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Chlordecone (CLD; C10Cl10O) is an organochlorine pesticide extensively used between 1960s and 1990s in the French West Indies (FWI). Its massive use led to soil and river pollution which prompted its ban in 1993. CLD has a bis-homocubane structure and various chlorine atoms making it highly recalcitrant in the environment. To date, several environmental compartments of the FWI continue facing the legacy of CLD pollution. This study aims at improving the monitoring of the degradation (or recalcitrance) extent of CLD in the soils of the FWI following in situ chemical reduction (ISCR). Multi-element compound-specific isotope analysis (ME-CSIA) was used to identify changes of stable isotopes of CLD (i.e., 13C/12C and 37Cl/35Cl) produced during distinct abiotic reductive transformation reactions. Reductive transformation of CLD was tested in abiotic microcosms in the presence of either zero-valent iron, ascorbic acid, vitamin B12, or persulfate activated by microwave irradiation. CLD transformation was evidenced by the detection of several hydrochlordecones (after losses of one or two chlorine atoms) under all conditions. Enrichment of the 13C isotopes of CLD relative to 12C revealed distinct signatures during transformation reactions of CLD to maximum Δδ13C of +7.2 ‰. A novel stable Cl isotope analysis was performed by liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS). Ongoing Cl isotope analysis may establish a multi-element assessment in which abiotic CLD degradation pathways may be distinguished based on stable C-Cl signatures. Altogether, our results may provide an improved strategy to elucidate CLD degradation in contaminated soils of the FWI.

International audience

International audience; The transfer of pesticides from agricultural soils to food and drinking water is a major health issue. There are actually few robust methods to identify, characterize and quantify the dissipation of pesticides in complex media such as soils, waters and sediments. Here, we review multi-elemental compound-specific isotope analysis to study sources and transformations of pesticides in agricultural soils. First, we discuss advanced extraction and purification techniques for pesticides in soils. Then, analytical techniques for reliable measurements of the stable isotope composition of the pesticides are presented. We report a unique dataset of 547 isotopic compositions of 71 active molecules produced by various pesticide manufacturers, for the following isotopes: 13C, 15N, 37Cl, and 2H. We also report 270 isotope fractionation values for 33 compounds, which might help to elucidate the mechanisms of pesticide transformation by biodegradation, photodegradation and other abiotic processes. Compounds include legacy pesticides such as atrazine, lindane, dichlorodiphenyltrichloroethane, chlordecone and organophosphorus compounds. Transformation processes may be identified and quantified using the Rayleigh concept for isotope fractionation during reaction.

International audience; This work proposes a suitable treatment for the leachates from a sewage sludge composting process using a specific windrow (biopile). The biopile's evolution and organic content degradation were followed for 2 months with regular leachate spraying to assess the physico-chemical and biological impacts, and determine the risk of enrichment with certain monitored pollutants. The final objective was the valorization of the biopile substrates in the composting process, while respecting the quality standards of use in a circular economy way. Classical physico-chemical parameters (pH, conductivity, dissolved organic carbon (DOC), total dissolved nitrogen (TDN), etc.) were measured in the leachates and in the water-extractable and dry-solid fractions of the biopile, and the catabolic evolution of the microorganisms (diversity and activities), as well as the enrichment with persistent organic pollutants (POPs) (prioritized PAHs (polycyclic aromatic hydrocarbons) and PCBs (polychlorinated biphenyls)), were determined. The results showed that the microbial populations that were already present in the biopile, and that are responsible for biodegradation, were not affected by leachate spraying. Even when the studied compost leachate was highly concentrated with ammonium nitrogen (10.4 gN L −1 on average), it significantly decreased in the biopile after 2 weeks. A study on the evolution of the isotopic signature (δ 15 N) confirmed the loss of leachate nitrogen in its ammoniacal form. The bio-physico-chemical characteristics of the biopile at the end of the experiment were similar to those before the first spraying with leachate. Moreover, no significant enrichment with contaminants (metal trace elements, volatile fatty acids, or persistent organic pollutants) was observed. The results show that it would be possible for composting platforms to implement this inexpensive and sustainable process for the treatment of leachates.

Analytical and numerical models describing the evolution of contaminant concentrations in the plume associated with the dissolution of NAPL source and degradation processes were presented in the literature. At real sites and particularly in complex aquifers like chalk, it is difficult to understand how the sources of contaminants evolve with time. 1,1,1-Trichloroethane (1,1,1-TCA) is one of the few compounds with a well-known hydrolysis constant, that can help to improve knowledge of the contaminant sources and transport rates of dissolved contaminants in groundwater by dating the spill. In this work, different scenarios that could explain the evolution of the concentrations of 1,1,1-TCA and its degradation product 1,1-Dichloroethene (1,1-DCE) at a real contaminated site were investigated by analytical and numerical modelling. The results show that (1) the peaks of concentration time series do not correspond to a single contamination event even in the case of a complex medium, (2) the multiphasic behavior of the concentration time series is dictated by the dissolution in a heterogeneous medium, and (3) the persistence of the concentrations can arise from a small residual organic phase or transport in dual domain medium.

International audience; Bromoform (CHBr3) belongs to very-short-lived substances (VSLSs), which are important precursors of reactive bromine species (BrOx) contributing to tropospheric and stratospheric chemistry. To date, most models calculating bromine product emissions to the atmosphere only consider the natural production of CHBr3 from marine organisms such as macroalgae and phytoplankton. However, CHBr3 has many other anthropogenic sources (coastal industrial sites, desalination and wastewater plants, ballast waters, and seawater toilets) that may drastically increase the amounts emitted in the atmosphere. Here, we report the levels of CHBr3 released in water and air (according to real-time and offline measurements by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and gas chromatography with electron capture detection (GC-ECD)) in a highly industrialized area where 3 million cubic meters of chlorinated seawater is released each day, which were measured during six field campaigns (at sea and on land) distributed over 3 years. The highest levels found during this survey (which were correlated to the physical–chemical characteristics of the water, meteorological and hydrological conditions, salinity, and temperature gradients along the water column) reached 34.6 μg L–1 in water (100–10 000 times higher than reported natural levels) and 3.9 ppbv in the air (100 times higher than the maximum reported value to date). These findings suggest the need to undertake sampling and analysis campaigns as close as possible to chlorinated discharges, as anthropogenic CHBr3 sources from industrial discharges may be a missing factor in global flux estimates or organic bromine to the atmosphere.

International audience; 2,4,6-tribromophenol (TBP) is implied in the production of brominated flame retardants but is also a major chlorination by-product in seawater. A growing number of studies indicate that TBP is highly toxic to the marine biota, but the contribution of anthropogenic sources among natural production is still under question concerning its bioaccumulation in marine organisms. Here, several water sampling campaigns were carried out in the industrialized Gulf of Fos and clearly showed the predominant incidence of industrial chlorination discharges on the TBP levels in water, at the 1-10 ng L-1 level in average and reaching up to 580 ng L-1 near the outlets. The bioaccumulation of TBP was measured in 90 biota samples of the Gulf of Fos. The concentrations found in European conger muscle tissues (140 to 1000 ng g-1 lipid weight, in average), purple sea urchin gonads (830 to 880 ng g-1 lipid weight, in average), and Mediterranean mussel body (1500 to 2000 ng g-1 lipid weight, in average) were above all published references. Significant correlations with fish length (European conger) and gonad somatic index (purple sea urchin) were also identified. Comparatively, fish, urchins and mussels from other Mediterranean sites analyzed within this study showed a lower bioaccumulation level of TBP, consistently with what found elsewhere. Industrial outflows were thus identified as hotspots for TBP in seawater and marine organisms. The environmental risk assessment indicated a high potential toxicity in the industrial Gulf of Fos, in particular near the outlets, and a limited threat to human but toxicological references are lacking.

International audience; The biodegradation of hexachlorocyclohexanes (HCHs) is known to be accompanied by isotope fractionation of carbon (13C/12C), but no systematic studies were performed on abiotic degradation of HCH isomers by iron (II) minerals. In this study, we explored the carbon isotope fractionation of α-HCH during dechlorination by FeS nanoparticles at different pH values. The results of three different experiments showed that the apparent rate constants during dehalogenation of α-HCH by FeS increased with pH. The lowest apparent rate constant value α-HCH during dehalogenation by FeS was 0.009 d−1 at pH value of 2.4, while the highest was 1.098 d−1 at pH 11.8. α-HCH was completely dechlorinated by FeS only at pH values 9.9 and 11.8, while the corresponding apparent rate constants were 0.253 d−1 and 1.098 d−1, respectively. Regardless of the pH used, the 1,2,4-trichlorobenzene (1,2,4-TCB), 1,2-dichlorobenzene (1,2-DCB), and benzene were the dominant degradation products of α-HCH. An enrichment factor (εC) of −4.7 ± 1.3‰ was obtained for α-HCH using Rayleigh model, which is equivalent to an apparent kinetic isotope effect (AKIEC) value of 1.029 ± 0.008 for dehydrohalogenation, and of 1.014 ± 0.004 for dihaloelimination, respectively. The magnitude of isotope fractionation from this study suggests that abiotic isotope fractionation by FeS must be taken into account in anoxic sediments and aquifers contaminated with HCH isomers, when high concentrations of FeS are present in the above-mentioned anoxic environments.

International audience; Soils and groundwater are often contaminated by complex organic mixtures also called Non Aqueous Phase Liquids (NAPLs). Several techniques such as drilling, monitoring of soil gas or injection of tracers are traditionally used to quantify NAPLs in aquifers but are complex to perform. The use of natural soil gas such as 222Rn could be an easy and cheap alternative. This method requires the knowledge of the radon NAPL-water partitioning coefficients (Kn-w.). Once spilled on soil, NAPL will undergo degradation (evaporation, effects of sun light among others) and this degradation could impact the Kn-w. This study aims at investigating the partitioning coefficients of complex NAPLs such as commercial diesel fuel and gasoline in relation to degradation such as evaporation and UV-degradation. For that purpose, batch experiments and GCMS investigations were carried out. The results show different Kn-w for the commercial diesel fuel (60.7 ± 6.1) and gasoline (37.4 ± 5.6). The results also show different Kn-w behaviors in relation with degradation. Degraded diesel fuel display opposite Kn-w values (74.8 ± 7.5 and 25.1 ± 2.5 for UV degraded and evaporated diesel fuel, respectively), compared to fresh one. Degraded gasoline shows no significant variations of the Kn-w compared to fresh one. The molecular investigation reveals the removal of the most volatile fraction for the evaporation treatment, whereas UV-degradation do not have pronounced effects on the chromatogram pattern. For the gasoline molecular investigation, no difference is observed between the treatments excepted a very slight removal of the lightest compounds under evaporation. These results show that NAPL degradation have effects on the Kn-w for diesel fuel and no significant effects for gasoline, at least with these degradation paths. This Kn-w variation will have in fine effects on 222Rn activity interpretation and NAPL subsurface quantification.

International audience; Groundwater contamination by chlorinated hydrocarbons is a worldwide problem that poses important challenges in remediation processes. In Italy, the Legislative Decree 152/06 defines the water quality limits to be obtained during the cleanup process. In situ bioremediation techniques are becoming increasingly important due to their affordability and, under the right conditions, because they can be more effective than conventional methodologies. In the initial feasibility study phase, the numerical modeling supports the reliability of each technique. Two different codes, BIOCHLOR and PHREEQC were discussed and compared assuming different field conditions. Isotopic Fractionation-Reactive Transport Models were then developed in one synthetic and one simple field case. From the results, the two codes were in agreement and also able to demonstrate the Monitored Natural Attenuation processes occurring at the dismissed site located in Italy. Finally, the PHREEQC model was used to forecast the remediation time frame by MNA, hypothesizing a complete source cleanup: a remediation time frame of about 10–11 years was achieved by means of natural attenuation processes.

International audience; Short-chain chlorinated paraffins (SCCPs) are under regulation through the European Water Framework Directive and were recently classified as POPs. Consecutively, the increasing use of middle-chain chlorinated paraffins (MCCPs) becomes of growing concern. Knowledge on the occurrence of chlorinated paraffins (CPs) is still scarce particularly in water phase. To achieve sufficient method sensitivity, the passive sampling approach, acting as a relevant alternative to usual grab sampling, has been considered only very recently for the monitoring of CPs in water. The present work aimed at determining the diffusion coefficients in silicone (D s) and the silicone-water partition coefficients (K sw) of various CP groups, having different chlorine contents and carbon chain lengths, in four commercial CP mixtures. Log D s (-10.78 to-10.21) was found to vary little and to be high for the groups of CPs studied. Thus, their uptake in silicone is controlled by the water boundary layer, which allows to consider the release of performance and reference compounds for infield estimation of the sampling rate. Moreover, CPs partitioned strongly towards silicone rubbers. Both the chlorination degree and the carbon chain length of CPs cause large uncertainties in the partitioning between silicone and water (log K sw between 4.85 and 6.30), indicating that instead of an average value, differentiated K sw should be used to estimate aqueous CPs more accurately. Even so, the probable influence of chlorine atoms position on polarity and partitioning may be an argument for favoring sampling in the kinetic stage.

Soils and groundwater are often contaminated by complex organic mixtures also called Non Aqueous Phase Liquids (NAPLs). Several techniques such as drilling, monitoring of soil gas or injection of tracers are traditionally used to quantify NAPLs in aquifers but are complex to perform. The use of natural soil gas such as

In multi-elemental compound-specific isotope analysis the lambda (Λ) value expresses the isotope shift of one element versus the isotope shift of a second element. In dual-isotope plots, the slope of the regression lines typical reveals the footprint of the underlying isotope effects allowing to distinguish degradation pathways of an organic contaminant molecule in the environment. While different conventions and fitting procedures are used in the literature to determine Λ, it remains unclear how they affect the magnitude of Λ. Here we generate synthetic data for benzene δ2H and δ13C with two enrichment factors eH and eC using the Rayleigh equation to examine how different conventions and linear fitting procedures yield distinct Λ. Fitting an error-free data set in a graph plotting the δ2H versus δ13C overestimates Λ by 0.225%⋅eH/eC, meaning that if eH/eCis larger than 22, Λ is overestimated by more than 5%. The correct fitting of Λ requires a natural logarithmic transformation of δ2H versus δ13C data. Using this transformation, the ordinary linear regression (OLR), the reduced major-axis (RMA) and the York methods find the correct Λ, even for large eH/eC. Fitting a dataset with synthetic data with typical random errors let to the same conclusion and positioned the suitability of each regression method. We conclude that fitting of non-transformed δ values should be discontinued. The validity of most previous Λ values is not compromised, although previously obtained Λ values for large eH/eC could be corrected using our error estimation to improve comparison.

International audience; In order to observe the relationships between the temporal variations of CO2 surface fluxes and the CO2 soil gas transport in soil profile before and during rainfall events, two experiments were conducted in a controlled natural environment at different time periods. These experiments consisted in injecting pure CO2 in a lysimeter at 160 cm depth and simulating heavy rainfall event at its surface for 2 weeks. During the whole experiments, CO2 soil gas concentrations and surface fluxes were continuously monitored. These measurements showed that the flux measured through the flux chamber were consistent with the concentration profiles. During simulated rainfall events, the concentrations and fluxes showed a clear change linked to the presence of water on the top of the water profile. The results clearly show a significant decrease of CO2 flux to atmosphere induced by rainfall infiltration and consequential wash-out of the CO2 present in the soil.

International audience; Position-specific isotope analysis by Nuclear Magnetic Resonance spectrometry was employed to study the 13C intramolecular isotopic fractionation associated with the migration of organic substrates through different stationary phases chromatography columns. Liquid chromatography is often used to isolate compounds prior to their isotope analysis and this purification step potentially alters the isotopic composition of target compounds introducing a bias in the later measured data. Moreover, results from liquid chromatography can yield the sorption parameters needed in reactive transport models that predict the transport and fate of organic contaminants to in the environment. The aim of this study was to use intramolecular isotope analysis to study both 13C and 15N isotope effects associated with the elution of paracetamol (acetaminophen) through different stationary phases and to compare them to effects observed previously for vanillin. Results showed very different intramolecular isotope fractionation profiles depending on the chemical structure of the stationary phase. The data also demonstrate that both the amplitude and the distribution of measured isotope effects depend on the nature of the non-covalent interactions involved in the migration process. Results provided by theoretical calculation performed during this study also confirmed the direct link between observed intramolecular isotope fractionation and the nature of involved intermolecular interactions. It is concluded that the nature of the stationary phase through which the substrate passes has a major impact on the intramolecular isotopic composition of organic compounds isolated by chromatography methods..

International audience; This study aimed at investigating whether stable isotopes can be used to monitor the progress of volatile organic compounds (VOCs) volatilization from contaminated sediment during venting. Batches of a dry aquifer sediment were packed into stainless steel HPLC columns, humidified with distilled water and later contaminated by either liquid toluene or propan-2-ol. The VOCs were then volatilized by a stream of gas at room temperature, and the concentrations and stable isotope ratios of gaseous VOCs were recorded by isotope-ratio mass spectrometry. During early stages of volatilization of toluene, the isotope ratios Δδ13C shifted to more negative values by about −3 to −5‰ and the Δδ2H by more than −40‰, while the concentration remained at or near initial saturated vapor concentration. Depletion of the isotope ratios in the gas was explained by the vapor-liquid fractionation process, which is amplified by successive self-partitioning steps of gaseous VOC into remaining liquid VOC. For propan-2-ol the carbon isotope shift was negative like for toluene, whereas the H shift was positive. Hydrogen bonding in the liquid propan-2-ol phase causes a normal vapor-liquid H isotope effect which was described already in classical literature. The isotope shifts in the present experiments are larger than previously reported shifts due to phase-change processes and reach the magnitude of shifts usually observed in kinetic isotope fractionation.

International audience; Stable isotopes have been widely used to monitor remediation of environmental contaminants over the last decades. This approach gives a good mechanistic description of natural or assisted degradation of organic pollutants, such as methyl tert-butyl ether (MTBE). Since abiotic degradation seems to be the most promising assisted attenuation method, the isotopic fractionation associated with oxidation and hydrolysis processes need to be further investigated in order to understand better these processes and make their monitoring more efficient. In this study, position-specific isotope effects (PSIEs) associated with permanganate oxidation and acid hydrolysis of MTBE were determined using isotope ratio monitoring by 13C Nuclear Magnetic Resonance Spectrometry (irm-13C NMR) combined with isotope ratio monitoring by Mass Spectrometry (irm-MS). The use of this Position-Specific Isotopic Analysis (PSIA) method makes it possible to observe a specific normal isotope effect (IE) associated with each of these two abiotic degradation mechanisms. The present work demonstrates that the 13C isotope pattern of the main degradation product, tert-butyl alcohol (TBA), depends on the chemical reaction by which it is produced. Furthermore, this study also demonstrates that PSIA at natural abundance can give new insights into reaction mechanisms and that this methodology is very promising for the future of modeling the remediation of organic contaminants.

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Several remediation techniques are available to treat source zones with Non-Aqueous Phase Liquids (NAPLs). Despite hundreds of treated sites, it is still quite difficult to estimate the potential efficiency of a treatment technique under a given context. In the literature, numerous papers deal with the potential limitations of one remediation technique at a laboratory scale or in the field, but only a few studies compared two or more different techniques. Thus, the objective of this chapter is to compare different treatment techniques in the same solid matrix and under the same conditions at three different experimental scales: batch, columns, and metric pilot tank experiments. The chosen techniques are among the most common ones, i.e., oxidation, sparging, surfactant flushing, and low-temperature thermal treatment. These four techniques were applied first at the batch and column scale in order to assess their potential efficiency under well-controlled conditions. These experiments are mandatory for choosing the best oxidant, the activating agents for this oxidant, the best concentration, and the determination of the limiting factors which can be encountered. All these lab experiments allowed a selection of favorable conditions for testing four techniques at the pilot scale. These treatment techniques were tested in the same configuration, in tanks of one cubic meter volume, filled with sand and emplaced sources containing a toluene/decane mixture as representative of a NAPL phase. The major findings of this study are: (1) Thermal treatment was the most efficient remediation technique; (2) Dissolution issues reduced the efficiency of the three other techniques; (3) Heterogeneity in the tanks caused a decrease in the removal efficiency for all treatments compared to efficiencies obtained at the column scale; (4) Density effects, which were not encountered at the column scale, caused problems for oxidant injection in the tanks; (5) Removal techniques that are equal for mass-based removal goal were quite different in lowering the dissolved contaminant flux from the system. Therefore, the ranking of techniques based on mass removal may not be appropriate and be replaced by a flux reduction selection; and (6) A need to perform experiments at three experimental scales is evidenced: batch studies allow sufficient variations in experimental conditions, the column experiments permitted the optimization of surfactant and oxidant injection, whereas tank experiments allow studies under heterogeneous flow conditions.

International audience; The potential of LNAPL delineation by 222Rn soil-gas monitoring in a chemically heterogeneous vadose zone was investigated in this study based on laboratory (batch and columns) experiments and numerical modelling. An enhanced version of the MIN3P reactive transport code was used to simulate Rn transport in both uncontaminated and NAPL-contaminated vadose zones and results were validated against analytical solutions and laboratory experiments. Results show that 222Rn activity profiles are mainly controlled by porous media 222Rn production, vadose zone fluid saturations and especially the type and distribution of NAPL in contaminated areas. The results also show that decreases in 222Rn activity and variations in activity gradients provide evidence for the presence and saturation of NAPL. This study demonstrates that LNAPL delineation via 222Rn gas surveys at contaminated sites works best, if gas measurements extend as deep as possible and include regions where 222Rn activity decreases due to elevated NAPL content. In addition, collection and analysis of depth-discrete gas samples allows the characterization of vertical NAPL distribution based on the 222Rn activity gradient. The determination of 222Rn production in the unsaturated zone, as well as water capillary pressure curves are of key importance in enabling the discrimination of an uncontaminated from a NAPL-contaminated area.

The potential of LNAPL delineation by

International audience; BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in ground-water, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chioroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes C-12,C-13, Cl-35, Cl-37 from a constant source. The model can consider secondary isotope effects that can occur in the breaking of C-Cl bonds. The model is correctly reproducing results for delta C-13 and delta Cl-37 modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication. (C) 2016 Elsevier B.V. All rights reserved.

BIOSCREEN is a well-known simple tool for evaluating the transport of dissolved contaminants in groundwater, ideal for rapid screening and teaching. This work extends the BIOSCREEN model for the calculation of stable isotope ratios in contaminants. A three-dimensional exact solution of the reactive transport from a patch source, accounting for fractionation by first-order decay and/or sorption, is used. The results match those from a previously published isotope model but are much simpler to obtain. Two different isotopes may be computed, and dual isotope plots can be viewed. The dual isotope assessment is a rapidly emerging new approach for identifying process mechanisms in aquifers. Furthermore, deviations of isotope ratios at specific reactive positions with respect to “bulk” ratios in the whole compound can be simulated. This model is named BIOSCREEN-AT-ISO and will be downloadable from the journal homepage.

Tracing the origin of iron-cyanide complexes in the environment is important because these compounds are potentially toxic. We determined the stable isotopic compositions of cyanide-carbon (CCN) and cyanide-nitrogen (NCN) in 127 contaminated solids and 11 samples of contaminated groundwater from coal carbonization sites, blast furnace operations, and commercial cyanide applications. Coal-carbonization-related cyanides had unique high mean δ(13)CCN values of -10.5 ± 3.5‰ for the solids and -16.1 ± 1.2‰ for the groundwater samples, while the values for blast furnace sludge (-26.9 ± 1.5‰), commercial cyanides (-26.0 ± 3.0‰), and their corresponding groundwaters were significantly lower. Determination of δ(13)CCN is a promising tool for identifying the source of cyanide contamination. However, for coal carbonization sites, historical research into the manufacturing process is necessary because a nonconventional gas works site exhibited exceptionally low δ(13)CCN values of -22.7 ± 1.7‰. The δ(15)NCN values for samples related to coal carbonization and blast furnaces overlapped within a range of +0.1 to +10.3‰, but very high δ(15)NCN values seemed to be indicative for a cyanide source in the blast furnace. In contrast, commercial cyanides tend to have lower δ(15)NCN values of -5.6 to +1.9‰ in solids and -0.5 to +3.0‰ in the groundwater.

International audience; The spatiotemporal structure of wind-driven circulation patterns and associated water exchanges can drive important bio-hydrodynamic interactions in shallow lagoons. The Vaccares lagoon system is a complex shallow hydrosystem located in the central part of the Rhone Delta (France). It is internationally recognized as part of a biosphere reserve within the framework of UNESCO's Man and Biosphere Programme, and as a RAMSAR site. Due to its frequent occurrence in this area, and considering the shallowness of the Vaccares lagoon system, wind is assumed to play a major role in the hydrodynamic and biological processes. In this study, a hydrodynamic model was developed to investigate the structure of wind-driven circulations in the Vaccares lagoon system, to provide insights into their role in transport and water exchange processes. The implementation and assessment (calibration and validation) of the model is presented first. Simulations were then performed for two typical steady wind conditions and for one measured unsteady wind event. The results illustrate the influence of the complex geometry of the Vaccares lagoon system on the wind-driven circulations, and the differences observed between the different sub-lagoons in this system. The differences in wind-induced water exchanges between these sub-lagoons are also discussed.

International audience; Position-specific isotope effects (PSIEs) have been measured by isotope ratio monitoring C-13 nuclear magnetic resonance spectrometry during the evaporation of 10 liquids of different polarities under 4 evaporation modes (passive evaporation, air-vented evaporation, low pressure evaporation, distillation). The observed effects are used to assess the validity of the Craig-Gordon isotope model for organic liquids. For seven liquids the overall isotope effect (IE) includes a vapor-liquid contribution that is strongly position specific in polar compounds but less so in apolar compounds and a diffusive IE that is not position-specific, except in the alcohols, ethanol and propan-1-ol. The diffusive IE is diminished under forced evaporation. The position-specific isotope pattern created by liquid-vapor IEs is manifest in five liquids, which have an air-side limitation for volatilization. For the alcohols, undefined processes in the liquid phase create additional PSIEs. Three other liquids with limitations on the liquid side have a lower, highly position-specific, bulk diffusive IE. It is concluded that evaporation of organic pollutants creates unique position-specific isotope patterns that may be used to assess the progress of remediation or natural attenuation of pollution and that the Craig-Gordon isotope model is valid for the volatilization of nonpolar organic liquids with air-side limitation of the volatilization rate.

International audience; Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by C-13 NMR (irm-C-13 NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. (C) 2015 Elsevier Ltd. All rights reserved.

International audience; We aim at predicting the effect of structure and isotopic substitutions on the equilibrium vapour pressure isotope effect of various organic compounds (alcohols, acids, alkanes, alkenes and aromatics) at intermediate temperatures. We attempt to explore quantitative structure property relationships by using artificial neural networks (ANN); the multi-layer perceptron (MLP) and compare the performances of it with multi-linear regression (MLR). These approaches are based on the relationship between the molecular structure (organic chain, polar functions, type of functions, type of isotope involved) of the organic compounds, and their equilibrium vapour pressure. A data set of 130 equilibrium vapour pressure isotope effects was used: 112 were used in the training set and the remaining 18 were used for the test/validation dataset Two sets of descriptors were tested, a set with all the descriptors: number of C-12, C-13, O-16, O-18, H-1, H-2, OH functions, OD functions, C=O functions, Connolly Solvent Accessible Surface Area (CSA) and temperature and a reduced set of descriptors. The dependent variable (the output) is the natural logarithm of the ratios of vapour pressures (ln R), expressed as light/heavy as in classical literature. Since the database is rather small, the leave-one-out procedure was used to validate both models. Considering higher determination coefficients and lower error values, it is concluded that the multi-layer perceptron provided better results compared to multi-linear regression. The stepwise regression procedure is a useful tool to reduce the number of descriptors. To our knowledge, a Quantitative Structure Property Relationship (QSPR) approach for isotopic studies is novel. (C) 2014 Elsevier Ltd. All rights reserved.

The enrichment factor (e) is a common way to express Isotope Effects (IEs) associated with a phenomenon. Many studies determine e using a Rayleigh-plot, which needs multiple data points. More recent articles describe an alternative method using the Rayleigh equation that allows the determination of e using only one experimental point, but this method is often subject to controversy. However, a calculation method using two points (one experimental point and one at t0) should lead to the same results because the calculation is derived from the Rayleigh equation. But, it is frequently asked “what is the valid domain of use of this two point calculation?” The primary aim of the present work is a systematic comparison of results obtained with these two methodologies and the determination of the conditions required for the valid calculation of e. In order to evaluate the efficiency of the two approaches, the expanded uncertainty (U) associated with determining e has been calculated using experimental data from three published articles. The second objective of the present work is to describe how to determine the expanded uncertainty (U) associated with determining e. Comparative methodologies using both Rayleigh-plot and two point calculation are detailed and it is clearly demonstrated that calculation of e using a single data point can give the same result as a Rayleigh-plot provided one strict condition is respected: that the experimental value is measured at a small fraction of unreacted substrate (f < 30%). This study will help stable isotope users to present their results in a more rigorous expression: e ± U and therefore to define better the significance of an experimental results prior interpretation.

11th International Symposium on Applied Isotope Geochemistry (AIG), French Geol Survey, Orleans, FRANCE, SEP 21-25, 2015; International audience; The common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio measurement by mass spectrometry leads to the loss of significant information of potential interest, since it is the position-specific fractionation which most closely reflects the effect of physicochemical processes. We have shown for MTBE, a common ground water contaminant, that isotopic quantitative C-13 NMR spectrometry can be effectively applied to obtain this position-specific data. It is found that different characteristic position-specific isotope fractionation patterns are introduced by different types of evaporative process or by oxidative degradation. (C) 2015 Published by Elsevier B.V.

A diesel fuel contaminated aquifer in Menziken, Switzerland was treated for 4.5 years by injecting aerated groundwater, supplemented with KNO3 and NH4H2PO4 to stimulate indigenous populations of petroleum hydrocarbon (PHC) degrading microorganisms. After dissolved PHC concentrations had stabilized at a low level, engineered in situ bioremediation was terminated. The main objective of this study was to evaluate the efficacy of intrinsic in situ bioremediation as a follow-up measure to remove PHC remaining in the aquifer after terminating engineered in situ bioremediation. In the first 7 months of intrinsic in situ bioremediation, redox conditions in the source area became more reducing as indicated by lower concentrations of SO24‾ and higher concentrations of Fe(II) and CH4. In the core of the source area, strongly reducing conditions prevailed during the remaining study period (3 years) and dissolved PHC concentrations were higher than during engineered in situ bioremediation. This suggests that biodegradation in the core zone was limited by the availability of oxidants. In lateral zones of the source area, however, gradually more oxidized conditions were reestablished again, suggesting that PHC availability increasingly limited biodegradation. The total DIC production rate in the aquifer decreased within 2 years to about 25% of that during engineered in situ bioremediation and remained at that level. Stable carbon isotope analysis confirmed that the produced DIC mainly originated from PHC mineralization. The total rate of DIC and CH4 production in the source area was more than 300 times larger than the rate of PHC elution. This indicates that biodegradation coupled to consumption of naturally occurring oxidants was an important process for removal of PHC which remained in the aquifer after terminating engineered measures.

The anaerobic biodegradation of hydrocarbons at mineral oil contaminated sites has gathered increasing interest as a naturally occurring remediation process. The aim of this study was to investigate biodegradation of hydrocarbons in laboratory aquifer columns in the absence of O2 and NO&#1753, and to calculate a mass balance of the anaerobic biodegradation processes. The laboratory columns contained aquifer material from a diesel fuel contaminated aquifer. They were operated at 25°C for 65 days with artificial groundwater that contained only SO24&#175 and CO2 as externally supplied oxidants. After 31 days of column operation, stable concentration profiles were found for most of the measured dissolved species. Within 14 h residence time, about 0.24 mM SO24&#175 were consumed and dissolved Fe(II) (up to 0.012 mM), Mn(II) (up to 0.06 mM), and CH4 (up to 0.38 mM) were produced. The alkalinity and the dissolved inorganic carbon (DIC) concentration increased and the DIC became enriched in 13C. In the column, n-alkanes were selectively removed while branched alkanes persisted, suggesting a biological degradation. Furthermore, based on changes of concentrations of aromatic compounds with similar physical–chemical properties in the effluent, it was concluded that toluene, p-xylene and naphthalene were degraded. A carbon mass balance revealed that 65% of the hydrocarbons removed from the column were recovered as DIC, 20% were recovered as CH4, and 15% were eluted from the column. The calculations indicated that hydrocarbon mineralization coupled to SO24&#175 reduction and methanogenesis contributed in equal proportions to the hydrocarbon removal. Hydrocarbon mineralization coupled to Fe(III) and Mn(IV) reduction was of minor importance. DIC, alkalinity, and stable carbon isotope balances were shown to be a useful tool to verify hydrocarbon mineralization.

In this paper, four treatment techniques commonly applied to Volatile Organic Compounds (VOC) removal from soil are compared in column experiments with pure sand containing a residual Light Non-Aqueous Phase Liquid (L-NAPL) contamination. Oxidation is tested through the injection of Fenton reagent, with persulfate, and combined with sparging with the injection of ozone. Surfactant treatment was conducted at low flow rates with Tween®80. Sparging was conducted by air injection but at a low flow rate of 1 mL min−1. Finally several columns were thermally treated at a temperature of 80 °C. The results showed high removal (>90%) for all techniques used, although only thermal treatment on BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) reached 100% efficiency. The main limiting factors of each technique were: (i) for oxidation, the solubility of the substance limited the removal; (ii) for surfactant both the solubility in the surfactant and the type of surfactant are important; (iii) for sparging, the main factors are contaminant vapor pressure and porous media grain size; (iv) for thermal treatment, the limitation arises from the contaminant vapor pressure and the medium hydraulic conductivity. A comparison with literature data shows that the results are consistent with most of the studies conducted on one technique.

The study focuses on the effect of volatilization, diffusion, and biodegradation on the isotope evolution of volatile organic compounds (VOCs) in a 1.06 m long column filled with alluvial sand. A liquid mixture of 10 VOCs was placed at one end of the column, and measurements of VOC vapor concentrations and compound-specific isotope ratios (δ13C) were performed at the source and along the column. Initially, the compounds became depleted in 13C by up to −4.8‰ along the column axis, until at 26 h, uniform isotope profiles were observed for most compounds, which is expected for steady-state diffusion. Subsequently, several compounds (n-pentane, benzene, n-hexane) became enriched in 13C throughout the column. For the same compounds, a significant decrease in the source vapor concentration and a gradual enrichment of 13C by up to 5.3‰ at the source over a period of 336 h was observed. This trend can be explained by a larger diffusive mass flux for molecules with light isotopes compared to those with a heavy isotope, which leads to a depletion of light isotopes in the source. The isotope evolution of the source followed closely a Rayleigh trend and the obtained isotope enrichment factor corresponded well to the ratio between the diffusion coefficients for heavy and light molecules as expected based on theory. In contrast to diffusion, biodegradation had generally only a small effect on the isotope profiles, which is expected because in a diffusion-controlled system the isotope shift per decrease of mass flux is smaller than in an advection-controlled system. These findings open interesting perspectives for monitoring source depletion with isotope and have implications for assessing biodegradation and source variability in the unsaturated zone based on isotopes.

The relationship between the strength of the intermolecular interaction in liquid and the position-specific

International audience; The relationship between the strength of the intermolecular interaction in liquid and the position-specific 13C fractionation observed during distillation was investigated. A range of molecules showing different intermolecular interactions in terms of mode and intensity were incorporated in the study. Although it had previously been suggested that during evaporation the diffusive 13C isotope effect in the thin liquid layer interfaced with vapor is not position-specific, herein we show that this is not the case. In particular, the position-specific effect was demonstrated for a series of alcohols. Our hypothesis is that intermolecular interactions in the liquid phase are the source of position-specific 13C fractionation observed on the molecule. A clear trend is observed between the 13C isotope effect of the carbon bearing the heteroatom of chemical function and the relative permittivity, the solvent hydrogen-bond acidity and the solvent hydrogen-bond basicity, while only a weak trend was observed when using the 13C content of the whole molecule. Furthermore two families of products appeared when using the hydrogen-bond acidity parameter for the correlation by distinguishing H-acceptors and H-donors molecules to those H-acceptors only. This strongly reinforces the hypothesis of an important role of the 13C positioned close to the interaction center.

International audience; Compound-specific isotope analysis (CSIA) is a state-of-the-art analytical tool that can be used to establish and quantify biodegradation of pollutants such as BTEX compounds at contaminated field sites. Using isotopes of two elements and characteristic Lambda values (A) in dual-isotope-plots can provide insight into reaction mechanisms because kinetic isotope effects (KIEs) of both elements are reflected. However, the concept's validity in the case of reactions that show strong isotope fractionation needs to be examined. The anaerobic ethylbenzene degradation pathway of Aromatoleum aromaticum is initiated by the ethylbenzene dehydrogenase-catalyzed monohydroxylation of the benzylic carbon atom. Measurements of stable isotope ratios revealed highly pronounced hydrogen fractionation, which could not be adequately described by the classical Rayleigh approach. This study demonstrates the nonlinear behavior of hydrogen isotope ratios caused by anaerobic ethylbenzene hydroxylation both mathematically and experimentally, develops alternative dual plots to enable the comparison of reactions by considering the reacting atoms, and illustrates the importance of the stereochemical aspects of substrate and product for the quantification of hydrogen fractionation in an enzymatic reaction. With regard to field application, proposals for an improved CSIA evaluation procedure with respect to pronounced hydrogen enrichment are given.

International audience; This study compared four treatment techniques for the removal of a toluene/n-decane as NAPL (Non Aqueous Phase Liquid) phase mixture in identical 1 cubic meter tanks filled with different kind of sand. These four treatment techniques were: oxidation with persulfate, surfactant washing with Tween80®, sparging with air followed by ozone, and thermal treatment at 80 °C. The sources were made with three lenses of 26 × 26 × 6.5 cm, one having a hydraulic conductivity similar to the whole tank and the two others a value 10 times smaller. The four techniques were studied after conditioning the tanks with tap water during approximately 80 days. The persulfate treatment tests showed average removal of the contaminants but significant flux decrease if density effects are considered. Surfactant flushing did not show a highly significant increase of the flux of toluene but allowed an increased removal rate that could lead to an almost complete removal with longer treatment time. Sparging removed a significant amount but suggest that air was passing through localized gas channels and that the removal was stagnating after removing half of the contamination. Thermal treatment reached 100% removal after the target temperature of 80 °C was kept during more than 10 d. The experiments emphasized the generation of a high-spatial heterogeneity in NAPL content. For all the treatments the overall removal was similar for both n-decane and toluene, suggesting that toluene was removed rapidly and n-decane more slowly in some zones, while no removal existed in other zones. The oxidation and surfactant results were also analyzed for the relation between contaminant fluxes at the outlet and mass removal. For the first time, this approach clearly allowed the differentiation of the treatments. As a conclusion, experiments showed that the most important differences between the tested treatment techniques were not the global mass removal rates but the time required to reach 99% decrease in the contaminant fluxes, which were different for each technique.; This study compared four treatment techniques for the removal of a toluene/n-decane as NAPL (Non Aqueous Phase Liquid) phase mixture in identical 1 cubic meter tanks filled with different kind of sand. These four treatment techniques were: oxidation with persulfate, surfactant washing with Tween80®, sparging with air followed by ozone, and thermal treatment at 80 °C. The sources were made with three lenses of 26 × 26 × 6.5 cm, one having a hydraulic conductivity similar to the whole tank and the two others a value 10 times smaller. The four techniques were studied after conditioning the tanks with tap water during approximately 80 days.The persulfate treatment tests showed average removal of the contaminants but significant flux decrease if density effects are considered. Surfactant flushing did not show a highly significant increase of the flux of toluene but allowed an increased removal rate that could lead to an almost complete removal with longer treatment time. Sparging removed a significant amount but suggests that air was passing through localized gas channels and that the removal was stagnating after removing half of the contamination. Thermal treatment reached 100% removal after the target temperature of 80 °C was kept during more than 10 d.The experiments emphasized the generation of a high-spatial heterogeneity in NAPL content. For all the treatments the overall removal was similar for both n-decane and toluene, suggesting that toluene was removed rapidly and n-decane more slowly in some zones, while no removal existed in other zones.The oxidation and surfactant results were also analyzed for the relation between contaminant fluxes at the outlet and mass removal. For the first time, this approach clearly allowed the differentiation of the treatments. As a conclusion, experiments showed that the most important differences between the tested treatment techniques were not the global mass removal rates but the time required to reach 99% decrease in the contaminant fluxes, which were different for each technique.

International audience; Source delineation of hydrocarbon contaminated sites is of high importance for remediation work. However, traditional methods like soil core extraction and analysis or recent Membrane Interface Probe methods are time consuming and costly. Therefore, the development of an in situ method based on soil gas analysis can be interesting. This includes the direct measurement of volatile organic compounds (VOCs) in soil gas taken from gas probes using a PID (Photo Ionization Detector) and the analysis of other soil gases related to VOC degradation distribution (CH4, O-2, CO2) or related to presence of Light Non-Aqueous Phase Liquid (LNAPL) as Rn-222. However, in widespread heterogeneous formations, delineation by gas measurements becomes more challenging. The objective of this study is twofold: (i) to analyse the potential of several in situ gas measurement techniques in comparison to soil coring for LNAPL source delineation at a heterogeneous contaminated site where the techniques might be limited by a low diffusion potential linked to the presence of fine sands and silts, and (ii) to analyse the effect of vertical sediment heterogeneities on the performance of these gas measurement methods. Thus, five types of gases were analysed: VOCs, their three related degradation products O-2, CO2 and CH4 and Rn-222. Gas measurements were compared to independent LNAPL analysis by coring. This work was conducted at an old industrial site frequently contaminated by a Diesel-Fuel mixture located in a heterogeneous fine-grained aquifer. Results show that in such heterogeneous media migration of reactive gases like VOCs occurs only across small distances and the VOC concentrations sampled with gas probes are mainly related to local conditions rather than the presence of LNAPL below the gas probe. Rn-222 is not well correlated with LNAPL because of sediment heterogeneity. Oxygen, CO2, and especially CH4, have larger lengths of diffusion and give the clearest picture for LNAPL presence at this site even when the gas probe is somewhat distant. (C) 2016 Elsevier B.V. All rights reserved.

BIOSCREEN is a well-known simple tool for evaluating the transport of dissolved contaminants in groundwater, ideal for rapid screening and teaching. This work extends the BIOSCREEN model for the calculation of stable isotope ratios in contaminants. A three-dimensional exact solution of the reactive transport from a patch source, accounting for fractionation by first-order decay and/or sorption, is used. The results match those from a previously published isotope model but are much simpler to obtain. Two different isotopes may be computed, and dual isotope plots can be viewed. The dual isotope assessment is a rapidly emerging new approach for identifying process mechanisms in aquifers. Furthermore, deviations of isotope ratios at specific reactive positions with respect to "bulk" ratios in the whole compound can be simulated. This model is named BIOSCREEN-AT-ISO and will be downloadable from the journal homepage.

Analytical models were developed that simulate stable isotope ratios of volatile organic compounds (VOCs) near a point source contamination in the unsaturated zone. The models describe diffusive transport of VOCs, biodegradation and source ageing. The mass transport is governed by Fick's law for diffusion, and the equation for reactive transport of VOCs in the soil gas phase was solved for different source geometries and for different boundary conditions. Model results were compared to experimental data from a one-dimensional laboratory column and a radial-symmetric field experiment, and the comparison yielded a satisfying agreement. The model results clearly illustrate the significant isotope fractionation by gas-phase diffusion under transient state conditions. This leads to an initial depletion of heavy isotopes with increasing distance from the source. The isotope evolution of the source is governed by the combined effects of isotope fractionation due to vaporization, diffusion and biodegradation. The net effect can lead to an enrichment or depletion of the heavy isotope in the remaining organic phase depending on the compound and element considered. Finally, the isotope evolution of molecules migrating away from the source and undergoing degradation is governed by a combined degradation and diffusion isotope effect. This suggests that in the unsaturated zone, the interpretation of biodegradation based on isotope data must always be based on a model combining gas-phase diffusion and degradation., 11 pages, 6 figures

In this comment, we revisit equations concerning the analytical solutions presented by Gutierrez-Neri and co-workers for reactive transport for a pollutant undergoing core and fringe degradations. We state that a correction needs to be made in Eq. (9) of the work of Gutierrez- Neri et al. in order that the equation follows closely previous work published by J. Bear (in 1-D) and P.A. Domenico (in 3-D). Furthermore we derive alternative solutions for Eqs. (13)–(16) which separate more clearly the first-order reaction and the instantaneous reaction. It is shown that the corrected solution agrees better with the results from the numerical model than the previous solution. An improvement is also made by giving a solution which avoids negative concentrations. Furthermore, the corresponding solution for the electron acceptor reacting with the pollutant is given.

Volatilization of toxic organic contaminants from groundwater to the soil surface is often considered an important pathway in risk analysis. Most of the risk models use simplified linear solutions that may overpredict the volatile flux. Although complex numerical models have been developed, their use is restricted to experienced users and for sites where field data are known in great detail. We present here a novel semianalytical model running on a spreadsheet that simulates the volatilization flux and vertical concentration profile in a soil based on the Van Genuchten functions. These widely used functions describe precisely the gas and water saturations and movement in the capillary fringe. The analytical model shows a good accuracy over several orders of magnitude when compared to a numerical model and laboratory data. The effect of barometric pumping is also included in the semianalytical formulation, although the model predicts that barometric pumping is often negligible. A sensitivity study predicts significant fluxes in sandy vadose zones and much smaller fluxes in other soils. Fluxes are linked to the dimensionless Henry's law constant H for H0.2 and increase by approximately 20% when temperature increases from 5 to 25 degrees C.

This work presents analytical models which are able to predict contours of concentrations and isotope ratios of organic pollutants in homogeneous aquifers. Four analytical solutions of the advective–dispersive transport equation for reactive transport from the literature differing in assumptions regarding biodegradation kinetics were used. Stable isotope ratios are computed after modelling the individual reactive transport of isotopic species in the aquifer, which respond differently to fractionation by biodegradation or sorption. The main finding of this study is that the isotope ratios in the plumes are very sensitive to the assumptions underlying the biodegradation kinetics in the models. When biodegradation occurs throughout the core of the plume as first-order reaction, the transversal gradients in isotope ratios are smooth. When biodegradation occurs in a bi-molecular reaction with an electron acceptor (modelled by double-Monod kinetics), steep transversal isotope gradients are predicted. When the reaction rates approach instantaneous reaction along the plume fringes, isotope shifts in the core of the plume disappear. A model incorporating plume and fringe degradation produces the most plausible predictions of isotope ratios in this study. It is shown furthermore that isotope fractionation by sorption causes an even different pattern of isotope ratios, with positive shifts restricted to near the forerunning front of an expanding plume. The models developed in this work can serve for the validation of numerical models and may be incorporated in natural attenuation support systems such as e.g. BIOSCREEN.