Patrick Höhener

Constructed wetlands to reduce metal pollution from industrial catchments in aquatic Mediterranean ecosystems: A review to overcome obstacles and suggest potential solutions

In the Mediterranean area, surface waters often have low discharge or renewal rates, hence metal contamination from industrialised catchments can have a high negative impact on the physico-chemical and biological water quality. In a context of climate and anthropological changes, it is necessary to provide an integrative approach for the prevention and control of metal pollution, in order to limit its impact on water resources, biodiversity, trophic network and human health. For this purpose, introduction of constructed wetlands (CWs) between natural aquatic ecosystems and industrialised zones or catchments is a promising strategy for eco-remediation. Analysis of the literature has shown that further research must be done to improve CW design, selection and management of wetland plant species and catchment organisation, in order to ensure the effectiveness of CWs in Mediterranean environments. Firstly, the parameters of basin design that have the greatest influence on metal removal processes must be identified, in order to better focus rhizospheric processes on specific purification objectives. We have summarised in a single diagram the relationships between the design parameters of a CW basin and the physico-chemical and biological processes of metal removal, on the basis of 21 mutually consistent papers. Secondly, in order to optimise the selection and distribution of helophytes in CWs, it is necessary to identify criteria of choice for the plant species that will best fit the remediation objectives and environmental and economic constraints. We have analysed the factors determining plant metal uptake efficiency in CWs on the basis of a qualitative meta-analysis of 13 studies with a view to determine whether the part played by metal uptake by plants is relevant in comparison with the other removal processes. Thirdly, we analysed the parameters to consider for establishing suitable management strategies for CWs and how they affect the whole CW design process. Finally, we propose monitoring and policy measures to facilitate the integration of CWs within Mediterranean industrialised catchments.

Semianalytical Model Predicting Transfer of Volatile Pollutants from Groundwater to the Soil Surface

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 Henrys law constant H for H < 0.2 and increase by approximately 20% when temperature increases from 5 to 25 degrees C.

Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by heavy divided by light, carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants.

In situ vadose zone bioremediation

Contamination of the vadose zone with various pollutants is a world-wide problem, and often technical or economic constraints impose remediation without excavation. In situ bioremediation in the vadose zone by bioventing has become a standard remediation technology for light spilled petroleum products. In this review, focus is given on new in situ bioremediation strategies in the vadose zone targeting a variety of other pollutants such as perchlorate, nitrate, uranium, chromium, halogenated solvents, explosives and pesticides. The techniques for biostimulation of either oxidative or reductive degradation pathways are presented, and biotransformations to immobile pollutants are discussed in cases of non-degradable pollutants. Furthermore, research on natural attenuation in the vadose zone is presented.

Rayleigh-Based Concept to Tackle Strong Hydrogen Fractionation in Dual Isotope Analysis—The Example of Ethylbenzene Degradation by Aromatoleum aromaticum

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 (Λ) in dual-isotope-plots can provide insight into reaction mechanisms because kinetic isotope effects (KIEs) of both elements are reflected. However, the concepts 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.

Insights into Mechanistic Models for Evaporation of Organic Liquids in the Environment Obtained by Position-Specific Carbon Isotope Analysis

Position-specific isotope effects (PSIEs) have been measured by isotope ratio monitoring (13)C 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.

Analytical model for site-specific isotope fractionation in 13C during sorption: Determination by isotopic 13C NMR spectrometry with vanillin as model compound

The aim of this study was to conceive a reactive transport model capable of providing quantitative site-specific enrichment factors for fractionation in (13)C isotopic content during sorption. As test compound the model treats vanillin, for which the (13)C isotopic content at natural abundance at each of the 8 carbon positions can be measured by quantitative (13)C nuclear magnetic resonance spectrometry. This technique determines the isotope ratios with a resolution better than ±1‰ (0.1%) at each carbon position. Site-specific isotope fractionations were recorded in chromatography column experiments with silica RP-18 as stationary phase. The one dimensional reactive transport model accounted for the sorption/desorption behavior of 8 individual (13)C-isotopomers and one (12)C-isotopomer of vanillin and reproduced satisfactorily the bulk (average over the whole compound) fractionation observed during elution. After model calibration, the enrichment factors were fitted for each carbon site where a significant fractionation was recorded. To show the interest of such a transport model for environmental studies, the model, extended to three dimensions, was exploited to simulate reactive transport in an aquifer. These results show that significant (13)C isotope fractionation is expected for 4 out of 8 (13)C-isotopomers in vanillin, and illustrate that bulk isotope ratios measured by conventional compound specific isotope analysis and mass spectrometry would hardly document significant isotope fractionations in vanillin. It is concluded that modeling of site-specific isotope ratios in molecules is a priori feasible and may help to quantify unknown processes in the environment.

In situ biostimulation of petroleum hydrocarbon degradation by nitrate and phosphate injection using a dipole well configuration.

The main aim of this study was to explore the feasibility of source zone bioremediation by nitrate and nutrient injection in a crude-oil contaminated aquifer using a recirculating well dipole. Groundwater pumped from a downgradient well at a rate of 2.5m(3)h(-1) was enriched with bromide (tracer), nitrate and ammonium phosphate and injected in a well 40 m upgradient. The test was run for 49 days with solute injection, followed by 65 days of dipole operation without solute addition. The resulting bromide breakthrough curve allowed quantifying a first-order leakage coefficient of 0.017 day(-1) from the dipole, whereas from the nitrate data a first-order nitrate consumption rate of 0.075 day(-1) was determined. Dissolved hydrocarbon concentrations including benzene decreased to non-detect in 84days but experienced important rebounds after ending circulation. Nitrite accumulated temporarily but was consumed entirely when solute injection stopped. The mass balance calculations revealed that about 83% of the nitrate was used for hydrocarbon degradation, with the remaining being used for oxidation of reduced sulfur. A reactive transport model was used for the delineation of the treated zone. This model suggested that denitrification influenced flow and transport in the dipole. It is concluded that successful promotion of denitrifying hydrocarbon degradation is easily obtained in this aquifer and enables to abate dissolved concentrations, and that dipole configuration is a good option.

Removal of NAPL from columns by oxidation, sparging, surfactant and thermal treatment

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 1xa0mLxa0min-1. Finally several columns were thermally treated at a temperature of 80xa0°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.

Does phosphate enhance the natural attenuation of crude oil in groundwater under defined redox conditions

After a crude oil spill caused by a broken pipeline in 2009 to a gravel aquifer in southern France, degradation processes under various redox conditions progressively established, but at rates that predict a long life-time of the source under natural attenuation after partial source removal. In this study, we aimed at identifying the rate-limiting factors for each redox condition, with special emphasis on phosphate as limiting nutrient. The study was conducted in laboratory microcosms assembled with material collected on site: sediments, water from monitoring wells, oil and microbial sludge. Redox conditions were promoted by adding electron acceptors (either oxygen, nitrate, limonite (FeO(OH)), cryptomelane (K(Mn(4+),Mn(2+))8O16), or sulfate). For each condition, the role of phosphate was studied by repeated additions for up to 290days. The results showed a very strong stimulation of aerobic and denitrifying rates of oil degradation by phosphate, provided that oxygen and nitrate were repeatedly supplied. Phosphate caused also a marked stimulation of methanogenic degradation, and a relatively small stimulation of metal reduction. These anaerobic processes started only after marked lag phases, and phosphate shortened the lag phase for methanogenic degradation. Degradation of aromatic and aliphatic hydrocarbons with less than 8 carbons, including benzene, was confirmed even under unstimulated conditions. It is concluded that degradation rates at the site are limited by both, availability of electron acceptors and availability of phosphate needed for promoting microbial growth.