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.

Hydrogeochemical and isotopic evaluation of VOC commingled plumes in a weathered fractured bedrock aquifer treated with thermal and bioremediation.

Chlorinated ethanes and ethenes isotopic analyses in groundwater and hydrogeochemical results from a former industrial area in Sao Paulo (Brazil) were used to confirm the existence and allow further characterization of source areas and their commingled plumes, both before and after thermal and bioremediation treatments. Prior to full scale remediation, a recently identified off-site source area with unknown history and limited access for further intrusive works presented lower δ13C values (-6.5‰ to -1.8‰ for 1,2-DCA) than the downgradient on-site source area (+8.6‰ to +20.0‰). Intermediate δ13C values for 1,2-DCA were identified further downgradient from the sources, within commingled plumes patterns. The isotope and concentration results show the typical degradation patterns associated with biotic reductive dechlorination for chlorinated ethenes and dihaloelimination for 1,2-DCA. Results following remediation treatments show further levels of isotopic enrichment, for chlorinated ethenes and chlorinated ethanes in the tropically weathered and deeper fractured bedrock (gneisses) groundwater. Hydrogeochemical results, isotopic mass balance and Carbon-Chlorine isotope slopes data are coherent with remediation treatment and a complex commingled plume setting. The results of this study confirmed the Temporal Conceptual Model proposed by Hart et al. (2021) and identified the need for further studies to evaluate isotopic dynamics under thermal remediation, including thermal-induced hydrolysis processes.

Identification of degrader bacteria and fungi enriched in rhizosphere soil from a toluene phytoremediation site using DNA stable isotope probing.

Improved knowledge of the ecology of contaminant-degrading organisms is paramount for effective assessment and remediation of aromatic hydrocarbon-impacted sites. DNA stable isotope probing was used herein to identify autochthonous degraders in rhizosphere soil from a hybrid poplar phytoremediation system incubated under semi-field-simulated conditions. High-throughput sequencing of bacterial 16S rRNA and fungal internal transcribed spacer (ITS) rRNA genes in metagenomic samples separated according to nucleic acid buoyant density was used to identify putative toluene degraders. Degrader bacteria were found mainly within the Actinobacteria and Proteobacteria phyla and classified predominantly as Cupriavidus, Rhodococcus, Luteimonas, Burkholderiaceae, Azoarcus, Cellulomonadaceae, and Pseudomonas organisms. Purpureocillium lilacinum and Mortierella alpina fungi were also found to assimilate toluene, while several strains of the fungal poplar endophyte Mortierella elongatus were indirectly implicated as potential degraders. Finally, PICRUSt2 predictive taxonomic functional modeling of 16S rRNA genes was performed to validate successful isolation of stable isotope-labeled DNA in density-resolved samples. Four unique sequences, classified within the Bdellovibrionaceae, Intrasporangiaceae, or Chitinophagaceae families, or within the Sphingobacteriales order were absent from PICRUSt2-generated models and represent potentially novel putative toluene-degrading species. This study illustrates the power of combining stable isotope amendment with advanced metagenomic and bioinformatic techniques to link biodegradation activity with unisolated microorganisms. Novelty statement: This study used emerging molecular biological techniques to identify known and new organisms implicated in aromatic hydrocarbon biodegradation from a field-scale phytoremediation system, including organisms with phyto-specific relevance and having potential for downstream applications (amendment or monitoring) in future and existing systems. Additional novelty in this study comes from the use of taxonomic functional modeling approaches for validation of stable isotope probing techniques. This study provides a basis for expanding existing reference databases of known aromatic hydrocarbon degraders from field-applicable sources and offers technological improvements for future site assessment and management purposes.

Use of isotopes techniques to reveal the origin of water salinity in an arid region of Central-Western Argentina.

Groundwater is a strategic and vital resource for agriculture and oil production in the arid region of Carrizal sub-basin (CSB) in Argentina. Increasing groundwater salinity in some areas has created legal conflicts between water users over the source of the salinity. A multidisciplinary approach using hydrogeological, chemical and isotope tools were used to evaluate the source of groundwater salinity in CSB. The Mendoza River is the main source of recharge to the CSB aquifer. Groundwater and surface water from the recharge area near the Mendoza River to the discharge area of the CSB were analyzed for the study. The groundwater salinity varies between ~1000 µS/cm in the north (recharge area) to ~4000 µS/cm in the central region. There is a clear correlation between high level of nitrate and the high salinity spots in the aquifer. These data and the stable isotopes data suggests the source of groundwater salinity is associated with irrigation return flows from the agriculture areas. This is fully supported by the carbon isotopes data that showed clearly the input of carbon from the irrigated agriculture areas in the aquifer. No evidence was found about the role of the oil industry in the salinization of groundwater in the study area. However, a groundwater of different origin than the recharge from the Mendoza River was found down-gradient of the oil field which needs further investigation. The results of this study have implications for improving water management in agriculture areas in arid environments where water resources are under significant pressure due to more demand by an increase in population and agriculture activities under a scenario of a cycle of droughts and climate change.

Use of environmental isotopes to assess groundwater pollution caused by agricultural activities.

This work applied environmental isotope techniques to validate the results of previous studies on recharge sources in a rural area in central Chile (34.3° S and 71.3° W) and discern the origin of nitrate contamination in wells. Stream water and groundwater samples were taken during three surveys, two during spring snowmelt and one in low-water conditions. Chemical analyses included major cations and anions, isotope analyses included 18O-H2O; 2H-H20; 3H-H20; 18O-NO3 - and 15N-NO3 -. The stable isotope data show that surface water and deep groundwater present depleted isotope values associated with recharge from the Andes Mountains and that shallow groundwater has more enriched isotope values that reflect the contribution of local recharge from rainwater infiltration. Depleted isotope values observed in shallow groundwater show the effect of recirculated river water used for irrigation. These results are consistent with the conceptual groundwater model developed in previous studies. Some wells have nitrate concentrations above the allowable limit for drinking water. The stable nitrogen isotopes indicate that nitrate is associated mainly with urea and ammoniacal fertilizers, and nitrate is attenuated by denitrification. The results of this study are relevant to improving management of groundwater resources used for drinking water.

Quantification of toluene phytoextraction rates and microbial biodegradation functional profiles at a fractured bedrock phytoremediation site.

This field study evaluated the efficacy of a mature hybrid poplar phytoremediation system for the remediation of toluene in a fractured bedrock aquifer site. Phytoextraction activity of the trees and the ecology and biodegradation potential of root-colonizing bacteria that ultimately influence how much toluene is transported from the roots and phytoextracted to the aboveground point of measurement were explored. Peak-season toluene mass removal rates ranging from 313 to 743 µg/day were quantified using passive in planta contaminant sampling techniques and continuous heat dissipation transpiration measurements in tree stems. Root bacterial microbiome structure and biodegradation potential were evaluated via high-throughput sequencing and predictive metagenomic functional modelling of bacterial 16S rRNA genes in roots. Poplar roots were colonized mostly by Proteobacteria, Actinobacteria, and Bacteroidetes. Distinct, more uniform communities were observed in roots associated with trees planted in the toluene source area compared to other areas, with differences apparent at lower taxonomic levels. Significant enrichment of Streptomyces in roots was observed in the source area, implicating that genus as a potentially important poplar endophyte at toluene-impacted sites. Moreover, significantly greater aerobic toluene biodegradation capacity was predicted in these roots compared to other areas using taxonomic functional modelling. Together with passive sampling, the molecular results provided supporting evidence of biodegradation activity in the source area and contextualized the detected phytoextraction patterns. These results support the application of phytoremediation systems for aromatic hydrocarbons in environments with complex geology and demonstrate field-validated monitoring techniques to assess phytoextraction and biodegradation in these systems.

Contrasting biogeochemical processes revealed by stable isotopes of H2O, N, C and S in shallow aquifers underlying agricultural lowlands.

Lowland coastal areas as the Po Delta (Italy) are often intensively cultivated and affected by nitrogen imbalance due to fertilizers leaching to groundwater and export via run-off. To address this issue several agricultural best practices have been proposed, like limiting the amount of fertilizers and increasing soil organic matter content. In this study, groundwater samples were analysed for major ions and stable isotopes of H2O, C, N and S using multi-level sampler (MLS) from two contrasting depositional environments, one representative of alluvial plain (AP) and the other representative of a reclaimed coastal plain (RCP). In each site, controlled plots with different agriculture practice including fertilizers and tillage and compost amendment and no tillage were considered in the study. Tracer test results highlight that recharge water infiltrated at the start of the controlled study has not yet reached the saturated zone, thus current groundwater concentrations are representative of former agricultural practices. Stable isotopes show a clear distinction between different sources of nitrogen in both sites, from synthetic fertilizers to sedimentary nitrogen pool and atmospheric input. The main source of sulphate in groundwater is pyrite and fertilizers. Denitrification, sulphate reduction and methanogenesis were involved in the C, N and S cycle in the RCP site characterized by low hydraulic conductivity sediments and high SOM. These processes were not relevant in the AP site characterized by oxic condition and low SOM, but some evidence of denitrification was found in one of the AP sites. High resolution monitoring was a key tool to identify the different redox zones responsible for N, C and S cycling in these aquifers. This study shows that a clear understanding of transit times in the vadose zone is a key prerequisite to evaluate the effect of controlled agriculture practice on the quality of shallow groundwater.

Assessing toluene biodegradation under temporally varying redox conditions in a fractured bedrock aquifer using stable isotope methods.

In complex hydrogeological settings little is known about the extent of temporally varying redox conditions and their effect on aromatic hydrocarbon biodegradation. This study aims to assess the impact of changing redox conditions over time on aromatic hydrocarbon biodegradation in a fractured bedrock aquifer using stable isotope methods. To that end, four snapshots of highly spatio-temporally resolved contaminant and redox sensitive species concentrations, as well as stable isotope ratio profiles, were determined over a two-years time period in summer 2016, spring 2017, fall 2017 and summer 2018 in a toluene contaminated fractured bedrock aquifer. The concentration profiles of redox sensitive species and stable isotope ratio profiles for dissolved inorganic carbon (DIC) and sulfate (δ13CDIC, δ34SSO4, δ18OSO4) revealed that the aquifer alternates between oxidising (spring 2017/summer 2018) and reducing conditions (summer 2016/fall 2017). This alternation was attributed to a stronger aquifer recharge with oxygen-rich meltwater in spring 2017/summer 2018 compared to summer 2016/fall 2017. The temporally varying redox conditions coincided with various extents of toluene biodegradation revealed by the different magnitude of heavy carbon (13C) and hydrogen (2H) isotope enrichment in toluene. This indicated that the extent of toluene biodegradation and its contribution to plume attenuation was controlled by the temporally changing redox conditions. The highest toluene biodegradation was observed in summer 2016, followed by spring 2017 and fall 2017, whereby these temporal changes in biodegradation occurred throughout the whole plume. Thus, under temporally varying recharge conditions both the core and the fringe of a contaminant plume can be replenished with terminal electron acceptors causing biodegradation in the whole plume and not only at its distal end as previously suggested by the plume fringe concept. Overall, this study highlights the importance of highly temporally resolved groundwater monitoring to capture temporally varying biodegradation rates and to accurately predict biodegradation-induced contaminant attenuation in fractured bedrock aquifers.

Toluene biodegradation in the vadose zone of a poplar phytoremediation system identified using metagenomics and toluene-specific stable carbon isotope analysis.

Biodegradation is an important mechanism of action of phytoremediation systems, but performance evaluation is challenging. We applied metagenomic molecular approaches and compound-specific stable carbon isotope analysis to assess biodegradation of toluene in the vadose zone at an urban pilot field system where hybrid poplars were planted to remediate legacy impacts to an underlying shallow fractured bedrock aquifer. Carbon isotope ratios were compared spatio-temporally between toluene dissolved in groundwater and in the vapor phase. Enrichment of 13C from toluene in the vapor phase compared to groundwater provided evidence for biodegradation in the vadose zone. Total bacterial abundance (16S rRNA) and abundance and expression of degradation genes were determined in rhizosphere soil (DNA and RNA) and roots (DNA) using quantitative PCR. Relative abundances of degraders in the rhizosphere were on average higher at greater depths, except for enrichment of PHE-encoding communities that more strongly followed patterns of toluene concentrations detected. Quantification of RMO and PHE gene transcripts supported observations of active aerobic toluene degradation. Finally, spatially-variable numbers of toluene degraders were detected in poplar roots. We present multiple lines of evidence for biodegradation in the vadose zone at this site, contributing to our understanding of mechanisms of action of the phytoremediation system.

Identification of Degradation Pathways of Chlorohydrocarbons in Saturated Low-Permeability Sediments Using Compound-Specific Isotope Analysis.

This study aims to investigate whether compound-specific carbon isotope analysis (CSIA) can be used to differentiate the degradation pathways of chlorohydrocarbons in saturated low-permeability sediments. For that purpose, a site was selected, where a complex mixture of chlorohydrocarbons contaminated an aquifer-aquitard system. Almost 50 years after contaminant releases, high-resolution concentration, CSIA, and microbial profiles were determined. The CSIA profiles showed that in the aquitard cis-dichloroethene (cDCE), first considered as a degradation product of trichloroethene (TCE), is produced by the dichloroelimination of 1,1,2,2-tetrachloroethane (TeCA). In contrast, TeCA degrades to TCE via dehydrohalogenation in the aquifer, indicating that the aquifer-aquitard interface separates two different degradation pathways for TeCA. Moreover, the CSIA profiles showed that chloroform (CF) is degraded to dichloromethane (DCM) via hydrogenolysis in the aquitard and, to a minor degree, produced by the degradation of carbon tetrachloride (CT). Several microorganisms capable of degrading chlorohydrocarbons were detected in the aquitard, suggesting that aquitard degradation is microbially mediated. Furthermore, numerical simulations reproduced the aquitard concentration and CSIA profiles well, which allowed the determination of degradation rates for each transformation pathway. This improves the prediction of contaminant fate in the aquitard and potential magnitude of impacts on the adjacent aquifer due to back-diffusion.

DFN-M field characterization of sandstone for a process-based site conceptual model and numerical simulations of TCE transport with degradation.

Plumes of trichloroethene (TCE) with degradation products occur at a large industrial site in California where TCE as a dense non-aqueous phase liquid (DNAPL) entered the fractured sandstone bedrock at many locations beginning in the late 1940s. Groundwater flows rapidly in closely spaced fractures but plume fronts are strongly retarded relative to groundwater flow velocities owing largely to matrix diffusion in early decades and degradation processes in later decades and going forward. Multiple data types show field evidence for both biotic and abiotic dechlorination of TCE and its degradation products, resulting in non-chlorinated compounds. Analyses were conducted on groundwater samples from hundreds of monitoring wells and on thousands of rock samples from continuous core over depths ranging from 6 to 426 metres below ground surface. Nearly all of the present-day mass of TCE and degradation products resides in the water-saturated, low-permeability rock matrix blocks. Although groundwater and DNAPL flow primarily occur in the fractures, DNAPL dissolution followed by diffusion and sorption readily transfers contaminant mass into the rock matrix. The presence of non-chlorinated degradation products (ethene, ethane, acetylene) and compound specific isotope analysis (CSIA) of TCE and cis-1,2-dichloroethene (cDCE) indicate at least some complete dechlorination by both biotic and abiotic pathways, consistent with the observed mineralogy and hydrogeochemistry and with published results from crushed rock microcosms. The rock matrix contains abundant iron-bearing minerals and solid-phase organic carbon with large surface areas and long contact times, suggesting degradation processes are occurring in the rock matrix. Multiple, high-resolution datasets provide strong evidence for spatially heterogeneous distributions of TCE and degradation products with varying degrees of degradation observed only when using new methods that achieve better detection of dissolved gases (i.e., Snap Sampler™) and contaminant mass stored in the low permeability rock matrix (i.e., CORE-DFN™). Simulations using a discrete fracture-matrix (DFN-M) numerical model capable of rigorously simulating flow and transport in both the fractures and matrix, including interactions, show that even slow, first-order degradation rates (i.e., 5- to 20-year half-lives) informed by site-derived parameters can contribute strongly to natural attenuation, resulting in TCE plumes that become stationary in space and might even retreat after 50 to 100 years, if the DNAPL sources become depleted due to the combination of diffusion and degradation processes.

37Cl-compound specific isotope analysis and assessment of functional genes for monitoring monochlorobenzene (MCB) biodegradation under aerobic conditions.

A laboratory approach was adopted in this study to explore the potential of 37Cl-CSIA in combination with 13C-CSIA and Biological Molecular Tools (BMTs) to estimate the occurrence of monochloroenzene (MCB) aerobic biodegradation. A new analytical method for 37Cl-CSIA of MCB was developed in this study. This methodology using a GC-IRMS allowed to determine δ37Cl values within an internal error of ±0.3‰. Samples from a heavily MCB contaminated site were collected and MCB aerobic biodegradation microcosms with indigenous cultures in natural and enhanced conditions were set up. The microcosms data show a negligible fractionation for 13C associated to MCB mass decrease of >95% over the incubation time. Conversely, an enrichment factor of -0.6±0.1‰ was estimated for 37Cl, which is a reflection of a secondary isotope effect. Moreover, the dual isotope approach showed a pattern for aerobic degradation which differ from the theoretical trend for reductive dehalogenation. Quantitative Polymerase Chain Reaction (qPCR) results showed a significant increase in todC gene copy number with respect to its initial levels for both natural attenuation and biostimulated microcosms, suggesting its involvement in the MCB aerobic degradation, whereas phe gene copy number increased only in the biostimulated ones. Indeed, 37Cl fractionation in combination with the dual carbon­chlorine isotope approach and the todC gene copy number represent valuable indicators for a qualitative assessment of MCB aerobic biodegradation in the field.

Hydrogen Isotope Fractionation during the Biodegradation of 1,2-Dichloroethane: Potential for Pathway Identification Using a Multi-element (C, Cl, and H) Isotope Approach.

Even though multi-element isotope fractionation patterns provide crucial information with which to identify contaminant degradation pathways in the field, those involving hydrogen are still lacking for many halogenated groundwater contaminants and degradation pathways. This study investigates for the first time hydrogen isotope fractionation during both aerobic and anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) using five microbial cultures. Transformation-associated isotope fractionation values (εbulkH) were -115 ± 18‰ (aerobic C-H bond oxidation), -34 ± 4‰ and -38 ± 4‰ (aerobic C-Cl bond cleavage via hydrolytic dehalogenation), and -57 ± 3‰ and -77 ± 9‰ (anaerobic C-Cl bond cleavage via reductive dihaloelimination). The dual-element C-H isotope approach (ΛC-H = Δδ2H/Δδ13C ≈ εbulkH/εbulkC, where Δδ2H and Δδ13C are changes in isotope ratios during degradation) resulted in clearly different ΛC-H values: 28 ± 4 (oxidation), 0.7 ± 0.1 and 0.9 ± 0.1 (hydrolytic dehalogenation), and 1.76 ± 0.05 and 3.5 ± 0.1 (dihaloelimination). This result highlights the potential of this approach to identify 1,2-DCA degradation pathways in the field. In addition, distinct trends were also observed in a multi- (i.e., Δδ2H versus Δδ37Cl versus Δδ13C) isotope plot, which opens further possibilities for pathway identification in future field studies. This is crucial information to understand the mechanisms controlling natural attenuation of 1,2-DCA and to design appropriate strategies to enhance biodegradation.

Quantification of Degradation of Chlorinated Hydrocarbons in Saturated Low Permeability Sediments Using Compound-Specific Isotope Analysis.

This field and modeling study aims to reveal if degradation of chlorinated hydrocarbons in low permeability sediments can be quantified using compound-specific isotope analysis (CSIA). For that purpose, the well-characterized Borden research site was selected, where an aquifer-aquitard system was artificially contaminated by a three component chlorinated solvent mixture (tetrachloroethene (PCE) 45 vol %, trichloroethene (TCE) 45 vol %, and chloroform (TCM) 10 vol %). Nearly 15 years after the contaminant release, several high-resolution concentration and CSIA profiles were determined for the chlorinated hydrocarbons that had diffused into the clayey aquitard. The CSIA profiles showed large shifts of carbon isotope ratios with depth (up to 24‰) suggesting that degradation occurs in the aquitard despite the small pore sizes. Simulated scenarios without or with uniform degradation failed to reproduce the isotope data, while a scenario with decreasing degradation with depth fit the data well. This suggests that nutrients had diffused into the aquitard favoring stronger degradation close to the aquifer-aquitard interface than with increasing depth. Moreover, the different simulation scenarios showed that CSIA profiles are more sensitive to different degradation conditions compared to concentration profiles highlighting the power of CSIA to constrain degradation activities in aquitards.

Transport of through a Thick Vadose Zone.

Livestock manure applications on fields can be a source of contamination in water resources, including groundwater. Although fecal indicators like have often been detected in tile drainage systems, few studies have monitored groundwater at depth after manure treatments, especially at sites with a deep, heterogeneous vadose zone. Our hypothesis was that microbial transport through a thick vadose zone would be limited or nonexistent due to attenuation processes, subsurface thickness, and heterogeneity. This study tested this hypothesis by monitoring concentrations beneath a 12-m-thick vadose zone of coarse, heterogeneous glacial sediments after surface application of liquid swine manure. was detected on all 23 sample dates over the 5-mo period (4 Apr. 2012-13 Aug. 2012), with particularly elevated concentrations 1 wk after application and lasting for 5 wk. Variable low-level concentrations before and after the elevated period suggest remobilization and delayed transport of microorganisms to the water table without additional loadings within the flow field. These findings suggest preferential flow pathways allowing deep infiltration of manure bacteria as well as a continued source of bacteria, with variable retention and travel times, over several months. Preferential flow pathways at this site include soil macropores, depression focused infiltration, and pathways related to subsurface heterogeneity and/or fracture flow through finer-grained diamict beds. Further research is needed to confirm the relative contribution of sources, constrain travel times, and define specific transport pathways.

Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes.

The use of compound specific multi-isotope approach (C and Cl) in the characterization of a chlorinated ethenes contaminated fractured aquifer allows the identification of several sources and contaminant plumes, as well as the occurrence of biodegradation and mixing processes. The study site is located in Spain with contamination resulting in groundwater concentrations of up to 50mg/L of trichloroethene (TCE), the most abundant chlorinated ethene, and 7 mg/L of tetrachloroethene (PCE). The potential sources of contamination including abandoned barrels, an underground tank, and a disposal lagoon, showed a wide range in δ(13)C values from -15.6 to -40.5‰ for TCE and from -18.5 to -32.4‰ for PCE, allowing the use of isotope fingerprinting for tracing of the origin and migration of these contaminants in the aquifer. In contrast, there is no difference between the δ(37)Cl values for TCE in the contaminant sources, ranging from +0.53 to +0.66‰. Variations of δ(37)Cl and δ(13)C in the different contaminant plumes were used to investigate the role of biodegradation in groundwater. Moreover, the isotopic data were incorporated into a reactive transport model for determination of whether the isotope pattern observed downstream from the tank's source could be explained by the simultaneous effect of mixing and biodegradation. The results demonstrate that a multi-isotope approach is a valuable tool for characterization of complex sites such as fractured bedrock aquifer contaminated by multiple sources, providing important information which can be used by consultants and site managers to prioritize and design more successful remediation strategies.

Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment.

The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S2O8(2-)) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S2O8(2-) molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S2O8(2-) molar ratio of -7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S2O8(2-) molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system.

Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe2+ activated persulfate.

The increased use of persulfate (S(2)O(8)(2-)) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe(2+)). An average carbon isotope enrichment factor ε(bulk) of -4.9‰ for PCE, -3.6‰ for TCE and -7.6‰ for cis-DCE were obtained in batch experiments. Variations in the initial S(2)O(8)(2-)/Fe(2+)/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S(2)O(8)(2-)/Fe(2+)/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe(2+) activated persulfate.

Fingerprinting TCE in a bedrock aquifer using compound-specific isotope analysis.

A dual isotope approach based on compound-specific isotope analysis (CSIA) of carbon (C) and chlorine (Cl) was used to identify sources of persistent trichloroethylene (TCE) that caused the shut-down in 1994 of a municipal well in an extensive fractured dolostone aquifer beneath Guelph, Ontario. Several nearby industrial properties have known subsurface TCE contamination; however, only one has created a comprehensive monitoring network in the bedrock. The impacted municipal well and many monitoring wells were sampled for volatile organic compounds (VOCs), inorganic parameters, and CSIA. A wide range in isotope values was observed at the study site. The TCE varies between -35.6‰ and -21.8‰ and from 1.6‰ to 3.2‰ for δ(13) C and δ(37) Cl, respectively. In case of cis-1,2-dichloroethene, the isotope values range between -36.3‰ and -18.9‰ and from 2.4‰ to 4.7‰ for δ(13) C and δ(37) Cl, respectively. The dual isotope approach represented by a plot of δ(13) C vs. δ(37) Cl shows the municipal well samples grouped in a domain clearly separate from all other samples from the property with the comprehensive well network. The CSIA results collected under non-pumping and short-term pumping conditions thus indicate that this particular property, which has been studied intensively for several years, is not a substantial contributor of the TCE presently in the municipal well under non-pumping conditions. This case study demonstrates that CSIA signatures would have been useful much earlier in the quest to examine sources of the TCE in the municipal well if bedrock monitoring wells had been located at several depths beneath each of the potential TCE-contributing properties. Moreover, the CSIA results show that microbial reductive dechlorination of TCE occurs in some parts of the bedrock aquifer. At this site, the use of CSIA for C and Cl in combination with analyses of VOC and redox parameters proved to be important due to the complexity introduced by biodegradation in the complex fractured rock aquifer. It is highly recommended to revisit the study when the municipal well is back into full operation.

Carbon and chlorine isotope ratios of chlorinated ethenes migrating through a thick unsaturated zone of a sandy aquifer.

Compound-specific isotope analysis (CSIA) can potentially be used to relate vapor phase contamination by volatile organic compounds (VOCs) to their subsurface sources. This field and modeling study investigated how isotope ratios evolve during migration of gaseous chlorinated ethenes across a 18 m thick unsaturated zone of a sandy coastal plain aquifer. At the site, high concentrations of tetrachloroethene (PCE up to 380 µg/L), trichloroethene (TCE up to 31,600 µg/L), and cis-1,2-dichloroethene (cDCE up to 680 µg/L) were detected in groundwater. Chlorinated ethene concentrations were highest at the water table and steadily decreased upward toward the land surface and downward below the water table. Although isotopologues have different diffusion coefficients, constant carbon and chlorine isotope ratios were observed throughout the unsaturated zone, which corresponded to the isotope ratios measured at the water table. In the saturated zone, TCE became increasingly depleted along a concentration gradient, possibly due to isotope fractionation associated with aqueous phase diffusion. These results indicate that carbon and chlorine isotopes can be used to link vapor phase contamination to their source even if extensive migration of the vapors occurs. However, the numerical model revealed that constant isotope ratios are only expected for systems close to steady state.