Isotope Fractionation Patterns Research Articles

Direct Phototransformation of Sulfamethoxazole Characterized by Four-Dimensional Element Compound Specific Isotope Analysis.

The antibiotic sulfamethoxazole (SMX) undergoes direct phototransformation by sunlight, constituting a notable dissipation process in the environment. SMX exists in both neutral and anionic forms, depending on the pH conditions. To discern the direct photodegradation of SMX at various pH levels and differentiate it from other transformation processes, we conducted phototransformation of SMX under simulated sunlight at pH 7 and 3, employing both transformation product (TP) and compound-specific stable isotope analyses. At pH 7, the primary TPs were sulfanilic acid and 3A5MI, followed by sulfanilamide and (5-methylisoxazol-3-yl)-sulfamate, whereas at pH 3, a photoisomer was the dominant product, followed by sulfanilic acid and 3A5MI. Isotope fractionation patterns revealed normal 13C, 34S, and inverse 15N isotope fractionation, which exhibited significant differences between pH 7 and 3. This indicates a pH-dependent transformation process in SMX direct phototransformation. The hydrogen isotopic composition of SMX remained stable during direct phototransformation at both pH levels. Moreover, there was no variation observed in 33S between the two pH levels, indicating that the 33S mass-independent process remains unaffected by changes in pH. The analysis of main TPs and single-element isotopic fractionation suggests varying combinations of bond cleavages at different pH values, resulting in distinct patterns of isotopic fractionation. Conversely, dual-element isotope values at different pH levels did not significantly differ, indicating cleavage of several bonds in parallel. Hence, prudent interpretation of dual-element isotope analysis in these systems is warranted. These findings highlight the potential of multielement compound-specific isotope analysis in characterizing pH-dependent direct phototransformation of SMX, thereby facilitating the evaluation of its natural attenuation through sunlight photolysis in the environment.

Pyrolysis experiments of model compounds to explore carbon isotope fractionation in propane from natural gas

Investigating the mechanisms that determine the bulk and position-specific carbon isotopic distributions of propane in natural gas will help elucidate its formation and evolution. We used octadecane and squalane as model compounds that give simple precursors for gas production in gold-tube isothermal pyrolysis experiments to study the variations in intermolecular and intramolecular distributions of isotopes in the generated gaseous hydrocarbons. The δ13C values of the products and inverses of their carbon numbers (1/n where n = C1–C5) showed a negative linear relationship versus maturity, indicating that they formed by homolytic cleavage of C–C bonds and that the precursors showed homogeneous distributions of carbon isotopes. However, the significant difference in the kinetic isotopic effects (KIEs) of the gas generated by cracking of two model compounds under the same experimental conditions is not readily explained by single homolytic bond cleavage. The results indicate that besides the KIE of C–C bond cleavage, the bulk and position-specific carbon isotopic compositions of propane are related to the chemical and isotopic structures of the precursors and the propane transformation ratio. Based on the sites of C–C bond cleavage, two isotopic fractionation patterns (i.e., normal propyl and isopropyl models) may explain the bulk and position-specific carbon isotopic distributions of the generated propane. According to the propyl model, propane originates from (normal) propyl structures (CH3CH2CH2*) in the precursor via C–C bond cleavage at a terminal site of a propyl group, while the isopropyl model involves propane derived from isopropyl structures (CH3CH*CH3) in the precursor, with C–C bond cleavage at the central site. Simulations show that these distributions for propane cracked from octadecane closely follow the propyl model, whereas propane generated from squalane showed mixed contributions from both models, and its bulk and position-specific carbon isotopic distributions depend on the proportions of propyl and isopropyl structures in the precursors. Variations of propane’s position-specific carbon isotopic distributions during the main stage of propane generation indicate that free radical reactions are the main pathway for thermogenic propane formation, resulting in similar KIEs for propane terminal and central carbons. Therefore, the position-specific carbon isotopic distribution of propane can provide evidence of its formation mechanism and shows potential for revealing the origin and evolution of natural gas.

Efficient atrazine removal in bioaugmentation constructed wetland: Insight from stable isotope fractionation analysis

Constructed wetlands (CW) provides a sustainable approach to remove pesticides from agricultural or urban runoff, while the low efficiency of the herbicide atrazine remains a challenge. Focused on improving atrazine removal in CW, a bioaugmentation strategy was implemented using the mixed culture of atrazine-degrading bacteria. The results shown a significant increase in atrazine removal from 26.2 ± 6.9% to 60.9 ± 8.7–90.6 ± 4.1% during the bioaugmentation phases. To investigate in-situ degradation processes of atrazine, compound-specific stable isotope analysis (CSIA) was conducted. The carbon and nitrogen isotope fractionation pattern revealed atrazine was primarily degraded via a hydrolysis pathway mediated by microorganisms. The biodegradation extent of atrazine calculated from δ13C signatures suggested that 90% of atrazine was removed via the hydrolysis pathway, with only a small portion being removed abiotically. This was additionally supported by an increase in microbial diversity and the abundance of specific bacteria (such as Rhizobium sp. and Pseudomonas sp.) capable of degrading atrazine. Altogether, this study demonstrated the effectiveness of atrazine-degrading mixed culture and its feasibility on bioaugmentation atrazine removal in CW. This work highlights the potential of bioaugmentation in sustainable pesticide removal approaches and CSIA can contribute to an understanding of in-situ pesticide transformation processes in wetland systems.

Sulfate-driven anaerobic oxidation of methane inferred from trace-element chemistry and nickel isotopes of pyrite

In marine sediments, formation of pyrite (FeS2) is promoted by both organoclastic sulfate reduction (OSR) and sulfate-driven anaerobic oxidation of methane (SD-AOM), and these two microbial pathways might yield differing patterns of sulfur and nickel isotopic fractionation and trace-element enrichment. To better understand these pathways, we analyzed the geochemistry of authigenic pyrite aggregates from the Upper Quaternary of the western Andaman Sea (International Ocean Discovery Program, Expedition 353, Site U1447A). 34S-enriched pyrites (to ∼+41‰) in Unit Ib are interpreted as products of SD-AOM, and their enrichments in Co and Ni and low δ60Ni values (−0.63‰ to −0.09‰) may represent diagnostic signatures of a reverse-methanogenesis microbial pathway. In contrast, 34S-depleted pyrites (∼–46‰ to –38‰) in both Units I and II are consistent with sulfide formation through early diagenetic remineralization of organic matter, and their relative enrichments in Cu and V and heavier δ60Ni values (to +0.41‰) may be diagnostic of this alternative microbial pathway. This study reports for the first time a fractionation of Ni isotopes linked to preferential uptake of isotopically light Ni by the enzyme Mcr (M reductase enzyme) in reverse methanogenesis and demonstrates that OSR- and SD-AOM-associated pyrites are potentially distinguishable on the basis of their δ60Ni compositions. Such geochemical signatures may prove useful in determining processes of pyrite formation in paleo-depositional systems and in identifying ancient methane emission events.

From soil to cacao bean: Unravelling the pathways of cadmium translocation in a high Cd accumulating cultivar of Theobroma cacao L.

The research on strategies to reduce cadmium (Cd) accumulation in cacao beans is currently limited by a lack of understanding of the Cd transfer pathways within the cacao tree. Here, we elucidated the transfer of Cd from soil to the nib (seed) in a high Cd accumulating cacao cultivar. Here, we elucidated the transfer of Cd from soil to the nib (seed) in a high Cd accumulating cacao cultivar through Cd stable isotope fractionation, speciation (X-Ray Absorption Spectroscopy), and localization (Laser Ablation Inductively Coupled Plasma Mass Spectrometry). The plant Cd concentrations were 10-28 higher than the topsoil Cd concentrations and increased as placenta< nib< testa< pod husk< root< leaf< branch. The retention of Cd in the roots was low. Light Cd isotopes were retained in the roots whilst heavier Cd isotopes were transported to the shoots (Δ 114/110 Cd shoot-root = 0.27 ± 0.02 ‰ (weighted average ± standard deviation)). Leaf Cd isotopes were heavier than Cd in the branches (Δ 114/110 Cd IF3 leaves-branch = 0.18 ± 0.01 ‰), confirming typical trends observed in annual crops. Nibs and branches were statistically not distinguishable (Δ 114/110 Cd nib-branch = -0.08‰ ± 0.06 ‰), contrary to the leaves and nibs (Δ 114/110 Cd nib-IF3 leaves = -0.25‰ ± 0.05 ‰). These isotope fractionation patterns alluded to a more direct transfer from branches to nibs rather than from leaves to nibs. The largest fraction (57%) of total plant Cd was present in the branches where it was primarily bound to carboxyl-ligands (60-100%) and mainly localized in the phloem rays and phelloderm of the bark. Cadmium in the nibs was mainly bound to oxygen ligands (60-90%), with phytate as the most plausible ligand. The weight of evidence suggested that Cd was transferred like other nutrients from root to shoot and accumulated in the phloem rays and phelloderm of the branches to reduce the transfer to foliage. Finally, the data indicated that the main contribution of nib Cd was from the phloem tissues of the branch rather than from leaf remobilization. This study extended the limited knowledge on Cd accumulation in perennial, woody crops and revealed that the Cd pathways in cacao are markedly different than in annual crops.

Cadmium isotope fractionation during transport processes within agricultural soil profiles in a mining area: Implications for source tracing

Cadmium (Cd) isotope fractionation patterns within soil profiles and the underlying mechanisms remain unclear and poorly documented. Here, Cd concentrations and isotope compositions of metal ore, surface soils and soil profile samples around a lead-zinc mine in southwest China were determined, and the relationships between soil properties and Cd isotope fractionation within the soil profiles were investigated. Cadmium concentrations of eleven surface soil samples were 0.49–66.1 mg kg−1 and the samples with high Cd concentrations had Cd isotope compositions similar to the metal ore (δ114/110Cd = 0.02‰), indicating that mining activity was the main Cd source at the study areas. Within three soil profiles with different Cd pollution levels the δ114/110Cd values gradually increased with increasing depth from 0 to 40 cm (Δ114/110Cd = 0.08–0.18‰), reaching a maximum at 30–40 cm depth, and then remained fairly constant or decreased with increasing soil depth below 40 cm. Soil δ114/110Cd values were negatively correlated with free iron and manganese oxides contents, which decreased at 0–40 cm depth then increased below 40 cm. This indicates that light Cd isotopes within 0–40 cm depth preferentially migrated downward with free iron and manganese oxides, leaving the soils at a depth of 0–40 cm enriched in heavy Cd isotopes. At 40–90 cm depth the preferential retention of heavy Cd isotopes by hydroxides may be responsible for the gradual decrease in δ114/110Cd values with increasing soil depth. These observations demonstrate that the vertical migration of Cd can induce detectable isotope fractionation within soil profiles and alter the δ114/110Cd values including those of the surface soils. Our study highlights the need to consider Cd mobilization and transport in soil profiles when tracing metal sources using isotope techniques.

Stable Isotope Fractionation of Metals and Metalloids in Plants: A Review.

This work critically reviews stable isotope fractionation of essential (B, Mg, K, Ca, Fe, Ni, Cu, Zn, Mo), beneficial (Si), and non-essential (Cd, Tl) metals and metalloids in plants. The review (i) provides basic principles and methodologies for non-traditional isotope analyses, (ii) compiles isotope fractionation for uptake and translocation for each element and connects them to physiological processes, and (iii) interlinks knowledge from different elements to identify common and contrasting drivers of isotope fractionation. Different biological and physico-chemical processes drive isotope fractionation in plants. During uptake, Ca and Mg fractionate through root apoplast adsorption, Si through diffusion during membrane passage, Fe and Cu through reduction prior to membrane transport in strategy I plants, and Zn, Cu, and Cd through membrane transport. During translocation and utilization, isotopes fractionate through precipitation into insoluble forms, such as phytoliths (Si) or oxalate (Ca), structural binding to cell walls (Ca), and membrane transport and binding to soluble organic ligands (Zn, Cd). These processes can lead to similar (Cu, Fe) and opposing (Ca vs. Mg, Zn vs. Cd) isotope fractionation patterns of chemically similar elements in plants. Isotope fractionation in plants is influenced by biotic factors, such as phenological stages and plant genetics, as well as abiotic factors. Different nutrient supply induced shifts in isotope fractionation patterns for Mg, Cu, and Zn, suggesting that isotope process tracing can be used as a tool to detect and quantify different uptake pathways in response to abiotic stresses. However, the interpretation of isotope fractionation in plants is challenging because many isotope fractionation factors associated with specific processes are unknown and experiments are often exploratory. To overcome these limitations, fundamental geochemical research should expand the database of isotope fractionation factors and disentangle kinetic and equilibrium fractionation. In addition, plant growth studies should further shift toward hypothesis-driven experiments, for example, by integrating contrasting nutrient supplies, using established model plants, genetic approaches, and by combining isotope analyses with complementary speciation techniques. To fully exploit the potential of isotope process tracing in plants, the interdisciplinary expertise of plant and isotope geochemical scientists is required.

Photodegradation of phthalic acid esters under simulated sunlight: Mechanism, kinetics, and toxicity change

The photodegradation of two phthalic acid esters (PAEs), dimethyl phthalate (DMP) and di-n-octyl phthalate (DOP), under simulated sunlight in aqueous or organic phases (n-hexane (HEX) and dichloromethane (DCM)) was investigated. The mean photodegradation rates were ranked by half-lives as follows: DOP in DCM (3.77 h) < DMP in DCM (9.62 h) < DOP in H2O (3.99 days) < DMP in H2O (19.2 days) < DOP in HEX (21.0 days) < DMP in HEX (>30 days). Compound-specific stable isotope analysis (CSIA) combined with intermediate analysis was employed to explore the involved initial photoreaction mechanism. C–O bond cleavage, chlorine radical adduction to the aromatic ring, competing reactions of chlorine radical adduction to the aromatic ring and side chain, and a singlet oxygen-mediated pathway were mainly responsible for initial photodegradation mechanism of PAEs in H2O, DMP in DCM, DOP in DCM, and DOP in HEX, respectively. Furthermore, distinct isotope fractionation patterns of PAEs photodegradation open the possibility of using CSIA to differentiate the involved solvents in the field. More toxic and recalcitrant intermediates emerged during the photodegradation of DMP in DCM, while the risk to human health was reduced during the photochemical transformation of DOP in organic solvents.

Trichloromethane dechlorination by a novel Dehalobacter sp. strain 8M reveals a third contrasting C and Cl isotope fractionation pattern within this genus

Trichloromethane (TCM) is a pollutant frequently detected in contaminated aquifers, and only four bacterial strains are known to respire it. Here, we obtained a novel Dehalobacter strain capable of transforming TCM to dichloromethane, which was denominated Dehalobacter sp. strain 8M. Besides TCM, strain 8M also completely transformed 1,1,2-trichloroethane to vinyl chloride and 1,2-dichloroethane. Quantitative PCR analysis for the 16S rRNA genes confirmed growth of Dehalobacter with TCM and 1,1,2-trichloroethane as electron acceptors. Carbon and chlorine isotope fractionation during TCM transformation was studied in cultured cells and in enzymatic assays with cell suspensions and crude protein extracts. TCM transformation in the three studied systems resulted in small but significant carbon (εC = −2.7 ± 0.1‰ for respiring cells, −3.1 ± 0.1‰ for cell suspensions, and − 4.1 ± 0.5‰ for crude protein extracts) and chlorine (εCl = −0.9 ± 0.1‰, −1.1 ± 0.1‰, and − 1.2 ± 0.2‰, respectively) isotope fractionation. A characteristic and consistent dual CCl isotope fractionation pattern was observed for the three systems (combined ΛC/Cl = 2.8 ± 0.3). This ΛC/Cl differed significantly from previously reported values for anaerobic dechlorination of TCM by the corrinoid cofactor vitamin B12 and other Dehalobacter strains. These findings widen our knowledge on the existence of different enzyme binding mechanisms underlying TCM-dechlorination within the genus Dehalobacter and demonstrates that dual isotope analysis could be a feasible tool to differentiate TCM degraders at field studies.

Zinc isotope composition of the Proterozoic clastic-dominated McArthur River Zn-Pb-Ag deposit, northern Australia

This study provides a Zn isotope characterization (δ66Zn) of the c. 1,640 Ma clastic-dominated McArthur River Zn-Pb-Ag deposit. Dolomitic, siltstone-hosted sulfide ores were sampled in two separate drill cores. One intersects the stratiform, vertically stacked orebodies at the centre of the deposit, and the other one intersects the south-eastern periphery of the deposit. The analyzed ores show relatively invariable δ66Zn values typical of the continental crust (0.35 ‰ median with 0.05 ‰ standard deviation). This signature is consistent with (near-) quantitative sulfide (sphalerite) precipitation during ore formation, negligible Zn isotope fractionation during fluid transport, and perhaps muted fractionation associated with near-quantitative Zn extraction from the source. Hence, our data show that a pronounced Zn isotope fractionation pattern characterized by lower δ66Zn values closer to the hydrothermal source, as reported from other Zn-Pb deposits, is not developed within the McArthur River deposit. However, across some orebodies, we note a subtle Zn isotope fractionation trend that correlates with the relative abundances of several temperature-sensitive base and trace metals (Zn, Pb, and Ag). This trend can be explained by subtle influence of Rayleigh-type Zn isotope fractionation during fluid evolution and Zn sulfide precipitation. Previous studies have suggested that Zn isotopes may be useful in the exploration for economic mineralization, as these studies observed both a significant Zn isotope halo and δ66Zn values markedly different from the continental crust. However, because both characteristics are not observable at McArthur River, the Zn isotope system may not have been useful in finding this deposit.

Triple-Element Compound-Specific Stable Isotope Analysis (3D-CSIA): Added Value of Cl Isotope Ratios to Assess Herbicide Degradation.

Multielement isotope fractionation studies to assess pollutant transformation are well-established for point-source pollution but are only emerging for diffuse pollution by micropollutants like pesticides. Specifically, chlorine isotope fractionation is hardly explored but promising, because many pesticides contain only few chlorine atoms so that "undiluted" position-specific Cl isotope effects can be expected in compound-average data. This study explored combined Cl, N, and C isotope fractionation to sensitively detect biotic and abiotic transformation of the widespread herbicides and groundwater contaminants acetochlor, metolachlor, and atrazine. For chloroacetanilides, abiotic hydrolysis pathways studied under acidic, neutral, and alkaline conditions as well as biodegradation in two soils resulted in pronounced Cl isotope fractionation (εCl from -5.0 ± 2.3 to -6.5 ± 0.7‰). The characteristic dual C-Cl isotope fractionation patterns (ΛC-Cl from 0.39 ± 0.15 to 0.67 ± 0.08) reveal that Cl isotope analysis provides a robust indicator of chloroacetanilide degradation. For atrazine, distinct ΛC-Cl values were observed for abiotic hydrolysis (7.4 ± 1.9) compared to previous reports for biotic hydrolysis and oxidative dealkylation (1.7 ± 0.9 and 0.6 ± 0.1, respectively). The 3D isotope approach allowed differentiating transformations that would not be distinguishable based on C and N isotope data alone. This first data set on Cl isotope fractionation in chloroacetanilides, together with new data in atrazine degradation, highlights the potential of using compound-specific chlorine isotope analysis for studying in situ pesticide degradation.

δ60Ni and δ13C Composition of Serpentinites and Carbonates of the Tekirova Ophiolite, Turkey, and Meatiq Ophiolite, Egypt

Nickel isotope fractionation patterns in continental ultramafic environments generally show a depletion of δ60Ni in weathered rocks and an enrichment in bedrock samples. The present study focuses on stable Ni isotope fractionation patterns in carbonate-rich, ultramafic ophiolite samples with concomitant fluids at an active serpentinization site in southwestern Turkey, with a comparison to results from an inactive serpentinization site in the Eastern Desert of Egypt with carbonate-rich samples. All solid phase data from the inactive serpentinization area are consistent with previously reported values from serpentinites, whereas the solid precipitates in the active area (SW Turkey) give values slightly heavier than previously reported data. However, the Ni isotopic signatures in the active serpentinization system likely reflect the scavenging of light Ni by iron oxide and carbonate precipitation, as has been previously demonstrated in laboratory coprecipitation experiments. It is also possible that the active system results resemble previous laboratory experimental results that show a relatively strong initial fractionation between fluids and solids, which then diminishes with time due to aging of the precipitates.

Lithium and potassium isotope fractionation during silicate rock dissolution: An experimental approach

This study experimentally investigates the isotopic behaviors of Li and K during the dissolution of silicate rocks (i.e., basalt and granite). Proton-driven dissolution (in 0.8 M HNO3) and ligand-driven dissolution (in 5 mM critic acid or oxalic acid) experiments were performed in batch-closed systems over 15 days. We provide a time-series interpretation of Li and K isotope fractionation during silicate dissolution in ultra-acidic (unidirectional) and near-natural (biologically affected) environments. As the reaction progressed, we measured large isotope fractionation between the liquid (l) phase and the pristine silicate (s) phase, ranging from −10.3 to 0.1‰ (Δ7Lil-s) and from −1.01 to −0.11‰ (Δ41Kl-s) through the early stage of dissolution (<24 h). The enrichment of lighter Li and K isotopes in the solutions rapidly diminished as rock dissolution continued and gradually approached equilibrium to the end of experiments. In contrast, resorption of pre-leached isotopically lighter Li on silicate residuals during ligand-driven dissolution produced lighter isotope enrichment in the solutions compared to the initial rock by up to 2.8‰. Despite the preferential dissolution of specific minerals, the isotope fractionation patterns of Li and K do not vary with lithology, indicating limited inter-mineral isotopic differences. During the experiments, the Li and K isotopic pattern could be divided into two-to-three stages. The initial enrichment of light isotopes in the liquids can be ascribed to the kinetic isotope effect, confounded by diffusion and ion solvation. A later transition towards no isotope fractionation of Li and K may be explained by (i) the masking effect from dissolution, and (ii) an imprint from the destruction of 7Li/41K-enriched surface layers. Lateral resorption of solute Li after ~100 h reaction could be facilitated by the electrostatic attraction from increasing surface negative charges and active hydroxyls with increasing pH during ligand-driven dissolution (pH ~ 4) relative to proton-driven dissolution (pH ~ 0.2). Therefore, the presence of organic ligands impacts dissolution stoichiometry, and potentially modifies Li isotope fractionation in natural weathering environments. In comparison, K isotope fractionation driven by rock dissolution stops immediately (within days) after starting the experiments. This research helps to understand the mechanisms of Li and K isotope fractionation during chemical weathering and trace long-term climate change using geological records.

Nitrogen isotope fractionation of amino acids from a controlled study on the green turtle (Chelonia mydas): expanding beyond Glx/Phe for trophic position

Compound specific nitrogen isotope analysis of amino acids (AA CSIA) has been used to study the trophic ecology of many marine organisms because of its ability to characterize the δ15N value at the base of a food web while simultaneously providing trophic position information from a single tissue sample of a consumer. Although application of this method is becoming more widely used in trophic studies, critical assumptions such as amino acid designation and trophic discrimination factors remain unresolved for many taxa and tissue types. In this study, we used captive green turtles (Chelonia mydas) in a controlled feeding study to determine and evaluate individual amino acid isotope fractionation patterns and trophic discrimination factors (TDFs) for skin and plasma. Our data build on findings from previous studies that show that the traditional paradigm of using glutamic acid and phenylalanine as trophic and source amino acids, respectively, for trophic position estimation is consistent for green turtles; we also provide evidence to support the potential utility of other combinations of amino acids for trophic position calculations. Green turtle TDFs for glutamic acid and phenylalanine were 4.0 ± 0.5 ‰ and 6.6 ± 0.7 ‰ for skin and plasma, respectively. We found serine to have the largest Δδ15N (turtle-diet discrimination) value of all amino acids in both skin and plasma, while lysine Δδ15N values were consistent for use as a source amino acid in skin and plasma tissue. We evaluated our TDFs by estimating trophic position of four sea turtle species using previously published amino acid isotope data. These results indicate that for green turtles, the traditional use of glutamic acid and phenylalanine along with a combination of trophic amino acids paired with lysine can provide robust trophic position estimates. Moreover, we highlight the taxa and tissue-specific nature of amino acid nitrogen isotope fractionation patterns in green turtle tissues and underscore that well-approximated TDFs can refine trophic position estimates for sea turtles.

Dual Element (C/Cl) Isotope Analysis Indicates Distinct Mechanisms of Reductive Dehalogenation of Chlorinated Ethenes and Dichloroethane in Dehalococcoides mccartyi Strain BTF08 With Defined Reductive Dehalogenase Inventories.

Dehalococcoides mccartyi strain BTF08 has the unique property to couple complete dechlorination of tetrachloroethene and 1,2-dichloroethane to ethene with growth by using the halogenated compounds as terminal electron acceptor. The genome of strain BTF08 encodes 20 genes for reductive dehalogenase homologous proteins (RdhA) including those described for dehalogenation of tetrachloroethene (PceA, PteA), trichloroethene (TceA) and vinyl chloride (VcrA). Thus far it is unknown under which conditions the different RdhAs are expressed, what their substrate specificity is and if different reaction mechanisms are employed. Here we found by proteomic analysis from differentially activated batches that PteA and VcrA were expressed during dechlorination of tetrachloroethene to ethene, while TceA was expressed during 1,2-dichloroethane dehalogenation. Carbon and chlorine compound-specific stable isotope analysis suggested distinct reaction mechanisms for the dechlorination of (i) cis-dichloroethene and vinyl chloride versus (ii) tetrachloroethene. This differentiation was observed independent of the expressed RdhA proteins. Differently, two stable isotope fractionation patterns were observed for 1,2-dichloroethane transformation, for cells with distinct RdhA inventories. Conclusively, we could link specific RdhA expression with functions and provide an insight into the apparently substrate-specific reaction mechanisms in the pathway of reductive dehalogenation in D. mccartyi strain BTF08. Data are available via ProteomeXchange with identifiers PXD018558 and PXD018595.

Dual C–Cl isotope analysis for characterizing the anaerobic transformation of α, β, γ, and δ-hexachlorocyclohexane in contaminated aquifers

Hexachlorocyclohexanes (HCHs) are widespread and persistent environmental pollutants, which cause heavy contamination in soil, sediment and groundwater. An anaerobic consortium, which was enriched on β-HCH using a soil sample from a contaminated area of a former pesticide factory, was capable to transform α, β, γ, and δ-HCH via tetrachlorocyclohexene isomers stoichiometrically to benzene and chlorobenzene. The carbon and chlorine isotope enrichment factors (εC and εCl) of the dehalogenation of the four isomers ranged from −1.9 ± 0.3 to −6.4 ± 0.7‰ and from −1.6 ± 0.2 to −3.2 ± 0.6‰, respectively, and the correlation of δ37Cl and δ13C (Λ values) of the four isomers ranged from 1.1 ± 0.1 to 2.4 ± 0.2. The evaluation of Λ and the apparent kinetic isotope effects (AKIE) for carbon and chlorine may lead to the hypothesis that the two eliminated chlorine atoms of α- and γ-HCH were in axial positions, the same as for the β-HCH conformer which has six chlorine atoms in axial positions after ring flip. The dichloroelimination of δ-HCH resulted in distinct AKIE and Λ values as one chlorine atom is in axial whereas the other chlorine atoms are in the equatorial positions. Significant chlorine and carbon isotope fractionations of HCH isomers were observed in the samples from a contaminated aquifer (Bitterfeld, Germany). The 37Cl/35Cl and 13C/12C isotope fractionation patterns of HCH isomers from laboratory experiments were used diagnostically in a model to characterize microbial dichloroelimination in the field study. The comparison of isotope fractionation patterns indicates that the transformation of HCH isomers at the field was mainly governed by microbial dichloroelimination transformation.

Mechanism investigation and stable isotope change during photochemical degradation of tetrabromobisphenol A (TBBPA) in water under LED white light irradiation

Light driven degradation is very promising for pollutants remediation. In the present work, photochemical reaction of tetrabromobisphenol A (TBBPA) under LED white light (λ > 400 nm) irradiation system was investigated to figure out the TBBPA photochemical degradation pathways and isotope fractionation patterns associated with transformation mechanisms. Results indicated that photochemical degradation of TBBPA would happen only with addition to humic acid in air bubbling but not in N2 bubbling. For photochemical reaction of TBBPA, singlet oxygen (1O2) was found to be important reactive oxygen species for the photochemical degradation of TBBPA. 2,6-Dibromo-4-(propan-2-ylidene)cyclohexa-2,5-dienone and two isopropyl phenol derivatives were identified as the photochemical degradation intermediates by 1O2. 2,6-Dibromo-4-(1-methoxy-ethyl)-phenol was determined as an intermediate via oxidative skeletal rearrangement, reduction and O-methylation. Hydrolysis product hydroxyl-tribromobisphenol A was also observed in the reductive debromination process. In addition, to deeply explore the mechanism, carbon and bromine isotope analysis were performed using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) and gas chromatography-multicollector inductively coupled plasma mass spectrometry (GC/MC/ICPMS) during the photochemical degradation of TBBPA. The results showed that photochemical degradation could not result in statistically significant isotope fractionation, indicated that the bond cleavage of C-C and C-Br were not the rate controlling process. Stable isotope of carbon being not fractionated will be useful for distinguishing the pathways of TBBPA and tracing TBBPA fate in water systems. This work sheds light on photochemical degradation mechanisms of brominated organic contaminants.

Dual C-Cl Isotope Analysis for Characterizing the Reductive Dechlorination of α- and γ-Hexachlorocyclohexane by Two Dehalococcoides mccartyi Strains and an Enrichment Culture.

Hexachlorocyclohexanes (HCHs) are persistent organic contaminants that threaten human health. Microbial reductive dehalogenation is one of the most important attenuation processes in contaminated environments. This study investigated carbon and chlorine isotope fractionation of α- and γ-HCH during the reductive dehalogenation by three anaerobic cultures. The presence of tetrachlorocyclohexene (TeCCH) indicated that reductive dichloroelimination was the first step of bond cleavage. Isotope enrichment factors (εC and εCl) were derived from the transformation of γ-HCH (εC, from -4.0 ± 0.5 to -4.4 ± 0.6 ‰; εCl, from -2.9 ± 0.4 to -3.3 ± 0.4 ‰) and α-HCH (εC, from -2.4 ± 0.2 to -3.0 ± 0.4 ‰; εCl, from -1.4 ± 0.3 to -1.8 ± 0.2 ‰). During α-HCH transformation, no enantioselectivity was observed, and similar εc values were obtained for both enantiomers. The correlation of 13C and 37Cl fractionation (Λ = Δδ13C/Δδ37Cl ≈ εC/εCl) of γ-HCH (from 1.1 ± 0.3 to 1.2 ± 0.1) indicates similar bond cleavage during the reductive dichloroelimination by the three cultures, similar to α-HCH (1.7 ± 0.2 to 2.0 ± 0.3). The different isotope fractionation patterns during reductive dichloroelimination and dehydrochlorination indicates that dual-element stable isotope analysis can potentially be used to evaluate HCH transformation pathways at contaminated field sites.

Melt chemistry and redox conditions control titanium isotope fractionation during magmatic differentiation

Titanium offers a burgeoning isotope system that has shown significant promise as a tracer of magmatic processes. Recent studies have shown that Ti isotopes display significant mass-dependent variations linked to the crystallisation of Fe-Ti oxides during magma differentiation. We present a comprehensive set of Ti isotope data for a range of differentiation suites from alkaline (Ascension Island, Afar and Heard Island), calc-alkaline (Santorini) and tholeiitic (Monowai seamount and Alarcon Rise) magma series to further explore the mechanics of Ti isotope fractionation in magmas. Whilst all suites display an increase in δ49/47Ti (deviation in 49Ti/47Ti of a sample relative to the OL-Ti reference material) during magma differentiation relative to indices such as increasing SiO2 and decreasing Mg#, our data reveal that each of the three magma series have contrasting δ49/47Ti fractionation patterns over comparable ranges of SiO2 and Mg#. Alkaline differentiation suites from intraplate settings display the most substantial range of variation (δ49/47Ti = +0.01 to +2.32‰), followed by tholeiites (−0.01 to +1.06‰) and calc-alkaline magmas (+0.06 to +0.64‰). Alkaline magmas possess high initial melt TiO2 contents which enables early saturation of ilmenite + titanomagnetite and a substantial degree of oxide crystallisation, whereas tholeiitic and calc-alkaline suites crystallise fewer oxides and have titanomagnetite as the dominant oxide phase. Positive slopes of FeO*/TiO2 vs. SiO2 during magma differentiation are related to high degrees of crystallisation of Ti-rich oxides (i.e. ilmenite). Bulk solid-melt Ti isotope fractionation factors co-vary with the magnitude of the slope of FeO*/TiO2 vs. SiO2 during magma differentiation.This indicates that the modal abundance and composition of the Fe-Ti oxide phase assemblage, itself is controlled by melt composition, governs Ti isotope fractionation during magma differentiation. In addition to this overall control, hydrous, oxidised calc-alkaline suites display a resolvable increase in δ49/47Ti at higher Mg# relative to drier and more reduced tholeiitic arc suites. These subparallel Ti isotope fractionation patterns are best explained by the earlier onset of oxide segregation in arc magmas with a higher oxidation state and H2O content. This indicates the potential of Ti isotopes to be utilised as proxies for geodynamic settings of magma generation.

The paleolimnologist's guide to compound-specific stable isotope analysis – An introduction to principles and applications of CSIA for Quaternary lake sediments

The stable isotope composition of key chemical elements for life on Earth (e.g., carbon, hydrogen, nitrogen, oxygen, sulfur) tracks changes in fluxes and turnover of these elements in the biogeosphere. Over the past 15–20 years, the potential to measure these isotopic compositions for individual, source-specific organic molecules (biomarkers) and to link them to a range of environmental conditions and processes has been unlocked and amplified by increasingly sensitive, affordable and wide-spread analytical technology. Paleoenvironmental research has seen enormous step-changes in our understanding of past ecosystem dynamics. Vital to these paradigm shifts is the need for well-constrained modern and recent analogues. Through increased understanding of these environments and their biological pathways we can successfully unravel past climatic changes and associated ecosystem adaption.With this review, we aim to introduce scientists working in the field of Quaternary paleolimnology to the tools that compound-specific isotope analysis (CSIA) provides for the gain of information on biogeochemical conditions in ancient environments. We provide information on fundamental principles and applications of novel and established CSIA applications based on the carbon, hydrogen, nitrogen, oxygen and sulfur isotopic composition of biomarkers. While biosynthesis, sources and associated isotope fractionation patterns of compounds such as n-alkanes are relatively well-constrained, new applications emerge from the increasing use of functionalized alkyl lipids, steroids, hopanoids, isoprenoids, GDGTs, pigments or cellulose. Biosynthesis and fractionation are not always fully understood. However, although analytical challenges remain, the future potential of deeper insights into ecosystem dynamics from the study of these compounds is also emerging.