Soil and unsaturated zone as a long-term source for pesticide metabolites in groundwater.

Pesticide metabolites are frequently detected in groundwater, often exceeding the concentrations of their parent pesticides. Ceasing the application of certain pesticides has often not led to the expected decrease in metabolite concentrations in groundwater, which is potentially caused by residues in soil. Whereas pesticide residues in soils are well-documented, there are only few studies about metabolite residues. We investigated if the soil/unsaturated zone can act as a long-term source for metabolites in groundwater by combining soil analysis, groundwater analysis and numerical modelling. The field study focused on the herbicide chloridazon (CLZ) and its frequently detected metabolites desphenyl-chloridazon (DPC) and methyl-desphenyl-chloridazon (MDPC) while in the model additional pesticides and metabolites were considered. In soil samples from an agricultural area, where the last CLZ application was 5 to 10 years ago, we observed 10 times (DPC: 0.22 - 7.4 µg kg-1) and 6 times (MDPC: 0.12 - 3.1 µg kg-1) higher metabolite concentrations compared to CLZ (< 0.050 - 1.0 µg kg-1). Calculations suggested that the majority of the metabolites (DPC: 63 - 96%, MDPC: 74 - 97%) were sorbed despite their lower sorption tendency. The metabolite retention was in particular related to the organic carbon content. The calculated pore water concentrations were highest in the deepest part of the soil profile (75 - 100 cm) with median concentrations of 3.6 and 1.7 µg L-1 for DPC and MDPC, respectively. The groundwater concentrations of DPC and MDPC were 3 to 3.5 times higher in monitoring wells downgradient from the agricultural zone than upgradient of it. This increase highlights the potential of soil and unsaturated zone as a long-term metabolite source after the application stop of pesticides, consistent with the calculated elevated pore water concentrations. Numerical flow and transport model simulations suggested that this input from soil and unsaturated zone can cause elevated metabolite concentrations (> 0.1 µg L-1) in groundwater over more than one decade. The study highlights that soil and unsaturated zone can act as a long-term source of pesticide metabolites even if they have much higher mobility than the parent compound.

Field demonstration for the solvent-based sampling method to perform compound-specific isotope analysis on gas-phase VOC.

The solvent-based sampling method for collecting gas-phase volatile organic compounds (VOCs) and conducting compound-specific isotope analysis (CSIA) was deployed during a controlled field study. The solvent-based method used methanol as a sink to accumulate petroleum hydrocarbons during the sampling of soil air and effluent gas. For each gaseous sample collected, carbon isotope analysis (δ13C) was conducted for a selection of five VOCs (benzene, toluene, o-xylene, cyclopentane and octane) emitted by a synthetic hydrocarbon source emplaced in the subsurface. The δ13C values obtained for gaseous VOCs (collected from soil gas and effluent gas) were compared to measurements obtained for the same VOCs present in the source material (none aqueous phase liquid - NAPL) and dissolved in groundwater to evaluate the reliability of the solvent-based sampling method in providing accurate isotope measurements. Since the NAPL source was composed of only 12 VOCs, potential bias related to the analytical procedure (such as co-elution) were avoided, hence emphasizing on field-related bias. This field evaluation demonstrated the capacity of the solvent-based method to produce precise and accurate δ13C measurements. The isotopic discrepancies between the gaseous and the NAPL values were < 1 ‰ for 39 out of the 41 comparison points, thus deemed not statistically different based on a common isotopic uncertainty error of ±0.5 ‰. Moreover, the current field study is the first field study to report δ13C measurements for up to five gas-phase VOCs obtained from the same sample, which appears to be of interest for VOC fate or forensic studies. The possibility to use several VOC isotopic measurements enabled by the sampling method would contribute to strengthen the connection assessment between gaseous VOCs and the suspected emitting source. Accordingly, the field results presented herein support the application of this sampling methodology to conduct CSIA assessment in the frame of VOC vapor studies.

Climate change impacts on groundwater discharge-dependent streamflow in an alpine headwater catchment.

Climate change will have-and, in much of the world, is already having-a pronounced impact on alpine water resources. A deeper understanding of the future role of groundwater in alpine catchments, including quantification of climate change impacts on groundwater discharge, is vital for understanding the future of alpine water resources as a whole. Here, we develop and couple a geophysics-informed groundwater model with a net recharge model to investigate the impacts of climate change on a nival-regime alpine headwater catchment with significant unconfined Quaternary aquifer coverage. Flow in the groundwater-fed stream at the catchment outlet is analysed to determine changes in its annual dynamics. Comparing the periods 2020-2040 and 2080-2100 under ten RCP-8.5 climate models, we find a 35 % decrease in mean groundwater discharge and an increase in no-flow periods from ~0 % to 4.3 %. We also observe significant changes to the timing of monthly mean discharge maxima and minima, which shift ~1 month and ~5 months earlier, respectively. While groundwater has the potential to dampen the impacts of snow cover loss, currently perennial nival-regime alpine streams could be at risk of becoming intermittent by the end of the century. Our study underscores the increasingly critical role that groundwater will play in alpine catchments and emphasizes the need for quantitative understanding of the limits to its buffering capacity.

Exploring the reliability of 222Rn as a tracer of groundwater age in alluvial aquifers: Insights from the explicit simulation of variable 222Rn production.

Knowledge of groundwater residence times (GRT; the time elapsed since surface water infiltration) between losing rivers and pumping wells is crucial for management of water resources in alluvial aquifers. The radioactive noble gas radon-222 (222Rn) has been used for decades as a natural indicator of surface water infiltration, as it can provide quantitative information on GRT. However, models using 222Rn as a tracer of GRT are often based on a set of highly simplifying assumptions, including spatially homogenous 222Rn production and exclusively advective mass transport within the aquifer. In this paper, we use the integrated surface-subsurface hydrological model HydroGeoSphere (HGS) to simulate 222Rn transport, production, and decay in a bank filtration context. Spatially variable 222Rn production, based on experimental data, is explicitly considered. We show that variable 222Rn production rates, coupled with hydrodispersive mixing of groundwater, may lead to large biases in GRT estimates. Under certain transient conditions however, changes in tracer-derived GRTs correlate well with changes in mean groundwater age. Whereas 222Rn-derived GRTs may only be reliable under a narrow range of field conditions, 222Rn may serve as a powerful tracer of changes in mean GRT even in complex and heterogenous environments.

Dual C-Br Isotope Fractionation Indicates Distinct Reductive Dehalogenation Mechanisms of 1,2-Dibromoethane in Dehalococcoides- and Dehalogenimonas-Containing Cultures.

Brominated organic compounds such as 1,2-dibromoethane (1,2-DBA) are highly toxic groundwater contaminants. Multi-element compound-specific isotope analysis bears the potential to elucidate the biodegradation pathways of 1,2-DBA in the environment, which is crucial information to assess its fate in contaminated sites. This study investigates for the first time dual C-Br isotope fractionation during in vivo biodegradation of 1,2-DBA by two anaerobic enrichment cultures containing organohalide-respiring bacteria (i.e., either Dehalococcoides or Dehalogenimonas). Different εbulkC values (-1.8 ± 0.2 and -19.2 ± 3.5‰, respectively) were obtained, whereas their respective εbulkBr values were lower and similar to each other (-1.22 ± 0.08 and -1.2 ± 0.5‰), leading to distinctly different trends (ΛC-Br = Δδ13C/Δδ81Br ≈ εbulkC/εbulkBr) in a dual C-Br isotope plot (1.4 ± 0.2 and 12 ± 4, respectively). These results suggest the occurrence of different underlying reaction mechanisms during enzymatic 1,2-DBA transformation, that is, concerted dihaloelimination and nucleophilic substitution (SN2-reaction). The strongly pathway-dependent ΛC-Br values illustrate the potential of this approach to elucidate the reaction mechanism of 1,2-DBA in the field and to select appropriate εbulkC values for quantification of biodegradation. The results of this study provide valuable information for future biodegradation studies of 1,2-DBA in contaminated sites.

Stable carbon and hydrogen isotope fractionation of volatile organic compounds caused by vapor-liquid equilibrium.

Several types of laboratory experiments were conducted to evaluate isotope fractionation caused by phase transfer process for a selection of common environmental contaminants. Carbon and hydrogen isotope fractionation caused by vaporization of non-aqueous phase liquid (NAPL), by volatilization from water and by dissolution into an organic solvent (tetraethylene glycol dimethylether or TGDE) under equilibrium conditions was investigated with closed system experimental setups to isolate the air-liquid partitioning process. A selection of aromatic, aliphatic and chlorinated compounds along with one fuel oxygenate (methyl tert-butyl ether or MTBE) were evaluated to determine isotope enrichment factor related to respective phase transfer process. During NAPL vaporization, the residual mass of aromatic compounds, aliphatic compounds and MTBE became progressively depleted in heavy carbon and hydrogen isotopes. In contrast, during volatilization from water, the residual mass of aromatic compounds and MTBE dissolved in the water became progressively enriched in heavy hydrogen isotopes, whereas no significant change in carbon isotope was observed, except for MTBE showing a significant depletion. For the air-TGDE partitioning process, most of the aromatic compounds tested led to no significant carbon (except ethylbenzene) or hydrogen (except toluene and o-xylene) isotope fractionation. In contrast, significant carbon isotope fractionation was observed for aliphatic and chlorinated compounds and hydrogen isotope fractionation for aliphatic compounds, and are comparable to progressive NAPL vaporization in direction and magnitude. The isotope fractionation factors determined in this study are key for interpreting the change in isotope ratios when assessing the fate of gas-phase VOCs present in the soil air or when gas-phase VOCs are sampled using TGDE as the sink matrix. The results of this study contribute to expand the list of common environmental contaminants that can be assessed by the compound-specific isotope analysis (CSIA) method deployed in the frame of gas-phase studies.

Field-scale monitoring of nitrate leaching in agriculture: assessment of three methods.

Deterioration of groundwater quality due to nitrate loss from intensive agricultural systems can only be mitigated if methods for in-situ monitoring of nitrate leaching under active farmers' fields are available. In this study, three methods were used in parallel to evaluate their spatial and temporal differences, namely ion-exchange resin-based Self-Integrating Accumulators (SIA), soil coring for extraction of mineral N (Nmin) from 0 to 90 cm in Mid-October (pre-winter) and Mid-February (post-winter), and Suction Cups (SCs) complemented by a HYDRUS 1D model. The monitoring, conducted from 2017 to 2020 in the Gäu Valley in the Swiss Central Plateau, covered four agricultural fields. The crop rotations included grass-clover leys, canola, silage maize and winter cereals. The monthly resolution of SC samples allowed identifying a seasonal pattern, with a nitrate concentration build-up during autumn and peaks in winter, caused by elevated water percolation to deeper soil layers in this period. Using simulated water percolation values, SC concentrations were converted into fluxes. SCs sampled 30% less N-losses on average compared to SIA, which collect also the wide macropore and preferential flows. The difference between Nmin content in autumn and spring was greater than nitrate leaching measured with either SIA or SCs. This observation indicates that autumn Nmin was depleted not only by leaching but also by plant and microbial N uptake and gaseous losses. The positive correlation between autumn Nmin content and leaching fluxes determined by either SCs or SIA suggests autumn Nmin as a useful relative but not absolute indicator for nitrate leaching. In conclusion, all three monitoring techniques are suited to indicate N leaching but represent different transport and cycling processes and vary in spatio-temporal resolution. The choice of monitoring method mainly depends (1) on the project's goals and financial budget and (2) on the soil conditions. Long-term data, and especially the combination of methods, increase process understanding and generate knowledge beyond a pure methodological comparison.

Compound-specific carbon isotope analysis of volatile organic compounds in complex soil extracts using purge and trap concentration coupled to heart-cutting two-dimensional gas chromatography-isotope ratio mass spectrometry.

Compound-specific carbon isotope analysis (CSIA) is a powerful tool to track the origin and fate of organic subsurface contaminants including petroleum and chlorinated hydrocarbons and is typically applied to water samples. However, soil can form a significant contaminant reservoir. In soil samples, it can be challenging to recover sufficient amounts of volatile organic compounds (VOC) to perform CSIA. Soil samples often contain complex contaminant mixtures and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) is highly dependent on good chromatographic separation due to the conversion to a single analyte. To extend the applicability of CSIA to complex volatile organic compound mixtures in soil samples, and to recover sufficient amounts of target compounds for carbon CSIA, we compared two soil extraction solvents, tetraglyme (TGDE) and methanol, and developed a heart-cutting two-dimensional GC-GC-C-IRMS method. We used purge & trap concentration of solvent-water mixtures to increase the amount of analyte delivered to the column and thus lower method detection limits. We optimized purge & trap and chromatographic parameters for twelve target compounds, including one suffering from poor purge efficiency. By using a 30 m thick-film non-polar column in the first and a 15 m polar column in the second dimension, we achieved good chromatographic separation for the target compounds in difficult matrices and high accuracy (trueness and precision) for carbon isotopic analysis. Tetraglyme extraction was shown to offer advantages over methanol for purge & trap concentration, leading to lower target compound method detection limits for CSIA of soil samples. The applicability of the developed method was demonstrated for a case study on soil extracts from a former manufacturing facility. Our approach extends the applicability of CSIA to an important matrix that often controls the long-term fate of contaminants in the subsurface.

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.

Determination of chlorothalonil metabolites in soil and water samples.

Pesticide metabolites are frequently detected in groundwater at concentrations often exceeding those of their parent pesticides. A well-known example is the metabolites of chlorothalonil, a non-systematic, broad spectrum fungicide. Some of the chlorothalonil metabolites occur frequently and at elevated concentrations in groundwater, which is why the use of chlorothalonil was recently banned in the European Union. To estimate the long-term evolution of the concentration of the chlorothalonil metabolites in groundwater after this ban, it is important to know if metabolite residues in soil and unsaturated zone can affect the concentrations in groundwater. We developed and validated a method for the determination of 5 chlorothalonil metabolites in soil (R471811, R417888, SYN507900, SYN548580 and R611968), including those which are frequently detected in groundwater. The developed protocols, based on a solid phase extraction approach (for R471811, R417888, SYN507900, SYN548580) or a QuEChERS approach (for R611968) followed by UHPLC-MS/MS analysis, provided excellent sensitivity (LOQ of 0.5 µg/kg for all metabolites), precision (RSD<10 % at low, medium and high concentrations) and accuracy (84-115 %). In addition, we developed a simple but highly sensitive (LOQ of 5-10 ng/L) direct-injection method for the analysis of these 5 metabolites in water to compare their occurrence in soil and groundwater. The application of these methods to agricultural soil samples and groundwater samples showed that the detection frequency of the 5 chlorothalonil metabolites in soil and groundwater seems to be inversed and dependent on their sorption coefficient. The latter might control the amount of the chlorothalonil metabolites which is retained in the soil or which leaches towards groundwater. Our results provide insights to estimate the retention of the different chlorothalonil metabolites in soil and unsaturated zone and therefore, to assess the influence of the soil and unsaturated zone on the long-term concentration evolution of these metabolites in groundwater.

Dataset for laboratory treatability experiment with activated carbon and bioamendments to enhance biodegradation of chlorinated ethenes.

This dataset describes the outcome of a laboratory trichloroethene (TCE) treatability experiment with liquid activated carbon and bioamendments. The treatability experiment included unamended microcosms, bioamended microcosms with a Dehalococcoides containing culture and electron donor, and bioamended microcosms including liquid activated carbon (PlumeStop®). Data were collected frequently over an 85-day experimental period. Data were collected for the following parameters: redox sensitive species, chlorinated ethenes, non-chlorinated end-products, electron donors, compound specific isotopes, specific bacteria and functional genes. The reductive dechlorination of TCE could be described by a carbon isotope enrichment factor (εC) of -7.1 ‰. In the amended systems, the degradation rates for the TCE degradation were 0.08-0.13 d-1 and 0.05-0.09 d-1 determined by concentrations and isotope fractionation, respectively. Dechlorination of cis-DCE was limited. This dataset assisted in identifying the impact of different bioamendments and activated carbon on biodegradation of chlorinated ethenes. The dataset is useful in optimising design and setup for future laboratory and field investigations. This study provides novel information on the effect of low dose liquid activated carbon on chlorinated ethenes degradation by applying isotopic and microbial techniques, and by linking the outcome to a field case study. The data presented in this article are related to the research article "Assessment of chlorinated ethenes degradation after field scale injection of activated carbon and bioamendments: Application of isotopic and microbial analyses" (Ottosen et al., 2021).

Sorption- and diffusion-induced isotopic fractionation in chloroethenes.

Isotopic fractionation of groundwater contaminants can occur due to degradation, diffusion and sorption. Of these, only degradation has been extensively explored, yet diffusive isotopic fractionation (DIF) and sorptive isotopic fractionation (SIF) can have significant effects on the isotopic enrichment of groundwater contaminants. Understanding how to mathematically describe and model these processes is vital to the correct interpretation of compound-specific isotope analysis (CSIA) data in the field. Here, models for these physical fractionation processes are developed and described, including the definition of a sorption enrichment factor. These models are then implemented numerically using inverse and finite-element methods to investigate two scenarios, diffusion-sorption and diffusion-sorption-advection, that have been measured in the laboratory. Concentration, δ37Cl, and δ2H data from cis-dichloroethene (cDCE) and trichloroethene (TCE) are used as inputs to the models. Unknown transport parameters including diffusive fractionation exponents are determined from an inverse modelling approach. DIF is shown to have a stronger influence on chlorine isotopologues than on hydrogen isotopologues. For both cDCE and TCE, the sorption enrichment factor of chlorine is found to be negative while that of hydrogen is positive. The presented approach and results provide novel tools and insight into DIF and SIF and underline that these processes should be taken into account when using CSIA to assess contaminant fate.

Assessment of chlorinated ethenes degradation after field scale injection of activated carbon and bioamendments: Application of isotopic and microbial analyses.

Over the last decade, activated carbon amendments have successfully been applied to retain chlorinated ethene subsurface contamination. The concept of this remediation technology is that activated carbon and bioamendments are injected into aquifer systems to enhance biodegradation. While the scientific basis of the technology is established, there is a need for methods to characterise and quantify the biodegradation at field scale. In this study, an integrated approach was applied to assess in situ biodegradation after the establishment of a cross sectional treatment zone in a TCE plume. The amendments were liquid activated carbon, hydrogen release donors and a Dehalococcoides containing culture. The integrated approach included spatial and temporal evaluations on flow and transport, redox conditions, contaminant concentrations, biomarker abundance and compound-specific stable isotopes. This is the first study applying isotopic and microbial techniques to assess field scale biodegradation enhanced by liquid activated carbon and bioamendments. The injection enhanced biodegradation from TCE to primarily cis-DCE. The Dehalococcoides abundances facilitated characterisation of critical zones with insufficient degradation and possible explanations. A conceptual model of isotopic data together with distribution and transport information improved process understanding; the degradation of TCE was insufficient to counteract the contaminant input by inflow into the treatment zone and desorption from the sediment. The integrated approach could be used to document and characterise the in situ degradation, and the isotopic and microbial data provided process understanding that could not have been gathered from conventional monitoring tools. However, quantification of degradation through isotope data was restricted for TCE due to isotope masking effects. The combination of various monitoring tools, applied frequently at high-resolution, with system understanding, was essential for the assessment of biodegradation in the complex, non-stationary system. Furthermore, the investigations revealed prospects for future research, which should focus on monitoring contaminant fate and microbial distribution on the sediment and the activated carbon.

Influence of surface water - groundwater interactions on the spatial distribution of pesticide metabolites in groundwater.

In groundwater, pesticide metabolites tend to occur more frequently and at higher concentrations than their parent pesticides, due to their higher mobility and persistence. These properties might also favor their transfer across surface water - groundwater interfaces. However, the effect of surface water - groundwater interactions on the metabolite occurrence in groundwater and pumping wells has so far received little attention. We investigated the spatial distribution of metabolites in an unconsolidated aquifer, which interacts with two surface water bodies originating from catchments with contrasting land use. We focused on metabolites of the herbicide chloridazon, namely desphenyl-chloridazon (DPC) and methyl-desphenyl-chloridazon (MDPC) and characterized surface water - groundwater interactions with various environmental tracers (e.g. electrical conductivity, stable water isotopes, wastewater tracers). In zones influenced by a river from a mountainous area, metabolite concentrations were low (median values ≤0.50 µg L-1 for DPC, ≤0.19 µg L-1 for MDPC). In contrast, high concentrations occurred in areas dominated by recharge from agricultural fields and/or influenced by a stream from an adjacent intensely farmed catchment (median values up to 1.9 µg L-1 for DPC and up to 0.75 µg L-1 for MDPC). An endmember analysis using hydro-chemical data suggested that about 20% of the DPC mass in a pumping well originated from the neighboring catchment and on its own would cause a concentration above 0.1 µg L-1 for DPC. Our findings highlight that the mobile metabolites can be imported from zones with intense agriculture outside of the exploited aquifer via surface-water groundwater interactions influencing the metabolite concentration level and long-term dynamics in the aquifer.

Controls on the persistence of aqueous-phase groundwater contaminants in the presence of reactive back-diffusion.

The persistence of groundwater contaminants is influenced by several interacting processes. Physical, physico-chemical, and (bio-)chemical processes all influence the transport of contaminants in the subsurface. However, for a given hydrogeological system, it is generally unclear to which degree each of these phenomena acts as a control on plume behaviour. Here, we present a comprehensive investigation of these processes and their influences on plume behaviour and persistence in layered sedimentary systems. We investigate different scenarios that represent fundamental configurations of common contaminant situations. A confined aquifer over- and underlain by aquitard layers is investigated in a source-removal scenario and a constant-source equilibrium scenario. Additionally, an aquitard overlain and underlain by high permeability units is investigated in a source-removal scenario. In these investigations, we vary layer thickness, as well as parameters governing advection, (back-)diffusion, sorption, and degradation. Extensive analysis of these results enables quantification of the influence of these parameters on maximum down-gradient concentration, plume persistence duration, and plume spatial extent. Finally, parameter space dimensionality reduction is used to establish trends and regimes in which certain processes dominate as controls. A lower limit to plume extent as a function of a novel constructed parameter is also determined. These results provide valuable quantitative information for the assessment of the fate of groundwater contaminants and are applicable to a wide range of aqueous-phase solutes.

Dual-Element Isotope Analysis of Desphenylchloridazon to Investigate Its Environmental Fate in a Systematic Field Study: A Long-Term Lysimeter Experiment.

Desphenylchloridazon (DPC), the main metabolite of the herbicide chloridazon (CLZ), is more water soluble and persistent than CLZ and frequently detected in water bodies. When assessing DPC transformation in the environment, results can be nonconclusive if based on concentration analysis alone because estimates may be confounded by simultaneous DPC formation from CLZ. This study investigated the fate of DPC by combining concentration-based methods with compound-specific C and N stable isotope analysis (CSIA). Additionally, DPC formation and transformation processes were experimentally deconvolved in a dedicated lysimeter study considering three scenarios. First, surface application of DPC enabled studying its degradation in the absence of CLZ. Here, CSIA provided evidence of two distinct DPC transformation processes: one shows significant changes only in 13C/12C, whereas the other involves changes in both 13C/12C and 15N/14N isotope ratios. Second, surface application of CLZ mimicked a realistic field scenario, showing that during DPC formation, 13C/12C ratios of DPC were depleted in 13C relative to CLZ, while 15N/14N ratios remained constant. Finally, CLZ depth injection simulated preferential flow and demonstrated the importance of the topsoil for retaining DPC. The combination of the lysimeter study with CSIA enabled insights into DPC transformation in the field that are superior to those of studies of concentration trends.

Compound-specific chlorine isotope fractionation in biodegradation of atrazine.

Atrazine is a frequently detected groundwater contaminant. It can be microbially degraded by oxidative dealkylation or by hydrolytic dechlorination. Compound-specific isotope analysis is a powerful tool to assess its transformation. In previous work, carbon and nitrogen isotope effects were found to reflect these different transformation pathways. However, chlorine isotope fractionation could be a particularly sensitive indicator of natural transformation since chlorine isotope effects are fully represented in the molecular average while carbon and nitrogen isotope effects are diluted by non-reacting atoms. Therefore, this study explored chlorine isotope effects during atrazine hydrolysis with Arthrobacter aurescens TC1 and oxidative dealkylation with Rhodococcus sp. NI86/21. Dual element isotope slopes of chlorine vs. carbon isotope fractionation (Λ = 1.7 ± 0.9 vs. Λ = 0.6 ± 0.1) and chlorine vs. nitrogen isotope fractionation (Λ = -1.2 ± 0.7 vs. Λ = 0.4 ± 0.2) provided reliable indicators of different pathways. Observed chlorine isotope effects in oxidative dealkylation (εCl = -4.3 ± 1.8‰) were surprisingly large, whereas in hydrolysis (εCl = -1.4 ± 0.6‰) they were small, indicating that C-Cl bond cleavage was not the rate-determining step. This demonstrates the importance of constraining expected isotope effects of new elements before using the approach in the field. Overall, the triple element isotope information brought forward here enables a more reliable identification of atrazine sources and degradation pathways.

Tracking chlorinated contaminants in the subsurface using compound-specific chlorine isotope analysis: A review of principles, current challenges and applications.

Many chlorinated hydrocarbons have gained notoriety as persistent organic pollutants in the environment. Engineered and natural remediation efforts require a monitoring tool to track the progress of degradation processes. Compound-specific isotope analysis (CSIA) is a robust method to evaluate the origin and fate of contaminants in the environment and does not rely on concentration measurements. While carbon CSIA has established itself in the routine assessment of contaminated sites, studies incorporating chlorine isotopes have only recently become more common. Although some aspects of chlorine isotope analysis are more challenging than carbon isotope analysis, having additional isotopic data yields valuable information for contaminated site management. This review provides an overview of chlorine isotope fractionation of chlorinated contaminants in the subsurface by different processes and presents analytical techniques and unresolved challenges in chlorine isotope analysis. A summary of successful field applications illustrates the potential of using chlorine isotope data. Finally, approaches in modelling chlorine isotope fractionation due to degradation, diffusion, and sorption processes are discussed.

Compound-Specific Chlorine Isotope Analysis of the Herbicides Atrazine, Acetochlor, and Metolachlor.

A gas chromatography-single quadrupole mass spectrometry method was developed and validated for compound-specific chlorine isotope analysis (Cl-CSIA) of three chlorinated herbicides, atrazine, acetochlor, and metolachlor, which are widespread contaminants in the environment. For each compound, the two most abundant ions containing chlorine (202/200 for atrazine, 225/223 for acetochlor, and 240/238 for metolachlor) and a dwell time of 30 ms were determined as optimized MS parameters. A limit of precise isotope analysis for ethyl acetate solutions of 10 mg/L atrazine, 10 mg/L acetochlor, and 5 mg/L metolachlor could be reached with an associated uncertainty between 0.5 and 1‰. To this end, samples were measured 10-fold and bracketed with two calibration standards that covered a wide range of δ37Cl values and for which amplitudes matched those of the samples within 20% tolerance. The method was applied to investigate chlorine isotope fractionation during alkaline hydrolysis of metolachlor, which showed a shift in δ37Cl of +46‰ after 98% degradation, demonstrating that chlorine isotope fractionation could be a sensitive indicator of transformation processes even when limited degradation occurs. This method, combined with large-volume solid-phase extraction (SPE), allowed application of Cl-CSIA to environmentally relevant concentrations of widespread herbicides (i.e., 0.5-5 µg/L in water before extraction). Therefore, the combination of large-volume SPE and Cl-CSIA is a promising tool for assessing the transformation processes of these pollutants in the environment.

Chlorinated ethene plume evolution after source thermal remediation: Determination of degradation rates and mechanisms.

The extent, mechanism(s), and rate of chlorinated ethene degradation in a large tetrachloroethene (PCE) plume were investigated in an extensive sampling campaign. Multiple lines of evidence for this degradation were explored, including compound-specific isotope analysis (CSIA), dual C-Cl isotope analysis, and quantitative real-time polymerase chain reaction (qPCR) analysis targeting the genera Dehalococcoides and Dehalogenimonas and the genes vcrA, bvcA, and cerA. A decade prior to this sampling campaign, the plume source was thermally remediated by steam injection. This released dissolved organic carbon (DOC) that stimulated microbial activity and created reduced conditions within the plume. Based on an inclusive analysis of minor and major sampling campaigns since the initial site characterization, it was estimated that reduced conditions peaked 4 years after the remediation event. At the time of this study, 11 years after the remediation event, the redox conditions in the aquifer are returning to their original state. However, the DOC released from the remediated source zone matches levels measured 3 years prior and plume conditions are still suitable for biotic reductive dechlorination. Dehalococcoides spp., Dehalogenimonas spp., and vcrA, bvcA, and cerA reductive dehalogenase genes were detected close to the source, and suggest that complete, biotic PCE degradation occurs here. Further downgradient, qPCR analysis and enriched δ13C values for cis-dichloroethene (cDCE) suggest that cDCE is biodegraded in a sulfate-reducing zone in the plume. In the most downgradient portion of the plume, lower levels of specific degraders supported by dual C-Cl analysis indicate that the biodegradation occurs in combination with abiotic degradation. Additionally, 16S rRNA gene amplicon sequencing shows that organizational taxonomic units known to contain organohalide-respiring bacteria are relatively abundant throughout the plume. Hydraulic conductivity testing was also conducted, and local degradation rates for PCE and cDCE were determined at various locations throughout the plume. PCE degradation rates from sampling campaigns after the thermal remediation event range from 0.11 to 0.35 yr-1. PCE and cDCE degradation rates from the second to the third sampling campaigns ranged from 0.08 to 0.10 yr-1 and 0.01 to 0.07 yr-1, respectively. This is consistent with cDCE as the dominant daughter product in the majority of the plume and cDCE degradation as the time-limiting step. The extensive temporal and spatial analysis allowed for tracking the evolution of the plume and the lasting impact of the source remediation and illustrates that the multiple lines of evidence approach is essential to elucidate the primary degradation mechanisms in a plume of such size and complexity.