acid isotope signals in coals from different paleovegetational realms, e.g. Euramerica and Gondwana differed only marginally. Graphical abstract

The soil-air interfacial migration process of volatile PFAS at the contaminated sites: Evidence from stable carbon isotopes with CSIA

Volatile per- and polyfluoroalkyl substances (PFAS) are prone to transport among various environmental media, with the soil-air interfacial migration process being an important pathway that significantly influences their environmental fate. To assess the migration and transformations of target volatile PFAS at contaminated site using compound-specific stable isotope analysis (CSIA), it is necessary to understand the isotopic fractionation that occurs during their transfer from soil to air. We have established methods for pre-treatment and GC/CSIA analysis methods of target volatile PFAS in soil and air samples and ensured the accuracy of carbon isotope analysis. GC/IRMS δ13C measurements showed optimal precision at instrumental response above 1.35–2.75 Vs, with recommended minimum on-column C levels of 1.67–5.00 nmol for target volatile PFAS. Stable carbon isotope fractionation factors related to the soil-air interfacial migration process for target volatile PFAS were determined by performing laboratory simulations. The observed εsoil-air values are all negative, suggesting that the soil-air interfacial migration process for target volatile PFAS is kinetic fractionation, the removal of molecules containing lighter isotopes. By comparing the simulated and experimentally observed δ13C (‰) values of target volatile PFAS, we found consistent trends in the soil and inverse trends in the air. These δ13C (‰) values and the related isotope fractionation model provide valuable insights into the isotopic behavior of target volatile PFAS during soil-air interfacial migration process, aiding in the assessment of their environmental fate.

Unveiling the importance of heterotrophy for coral symbiosis under heat stress.

Global warming endangers reef-building corals as they lose their photosynthetic symbionts, which limits their ability to feed autotrophically. Consequently, heterotrophy, the capture of zooplankton, can become crucial for the energy budget of heat-stressed corals. However, it is difficult to assess the extent of the heterotrophic contribution in corals, as well as the dynamics of nutrient exchange between the host and its symbionts. In this pioneering study, we employed a suite of isotopic markers, including 13C- and 15N bulk tissue isotope measurements, compound-specific isotope analysis of amino acids (CSIA-AAs), and 13C- and 15N-labeled food incubations, to investigate nutrient acquisition and allocation in the coral Stylophora pistillata under controlled and heat-induced bleaching conditions. Bulk isotope values and inorganic carbon assimilation remained unchanged in the bleached corals compared to the control corals, overall indicating undisturbed autotrophic activity of the symbionts under heat stress. However, CSIA-AAs showed an increased dependence on heterotrophy for amino acid synthesis in both the host and the symbionts despite reduced assimilation of 15N-labeled food. Overall, these results suggest that although S. pistillata reduces its assimilation of heterotrophic food under heat stress, the acquisition of amino acids by the coral host and symbionts still relies on heterotrophy. This study emphasizes the importance of using multiple indicators to gain a comprehensive understanding of coral nutrition. It shows that coral dependence on heterotrophy is not only associated with a decline in autotrophic availability. Rather, it demonstrates the ability of S. pistillata to adapt its utilization of food sources to the prevailing environmental conditions.IMPORTANCEThis work highlights that every isotopic marker displays a piece of different information concerning the diet of the model coral S. pistillata. By combining all markers, we observed that although S. pistillata exhibited reduced heterotrophic assimilation under heat stress, amino acid acquisition and synthesis remained dependent on heterotrophy. The findings emphasize the adaptability of corals in utilizing different food sources, which is vital for their resilience and recovery in changing environmental conditions. This research underscores the complexity of coral symbiosis and highlights the need for multiple indicators to understand dietary dynamics comprehensively.

Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation.

Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B12 and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of 13C and 37Cl was observed in all abiotic reactions, with εC,bulk and εCl,bulk values ranging from -4.3 ± 0.4‰ to -2.3 ± 0.2‰ and from -2.6 ± 0.4‰ to -1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C10-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify in situ chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).

Dietary partitioning in sympatric Paradoxurinae civets in Borneo suggested by compound-specific nitrogen isotope analysis of amino acids

We applied stable carbon and nitrogen isotopic analyses to understand the faunivory of the four sympatric wild Paradoxurinae civet species in Borneo, which share similar ecological characteristics. We also employed compound-specific nitrogen isotope analysis of amino acids to estimate these species’ trophic positions (TPs). The bulk stable isotope analysis revealed distinctly lower nitrogen isotope ratios in binturongs than in the other three species. This suggests that binturongs exhibit the lowest degree of faunivory among the four species. Binturongs had the lowest TP estimated from the nitrogen isotope ratios of amino acids (2.0–2.1), followed by small-toothed palm civets (2.4–2.5), masked palm civets (2.7), and common palm civets (2.9). These results suggest that there is little faunivory in binturong and variations in faunivory in the other species. Although the number of samples measured for the nitrogen isotope ratios of amino acids is small (n = 2 for each species), our results suggest that the varying degree of consumption of animal food sources, such as insects, is the key mechanism of niche partitioning in these four Paradoxurinae civet species in Borneo. Such subtle but essential differences in closely related sympatric species would maintain high biodiversity in tropical regions.

Deciphering origins of hydrocarbon deposits by means of intramolecular carbon isotopes of propane adsorbed on sediments

Hydrocarbons are one of the important fluids within the Earth’s crust, and different biotic and abitoic processes can generate hydrocarbon during geological periods. Tracing the sources and sinks of hydrocarbons can help us better understand the carbon cycle of the earth. In this study, an improved approach of adsorbed hydrocarbons extraction from sediments was established. The improved thermal desorption approach, compound-specific isotope analysis and position-specific isotope analysis were integrated to investigate the molecular and intramolecular isotope fractionation between trace hydrocarbon gases within sediments and geological hydrocarbon deposits. The isotopic compositions of the terminal position carbon of propane (δ13Cterminal) serves as a correlation indicator between trace hydrocarbon gases within sediments and geological hydrocarbon deposits. The tight sandstone gas from the Turpan-Hami Basin is a first case study for the application of this novel method to trace hydrocarbon origins. The results showed that the hydrocarbons in the tight sandstone gases in the study area most likely originated from humic organic matter (type III kerogen) at an early mature stage. δ13Cterminal values of the thermally desorbed propane gases from different source rocks were distinguishable and the values of the tight sandstone gases significantly overlap with those of the Lower Jurassic Sangonghe source rocks, suggesting their genetic relationship. Overall, the results provided novel position-specific carbon isotopic constraints on origins of hydrocarbons.

Dual C and Cl compound-specific isotope analysis and metagenomic insights into the degradation of the pesticide methoxychlor

This study investigates the use of multi-element compound-specific isotope analysis (ME-CSIA) to monitor degradation processes of methoxychlor, a persistent organochlorine insecticide. Laboratory experiments examined the kinetics, release of transformation products, and carbon and chlorine isotope effects during methoxychlor degradation through alkaline hydrolysis, oxidation with alkaline-activated persulfate, and biotic reductive dechlorination. Results showed that hydrolysis and oxidation did not cause significant carbon and chlorine isotope fractionation, indicating that C-H rather than C-Cl bond cleavage was the rate-determining step. Conversely, biotic reductive dechlorination by a field-derived microcosm under strictly anoxic conditions displayed significant carbon (εC = −0.9 ± 0.3 ‰) and chlorine (εCl = −1.9 ± 1.0 ‰) isotope fractionation. Its corresponding calculated dual isotope slope (ΛC/Cl = 0.4 ± 0.1) and apparent kinetic isotope effects (AKIEC = 1.014 ± 0.005 and AKIECl = 1.006 ± 0.003) indicate a C-Cl bond cleavage as the rate-determining step, highlighting the difference with respect to the other studied degradation mechanisms. Changes in the microbial community diversity revealed that families such as Dojkabacteria, Anaerolineaceae, Dysgonomonadaceae, Bacteroidetes vadinHA17, Pseudomonadaceae, and Spirochaetaceae, may be potential agents of methoxychlor reductive dechlorination under anoxic conditions. This study advances the understanding of degradation mechanisms of methoxychlor and improves the ability to track its transformation in contaminated environments, including for the first time an isotopic perspective.

Terrigenous or not? δ13C reveals the origin of the retene and dehydroabietic acid methyl ester

Retene and dehydroabietic acid methyl ester (DAME) are biomarkers linked mostly to terrigenous organic matter. However, their aquatic origin from algae and/or cyanobacteria has been discussed in the past few years. The complex origin of retene and DAME can lead to misinterpretation during biomarker interpretation, which can be minimalised with the support of isotopic analyses. This study contains the results of thirty-two compound-specific isotope analyses (CSIA) of δ13C performed on retene and forty-six CSIA analyses of δ13C performed on DAME. Obtained δ13C results were compared with simple biomarker results to tie isotopic data with the origin of organic matter. Pure aquatic retene and DAME were present within the Middle Cambrian and Early Ordovician samples, as the first appearance of plants was noted in the Middle Ordovician.CSIA was performed on a wide spectrum of the Cambrian-Silurian, Late Triassic-Middle Jurassic, and Neogene samples. Cambrian-Silurian strata include aquatic-origin retene and DAME, as evidenced by their comparatively low carbon isotopic signature. The average δ13C for retene and DAME within Cambrian-Silurian strata was equal to −31.7 ‰ and − 30.8 ‰, respectively. The Late Triassic-Middle Jurassic strata were dominated by terrigenous organic matter, resulting in higher δ13C values in comparison with the Cambrian-Silurian strata. The average δ13C for retene and DAME within the Late Triassic–Middle Jurassic strata was equal to −25.2 ‰ and − 26.3 ‰, respectively. The average δ13C for retene and DAME within the Neogene strata was equal to −27.3 ‰ in both cases, as these strata also contain a significant input of terrigenous organic matter. Some Neogene samples containing strong aquatic organic matter admixture are characterised by a lower δ13C for retene and/or DAME, oscillating around −28.0 ‰ to −30.0 ‰ for both compounds. Despite possible terrigenous input within some Silurian samples, the δ13C for retene and DAME still shows values typical for aquatic origin. These results suggest that retene and DAME within the Silurian strata should not be linked with non-vascular plants or that, due to their affinity with algae and cyanobacteria, the early plants were characterised by a relatively low δ13C composition, characteristic for phytoplankton organic matter. δ13C of retene and DAME were compared with δ13C of C16-C30n-alkanes and stigmastane, which supported the thesis about isotopic differences in aquatic and terrigenous retene and DAME.

Resource omnivory in soil food webs and meta-ecosystem connections

Soil food webs were long considered an ecosystem sink for primary production and a black box of reticulated interactions. Quantification of multiple and changing interactions among consumers and resources within and beyond soil food webs stands up as a major challenge. In this mini-review/opinion paper, I present development of ideas on soil food-web structure focusing on resource omnivory – a central characteristic that is linked to food-web structure and stability. There is plenty of empirical evidence for trophic differentiation among soil invertebrates along different food-web dimensions (food resources, trophic levels, microhabitats, time). This comes along with the pervasive idea of widespread omnivory in soil food webs. I argue that we need to quantitatively assess multiple-resource feeding by soil consumers and related drivers across various taxa and different ecosystem types to come closer to predictions of soil food-web structure and dynamics. At the meta-ecosystem level, cross-ecosystem omnivory (i.e. feeding across energy fluxes from different ecosystems) plays an important role in connecting soil with aboveground and aquatic food webs. Aboveground-belowground studies have been focusing on the interfaces such as the rhizosphere and litter surface. Broader cascading impacts of the energy and organismic fluxes across these interfaces within the recipient ecosystem are, however, less understood. Of particular interest here are connections of vertebrate communities to soil food webs and the central role of soil-borne insects in cross-ecosystem energy exchange. Interactions between soil and aquatic food webs span for dozens to hundreds of meters from the terrestrial-aquatic interface, transferring significant amount of energy and matter between these ecosystems. Consequent changes of the structure and functioning in the recipient ecosystem requires more attention, especially how biodiversity-ecosystem functioning relationships manifest across ecosystems. Continuously developing methods, such as compound-specific isotopic analyses, can facilitate quantification of cross-ecosystem omnivory, helping to understand effects of food-web changes across the ecosystem borders. Overall, I present soil food webs as an open and dynamic pool with multiple cross-ecosystem connections and call for quantitative studies in this direction.

A long-term study of stable isotope ratios of fingernail keratin and amino acids in a mother-infant dyad.

To evaluate the potential of compound-specific isotope analysis of amino acids (CSIA-AA) for investigating infant feeding practices, we conducted a long-term study that compared infant and maternal amino acid (AA) nitrogen isotope ratios. Fingernail samples were collected from a single mother-infant dyad over 19 months postpartum. Carbon and nitrogen stable isotope ratios were measured in the bulk keratin of the fingernail samples. Selected samples were then hydrolyzed and derivatized for compound-specific nitrogen isotope analysis of keratin AAs. As in previous studies, infant bulk keratin nitrogen isotope values increased during exclusive breastfeeding and fell with the introduction of complementary foods and eventual cessation of breastfeeding. Infant trophic AAs had elevated nitrogen isotope values relative to the mother, while the source AAs were similar between the mother and infant. Proline and threonine appeared to track the presence of human milk in the infant's diet as the isotopic composition of these AAs remained offset from maternal isotope values until the cessation of breastfeeding. Although CSIA-AA is costly and labor intensive, it appears to hold potential for estimating the duration of breastfeeding, even after the introduction of complementary foods. Through the analysis of a full suite of AAs, it may also yield insights into infant physiology and AA synthesis.

Divergent dual C-H isotopic fractionation pattern during anaerobic biodegradation of toluene within Aromatoleum species under nitrate-reducing conditions

Toluene is a pollutant frequently detected in contaminated groundwater, mostly due to leakage from underground gasoline storage tanks and pipeline ruptures. Multi-element compound-specific isotope analysis provides a framework to understand transformation processes and design efficient remediation strategies. In this study, we enriched an anaerobic bacterial culture derived from a BTEX-contaminated aquifer that couples toluene and phenol oxidation with nitrate reduction and the concomitant production of carbon dioxide and biomass. The 16S rRNA gene amplicon data indicated that the toluene-degrading consortium was dominated by an Aromatoleum population (87 ± 2 % relative abundance), and metagenome sequencing confirmed that the genome of this Aromatoleum sp. encoded glycyl-radical enzyme benzylsuccinate synthase (BssABC) and phenylphospate synthase (PpsA1BC) homologous genes involved in the first step of toluene and phenol transformation, respectively. Carbon and hydrogen isotopic fractionation were εbulk, C = - 3.5 ± 0.6 ‰ and εrp, H = - 85 ± 11 ‰, respectively, leading to a dual C-H isotope slope of ΛH/C = 26 ± 2. This value fits with a previously reported value for a consortium dominated by an Azoarcus species (ΛH/C = 19 ± 5) but differs from that reported for Aromatoleum aromaticum (ΛH/C = 14 ± 1), both of which grow with toluene under nitrate-reducing conditions. Overall, this suggests the existence of different BssABC enzymes with different mechanistic motifs even within the same Aromatoleum genus.

Gelatinous filter feeders increase ecosystem efficiency

Gelatinous filter feeders (e.g., salps, doliolids, and pyrosomes) have high filtration rates and can feed at predator:prey size ratios exceeding 10,000:1, yet are seldom included in ecosystem or climate models. We investigated foodweb and trophic dynamics in the presence and absence of salp blooms using traditional productivity and grazing measurements combined with compound-specific isotopic analysis of amino acids estimation of trophic position during Lagrangian framework experiments in the Southern Ocean. Trophic positions of salps ranging 10–132 mm in size were 2.2 ± 0.3 (mean ± std) compared to 2.6 ± 0.4 for smaller (mostly crustacean) mesozooplankton. The mostly herbivorous salp trophic position was maintained despite biomass dominance of ~10-µm-sized primary producers. We show that potential energy flux to >10-cm organisms increases by approximately an order of magnitude when salps are abundant, even without substantial alteration to primary production. Comparison to a wider dataset from other marine regions shows that alterations to herbivore communities are a better predictor of ecosystem transfer efficiency than primary-producer dynamics. These results suggest that diverse consumer communities and intraguild predation complicate climate change predictions (e.g., trophic amplification) based on linear food chains. These compensatory foodweb dynamics should be included in models that forecast marine ecosystem responses to warming and reduced nutrient supply.

Tracking atrazine degradation in soil combining 14C-mineralisation assays and compound-specific isotope analysis

The quantification of pesticide dissipation in agricultural soil is challenging. In this study, we investigated atrazine biodegradation in both liquid and soil experiments bioaugmented with distinct atrazine-degrading bacterial isolates. This was achieved by combining 14C-mineralisation assays and compound-specific isotope analysis of atrazine. In liquid experiments, the three bacterial isolates mineralised over 40% of atrazine, demonstrating their potential for extensive degradation. However, the kinetics of mineralisation and degradation varied among the isolates. Carbon stable isotope fractionation was similar for Pseudomonas isolates ADPT34 and ADP2T0, but slightly higher for Chelatobacter SR27. In soil experiments, atrazine primarily degraded into atrazine-desethyl, while atrazine-hydroxy was mainly observed in experiments with SR27. Atrazine mineralisation in soil by ADPT34 and SR27 exceeded 40%, whereas ADP2T0 exhibited a mineralisation rate of 10%. In experiments with ADPT34 and SR27, atrazine 14C-residues were predominantly found in the non-extractable fraction, whereas they accumulated in the extractable fraction in the experiment with ADP2T0. Compound-specific isotope analysis (CSIA) relies on changes of stable isotope ratios and holds potential to evaluate herbicide transformation in soil. CSIA of atrazine indicated atrazine biodegradation in water and solvent extractable soil fractions and varied between 29% and 52%, depending on the bacterial isolate. Despite atrazine degradation in both soil fractions, a significant portion of atrazine residues persisted, depending on the bacterial degrader, initial cell concentration, and mineralisation and degradation rates. Overall, our approach can aid in quantifying atrazine persistence and degradation in soil, and in optimizing bioaugmentation strategies for remediating soils contaminated with persistent herbicides.

Quantifying remediation of chlorinated volatile compounds by sulfidated nano zerovalent iron treatment using numerical modeling and CSIA

Sulfidated nanoscale zerovalent iron (S-nZVI) has demonstrated promising reactivity and longevity for remediating chlorinated volatile compounds (cVOC) contaminants in laboratory tests. However, its effectiveness in field applications remains inadequately evaluated. This study provides the first quantitative evaluation of the long-term effectiveness of carboxymethyl cellulose-stabilized S-nZVI (CMC-S-nZVI) at a cVOC-contaminated field site. A reactive transport model-based numerical approach delineates the change in cVOC concentrations and carbon isotope values (i.e., δ13C from compound-specific stable isotope analysis (CSIA)) caused by dissolution of dense non-aqueous phase liquid, sorption, and pathway-specific degradation and production, respectively. This delineation reveals quantitative insights into remediation effectiveness typically difficult to obtain, including extent of degradation, contributions of different degradation pathways, and degradation rate coefficients. Significantly, even a year after CMC-S-nZVI application, degradation remains an important process effectively removing various cVOC contaminants (i.e., chlorinated ethenes, 1,2-dichloroethanes, and chlorinated methanes) at an extent varying from 5 %-62 %. Although the impacts of CMC-S-nZVI abundance on degradation vary for different cVOC and for different sampling locations at the site, for the primary site contaminants of tetrachloroethene and trichloroethene, their predominance of dichloroelimination pathway (≥ 88 %), high degradation rate coefficient (0.4–1.7 d-1), and occurrence at locations with relatively high CMC-S-nZVI abundance strongly indicate the effectiveness of abiotic remediation. These quantitative assessments support that CMC-S-nZVI supports sustainable ZVI-based remediation. Further, the novel numerical approach presented in this study provides a powerful tool for quantitative cVOC remediation assessments at complex field sites where multiple processes co-occur to control both concentration and CSIA data.

Source differentiation of BTEX compounds in groundwater contaminated due to refinery activities

This study aims to identify sources of groundwater contamination in a refinery area using integrated compound-specific stable isotope analysis (CSIA), oil fingerprinting techniques, hydrogeological data, and distillation analysis. The investigations focused on determination of the origin of benzene, toluene, ethylbenzene, and xylenes (BTEX), and aliphatic hydrocarbons as well. Groundwater and floating oil samples were collected from extraction wells for analysis. Results indicate presence of active leaks in both the northern and southern zones. In the northern zone, toluene was found to primarily originate from oil products like aviation turbine kerosene (ATK or aviation fuel), kerosene, regular gasoline, and diesel fuel. Additionally, stable isotope ratios of carbon and hydrogen for ethylbenzene, o-xylene (ortho xylene) and p-xylene (para xylene) in zone A suggested the pollution originated from gasoline within the northern zone. The origin of super gasoline (with higher octane) identified in southern zone using δ13C and δ2H values of toluene in the floating oil and groundwater samples. Further, biodegradation of toluene likely occurred in southern zone according to δ13C and δ2H. The findings underscore the critical importance of integrating CSIA and fingerprinting techniques to effectively address the challenges of source identification and relying solely on each method independently is insufficient. Accordingly, comparing the GC-MS results of floating oil samples with ATK and jet fuel (JP4) standards can be effectively utilized for source differentiation. However, this method showed no practical application to distinguish different types of diesel or gasoline. The accuracy and reliability of source identification of BTEX compounds may significantly improve when hydrogeological data incorporates with stable isotopes analysis. Additionally, the results of this study will elevate the procedures for fuel-related contaminants source identification of the polluted groundwater that is crucial to develop effective remediation strategies.

Dietary plasticity and broad North Atlantic origins inferred from bulk and amino acid-specific δ15N and δ13C favour killer whale range expansions into Arctic waters.

Killer whales (Orcinus orca) occur seasonally in the eastern Canadian Arctic (ECA), where their range expansion associated with declining sea ice have raised questions about the impacts of increasing killer whale predation pressure on Arctic-endemic prey. We assessed diet and distribution of ECA killer whales using bulk and compound-specific stable isotope analysis (CSIA) of amino acids (AA) of 54 skin biopsies collected from 2009 to 2020 around Baffin Island, Canada. Bulk ECA killer whale skin δ15N and δ13C values did not overlap with potential Arctic prey after adjustment for trophic discrimination, and instead reflected foraging history in the North Atlantic prior to their arrival in the ECA. Adjusted killer whale stable isotope (SI) values primarily overlapped with several species of North Atlantic baleen whales or tuna. Amino acid (AA)-specific δ15N values indicated the ECA killer whales fed primarily on marine mammals, having similar glutamic acid δ15N-phenylalanine δ15N (δ15NGlx-Phe) and threonine δ15N (δ15NThr) as mammal-eating killer whales from the eastern North Pacific (ENP) that served as a comparative framework. However, one ECA whale grouped with the fish-eating ENP ecotype based δ15NThr. Distinctive essential AA δ13C of ECA killer whale groups, along with bulk SI similarity to killer whales from different regions of the North Atlantic, indicates different populations converge in Arctic waters from a broad source area. Generalist diet and long-distance dispersal capacity favour range expansions, and integration of these insights will be critical for assessing ecological impacts of increasing killer whale predation pressure on Arctic-endemic species.