Cross-sphere modelling to evaluate impacts of climate and land management changes on groundwater resources.

Climate change affects both water resources and agricultural production. With rising temperatures and decreasing summer precipitation, it is expected that agricultural production will be increasingly limited by drought. Where surface- or groundwater resources are available for irrigation, an increase in water withdrawals for irrigation is to be expected. Therefore, quantitative approaches are required to anticipate and manage the expected conflicts related to increased water abstraction for irrigation. This project aims to investigate how agricultural production, water demand for irrigation, runoff and groundwater dynamics are affected by future climate change and how climate change impacts combined with changes in agricultural water use affect groundwater dynamics. To answer these research questions, a comprehensive, loosely coupled model approach was developed, combining models from three disciplines: an agricultural plant growth model, a hydrological model and a hydrogeological model. The model coupling was implemented and tested for an agricultural area located in Switzerland in which groundwater plays a significant role in providing irrigation water. Our suggested modelling approach can be easily adapted to other areas. The model results show that yield changes are driven by drought limitations and rising temperatures. However, an increase in yield may be realized with an increase in irrigation. Simulation results show that the water requirement for irrigation without climate protection (RCP8.5) could increase by 40% by the end of the century with an unchanged growing season and by up to 80% with varietal adaptations. With climate change mitigation (RCP2.6) the increase in water demand for irrigation would be limited to 7%. The increase in irrigation (+12 mm) and the summer decrease in recharge rates (~20 mm/month) with decreasing summer precipitation causes a lowering of groundwater levels (40 mm) in the area in the late summer and autumn. This impact may be accentuated by an intensification of irrigation and reduced by extensification.

Identification, spatial extent and distribution of fugitive gas migration on the well pad scale.

Global methane (CH4) emissions are becoming increasingly important due to the contribution of CH4 to global warming. Leaking oil and gas wells can lead to subsurface CH4 gas migration (GM), which can cause both aquifer contamination and atmospheric emissions. Despite the need to identify and quantify GM at oil and gas well pads, effective and reliable monitoring techniques are lacking. In this field study, we used CH4 and carbon dioxide (CO2) efflux measurements together with soil gas stable carbon isotopic signatures to identify the occurrence and to characterize the spatio-temporal migration of fugitive gas across 17 selected well pads in Northeastern British Columbia, Canada. At 13 of these sites, operators had previously reported the occurrence of GM; however, subsequent inspections based on visual, olfactory or auditory evidence only identified GM at two of these sites. Using the soil gas efflux method, evidence for GM was found at 15 of the 17 well pads with CH4 and CO2 effluxes ranging from 0.017 to 180µmolm-2s-1(0.024 to 250gCH4m-2d-1) and 0.50 to 32µmolm-2s-1 (1.9 to 122gCO2m-2d-1), respectively. Stable carbon isotopic composition was assessed at 10 of the 17 well pads with 9 well pads showing evidence of GM. The isotopic values indicated that CH4 in soil gas was from the same origin as CH4 in the surface casing vent flow gas. There was no correlation between CH4 effluxes and the distance from the well head; an equal portion of elevated effluxes were detected >10m from the well head as were detected <5m from the well head. In addition, CH4 effluxes varied temporally with values changing by up to an order of magnitude over 2h. Although the study was carried out in Northeastern British Columbia, the results are applicable on a global scale, suggesting that inspections mostly based on visual evidence (e.g. bubbling at the well head) are not reliable for the identification of GM and, that infrequent survey measurements at predefined locations close to the well head may overestimate, underestimate or even miss CH4 effluxes. Repetitive and relatively densely spaced gas efflux measurements using a dynamic closed chamber method proved to be a useful tool for detecting GM.

Distinct Dual C-Cl Isotope Fractionation Patterns during Anaerobic Biodegradation of 1,2-Dichloroethane: Potential To Characterize Microbial Degradation in the Field.

This study investigates, for the first time, dual C-Cl isotope fractionation during anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) via dihaloelimination by Dehalococcoides and Dehalogenimonas-containing enrichment cultures. Isotopic fractionation of 1,2-DCA (εbulkC and εbulkCl) for Dehalococcoides (-33.0 ± 0.4‰ and -5.1 ± 0.1‰) and Dehalogenimonas-containing microcosms (-23 ± 2‰ and -12.0 ± 0.8‰) resulted in distinctly different dual element C-Cl isotope correlations (Λ = Δδ13C/Δδ37Cl ≈ εbulkC/εbulkCl), 6.8 ± 0.2 and 1.89 ± 0.02, respectively. Determined isotope effects and detected products suggest that the difference on the obtained Λ values for biodihaloelimination could be associated with a different mode of concerted bond cleavage rather than two different reaction pathways (i.e., stepwise vs concerted). Λ values of 1,2-DCA were, for the first time, determined in two field sites under reducing conditions (2.1 ± 0.1 and 2.2 ± 2.9). They were similar to the one obtained for the Dehalogenimonas-containing microcosms (1.89 ± 0.02) and very different from those reported for aerobic degradation pathways in a previous laboratory study (7.6 ± 0.1 and 0.78 ± 0.03). Thus, this study illustrates the potential of a dual isotope analysis to differentiate between aerobic and anaerobic biodegradation pathways of 1,2-DCA in the field and suggests that this approach might also be used to characterize dihaloelimination of 1,2-DCA by different bacteria, which needs to be confirmed in future studies.

Regional water quality patterns in an alluvial aquifer: direct and indirect influences of rivers.

The influence of rivers on the groundwater quality in alluvial aquifers can be twofold: direct and indirect. Rivers can have a direct influence via recharge and an indirect one by controlling the distribution of fine-grained, organic-carbon rich flood deposits that induce reducing conditions. These direct and indirect influences were quantified for a large alluvial aquifer on the Swiss Plateau (50km(2)) in interaction with an Alpine river using nitrate as an example. The hydrochemistry and stable isotope composition of water were characterized using a network of 115 piezometers and pumping stations covering the entire aquifer. Aquifer properties, land use and recharge zones were evaluated as well. This information provided detailed insight into the factors that control the spatial variability of groundwater quality. Three main factors were identified: (1) diffuse agricultural pollution sources; (2) dilution processes resulting from river water infiltrations, revealed by the δ(18)OH2O and δ(2)HH2O contents of groundwater; and (3) denitrification processes, controlled by the spatial variability of flood deposits governed by fluvial depositional processes. It was possible to quantify the dependence of the nitrate concentration on these three factors at any sampling point of the aquifer using an end-member mixing model, where the average nitrate concentration in recharge from the agricultural area was evaluated at 52mg/L, and the nitrate concentration of infiltrating river at approximately 6mg/L. The study shows the importance of considering the indirect and direct impacts of rivers on alluvial aquifers and provides a methodological framework to evaluate aquifer scale water quality patterns.

The effects of acrylamide polyelectrolytes on aquatic organisms: relating toxicity to chain architecture.

Understanding the inherent toxicity of water-soluble synthetic polyelectrolytes is critical for adequate risk management as well as enhancing product design when biological activity is a key performance index (e.g. for application in biofouling bivalves' control). The toxicity of two cationic acrylamide copolymers with different chain branching degree was evaluated. Standard ecotoxicity tests were conducted with microalgae and daphnids. The susceptibility of Corbicula fluminea, as a biofouling bivalve, was also evaluated. The effect of polyelectrolyte on the test media viscosity and the polymer chain size distributions under the experimental conditions were also examined. The susceptibility of the microalgae to both polymers was similar. As the complexity and size of the test organisms increased, differences in toxicity due to different chain architecture were noticeable. The more branched polymer was significantly less toxic to both daphnids and the bivalves, which could be linked to the distinctive features of its bimodal size chain distribution. This architecture resulted in both more compact globular molecules and the formation of aggregates, which reduce the polymer interaction with the biological surfaces. The results of this study promote the incorporation of environmental considerations in polyelectrolyte development and contribute to the design of improved solutions for controlling biofouling bivalves.

Benzene dynamics and biodegradation in alluvial aquifers affected by river fluctuations.

The spatial distribution and temporal dynamics of a benzene plume in an alluvial aquifer strongly affected by river fluctuations was studied. Benzene concentrations, aquifer geochemistry datasets, past river morphology, and benzene degradation rates estimated in situ using stable carbon isotope enrichment were analyzed in concert with aquifer heterogeneity and river fluctuations. Geochemistry data demonstrated that benzene biodegradation was on-going under sulfate reducing conditions. Long-term monitoring of hydraulic heads and characterization of the alluvial aquifer formed the basis of a detailed modeled image of aquifer heterogeneity. Hydraulic conductivity was found to strongly correlate with benzene degradation, indicating that low hydraulic conductivity areas are capable of sustaining benzene anaerobic biodegradation provided the electron acceptor (SO4 (2-) ) does not become rate limiting. Modeling results demonstrated that the groundwater flux direction is reversed on annual basis when the river level rises up to 2 m, thereby forcing the infiltration of oxygenated surface water into the aquifer. The mobilization state of metal trace elements such as Zn, Cd, and As present in the aquifer predominantly depended on the strong potential gradient within the plume. However, infiltration of oxygenated water was found to trigger a change from strongly reducing to oxic conditions near the river, causing mobilization of previously immobile metal species and vice versa. MNA appears to be an appropriate remediation strategy in this type of dynamic environment provided that aquifer characterization and targeted monitoring of redox conditions are adequate and electron acceptors remain available until concentrations of toxic compounds reduce to acceptable levels.

Can soil gas VOCs be related to groundwater plumes based on their isotope signature?

The isotope evolution of tetrachloroethene (PCE) during its transport from groundwater toward the soil surface was investigated using laboratory studies and numerical modeling. During air-water partitioning, carbon and chlorine isotope ratios evolved in opposite directions, with a normal isotope effect for chlorine (ε = -0.20‰) and an inverse effect for carbon (ε = +0.46‰). During the migration of PCE from groundwater to the unsaturated zone in a 2D laboratory system, small shifts of carbon and chlorine isotope ratios (+0.8‰) were observed across the capillary fringe. Numerical modeling showed that these shifts are due to isotope fractionation associated with air-water partitioning and gas-phase diffusion. Carbon and chlorine isotope profiles were constant throughout the unsaturated zone once a steady state was reached. However, depending on the thickness of the unsaturated zone and its lithology, depletion in heavy isotopes may occur with distance during the transient migration of contaminants. Additionally, variations of up to +1.5‰ were observed in the unsaturated zone for chlorine isotopes during water table fluctuations. However, at steady state, it is possible to link a groundwater plume to gas-phase contamination and/or to differentiate sources of contamination based on isotope ratios.

Comments on "Analytical modelling of fringe and core biodegradation in groundwater plumes." by Gutierrez-Neri et al. in J. Contam. Hydrol. 107: 1-9.

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.

Carbon and chlorine isotope fractionation during aerobic oxidation and reductive dechlorination of vinyl chloride and cis-1,2-dichloroethene.

The study investigated carbon and chlorine isotope fractionation during aerobic oxidation and reductive dechlorination of vinyl chloride (VC) and cis-1,2-dichloroethene (cDCE). The experimental data followed a Rayleigh trend. For aerobic oxidation, the average carbon isotope enrichment factors were -7.2 per thousand and -8.5% for VC and cDCE, respectively, while average chlorine isotope enrichment factors were only -0.3 per thousand for both compounds. These values are consistent with an initial transformation by epoxidation for which a significant primary carbon isotope effect and only a small secondary chlorine isotope effect is expected. For reductive dechlorination, larger carbon isotope enrichment factors of -25.2 per thousand for VC and -18.5 per thousand for cDCE were observed consistent with previous studies. Although the average chlorine isotope enrichmentfactors were larger than those of aerobic oxidation (-1.8 per thousand for VC, -1.5 per thousand for cDCE), they were not as large as typically expected for a primary chlorine isotope effect suggesting that no cleavage of C-Cl bonds takes place during the initial rate-limiting step. The ratio of isotope enrichment factors for chlorine and carbon were substantially different for the two reaction mechanisms suggesting that the reaction mechanisms can be differentiated at the field scale using a dual isotope approach.

Polyvinylamine-based capsules: a mechanistic study of the formation using alginate and cellulose sulphate.

Capsules based on sodium alginate (SA) and sodium cellulose sulphate (SCS), have been prepared using polyvinylamines (PVAm) of varying intrinsic viscosities. The resulting capsules are relatively dense in nature, revealing a bursting force which is four times that observed for the classical SA/SCS/polymethylene-co-guanidine chemistry. Molar mass cutoffs were typically in the 10-70 kDa range. A mechanistic study was carried out where the reaction time, ionic strength and pH of the reaction mixture, as well as the stoichiometry of the polyanion blend and the PVAm molar mass were varied. It is postulated that both the SA-PVAm and the SCS-PVAm binary interactions contribute to the mechanical properties and the permeability of the resulting capsules. The polyvinylamine-based chemistry offers interesting alternatives to the PMCG system in that it provides a means to produce capsules at low, or zero, ionic strengths. Subtle changes in the pH, or the SA:SCS ratio, can also be used to tune the bursting force quite sensitively. The most appropriate capsules, for transplantation, would likely be formed at polyanion levels of 1.2 wt% with a PVAm molar mass below 17 kDa.

Alginate-cellulose sulphate-oligocation microcapsules: optimization of mass transport and mechanical properties.

Microcapsules based on polyelectrolyte complexation, where the inner phase involves a blend of alginate and sodium cellulose sulphate (SCS), have mechanical and transport properties which are relatively insensitive to the chemical composition of the rigid polyanion. Specifically, the bursting force of 400- and 1000 microm microcapsules increase slightly with the degree of substitution of the SCS, though the molar mass of the SCS appears to influence the transport properties more strongly than its composition. The concentration of the sodium chloride in the gelling batch can be varied rather extensively, with optimum properties at approximately half (i.e. 0.5 M) the level typically employed for the formation of cell-containing microcapsules. This indicates that the microcapsule properties can be tuned for biocompatability, without concern that changes to the polymer microstructure or reaction process conditions would adversely influence the bursting force or molar mass cut-off of the capsules. The alginate-SCS blend, which is typical equimass, can be slightly increased in favour of the SCS (to 55 wt%) if one seeks to mechanically optimize the system. The substitution of the oligocation polymethylene-co-guanidine with pDADMAC seems strongly undesirable. Similarly, the replacement of SCS with sulphoethylcellulose, while possible, offers no important advantages. The overall optimum conditions appear to be for a SCS with a DS of 2, prepared at 1.2 wt% of total cation with alginate. The ideal ratio, for mechanical and transport properties, of SCS to alginate is 55:45 (wt:wt), which represents a subtle modification from the classical formulation with very good biocompatability.

Polymethylene-co-guanidine based capsules: a mechanistic study of the formation using alginate and cellulose sulphate.

Capsules have been prepared based on a polyanion blend of sodium alginate and sodium cellulose sulphate, gelled in the presence of calcium chloride and sodium chloride. In a second step a membrane was formed via the addition of polymethylene-co-guanidine (PMCG), an oligocation. A mechanistic study examined the influences of pH, ionic strength, gelation and reaction times as well as the molar mass of the polyanions on the transport and mechanical properties. The ratio of alginate-to-cellulose sulphate in the polyanion blend was also varied and it was found that both mechanical resistance to compression as well as the pore size of the membrane decreased as the percentage of cellulose sulphate was reduced. The maximum mechanical strength was observed to correspond to the minimum in viscosity of the polyanion blend with, for low NaCl levels, a 3:1 alginate:cellulose sulphate level providing the largest resistance to deformation. The ability to decouple the molar mass cut-off and mechanical resistance is viewed as an important advantage of alginate/cellulose sulphate/PMCG capsules. Capsules were transplanted into mice to a maximum of 102 days, after which animals were sacrificed and capsules retrieved. Over 90% of the capsules were recovered from the peritoneal cavity with the mechanical properties of the explanted capsules observed to decrease as a function of implantation time, likely as a result of ion exchange. The capsules were, however, relatively free from any rejection which is a quite unusual result for cation containing systems. It is believed that the reason PMCG-based microcapsules function well in vivo is that they provide a net negative charge on the surface. Higher molar mass polycations such as poly-L-lysine provide a net positive charge, inducing inflammation.

Evidence for in situ degradation of mono-and polyaromatic hydrocarbons in alluvial sediments based on microcosm experiments with 13C-labeled contaminants.

A microcosm study was conducted to investigate the degradation of mono- and polyaromatic hydrocarbons under in situ-like conditions using alluvial sediments from the site of a former cokery. Benzene, naphthalene, or acenaphthene were added to the sediments as (13)C-labeled substrates. Based on the evolution of (13)C-CO(2) determined by gas chromatography isotope-ratio mass spectrometry (GC-IRMS) it was possible to prove mineralization of the compound of interest in the presence of other unknown organic substances of the sediment material. This new approach was suitable to give evidence for the intrinsic biodegradation of benzene, naphthalene, and acenaphthene under oxic and also under anoxic conditions, due to the high sensitivity and reproducibility of (13)C/(12)C stable isotope analysis. This semi-quantitative method can be used to screen for biodegradation of any slowly degrading, strongly sorbing compound in long-term experiments.

Deposition, persistence and turnover of pollutants: First results from the EU project AquaTerra for selected river basins and aquifers.

Deposition, turnover and movement of persistent organic pollutants (POP) were investigated in the EU integrated project "AquaTerra", which is among the first funded environmental projects within the 6th Framework Program by the European Commission. Project work integrates across various disciplines that range from biogeochemistry, environmental engineering, computer modelling and chemistry to socio-economic sciences. Field study areas are the river basins of the Ebro, the Meuse, the Elbe and the Danube as well as the 3-km(2) French catchment of the Brévilles Spring. Within the first 2 years of the project more than 1700 samples of atmospherically deposited particles, sediments, and water have been collected in the above-mentioned systems. Results show clear spatial patterns of deposition of polyaromatic hydrocarbons (PAHs) with the highest rates in the Meuse Basin. For local inputs, in the Brévilles sandy aquifer, the contamination of the groundwater by the pesticides atrazine (AT) and deethylatrazine did not decrease even 5 years after their agricultural inputs were stopped. On the other hand, herbicides such as mecroprop (MCPP), and PAHs, were at least partially degraded microbiologically in laboratory studies with soils and aquifer material from selected sites. For sediment transport of contaminants, new flood sampling techniques revealed highest deposition rates of beta-hexachlorocyclohexane (beta-HCH) in river sediments at hotspot areas on the Mulde River in the Bitterfeld region (Elbe Basin, Germany). These selected preliminary results of AquaTerra help to improve fundamental understanding of persistent organic pollutants (POP) in the environment.

Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers.

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.

Life cycle assessment part 1: framework, goal and scope definition, inventory analysis, and applications.

Sustainable development requires methods and tools to measure and compare the environmental impacts of human activities for the provision of goods and services (both of which are summarized under the term "products"). Environmental impacts include those from emissions into the environment and through the consumption of resources, as well as other interventions (e.g., land use) associated with providing products that occur when extracting resources, producing materials, manufacturing the products, during consumption/use, and at the products' end-of-life (collection/sorting, reuse, recycling, waste disposal). These emissions and consumptions contribute to a wide range of impacts, such as climate change, stratospheric ozone depletion, tropospheric ozone (smog) creation, eutrophication, acidification, toxicological stress on human health and ecosystems, the depletion of resources, water use, land use, and noise-among others. A clear need, therefore, exists to be proactive and to provide complimentary insights, apart from current regulatory practices, to help reduce such impacts. Practitioners and researchers from many domains come together in life cycle assessment (LCA) to calculate indicators of the aforementioned potential environmental impacts that are linked to products-supporting the identification of opportunities for pollution prevention and reductions in resource consumption while taking the entire product life cycle into consideration. This paper, part 1 in a series of two, introduces the LCA framework and procedure, outlines how to define and model a product's life cycle, and provides an overview of available methods and tools for tabulating and compiling associated emissions and resource consumption data in a life cycle inventory (LCI). It also discusses the application of LCA in industry and policy making. The second paper, by Pennington et al. (Environ. Int. 2003, in press), highlights the key features, summarises available approaches, and outlines the key challenges of assessing the aforementioned inventory data in terms of contributions to environmental impacts (life cycle impact assessment, LCIA).

Bioartificial organ grafts: a view at the beginning of the third millennium.

An immunoisolated collection of cells, which communicate and exchange essential factors, co-stimulatory hormones, as well as providing immunoprotection and immunomodulation, can be prepared, given existing scientific and medical know-how, within two decades. These "Bioartificial Organ Grafts" have advantages relative to isolated cell therapies, including beta-cell encapsulation for diabetes treatment, and xenotransplantation, which has a de facto moratorium. This paper documents that the majority of the research for the bioartificial organ grafts has been concluded, with the remaining hurdles minimum in comparison. The use of co-encapsulation and the induction of local immune-privilege will provide a more sensitive humoral hormonal response and graft survival, without systemic immunosuppression. A call for the staged implementation of bioartificial organ grafts, based on the best available medical practice, materials, tissue and technology available, is advocated. The implementation of bioartificial organ grafts can begin within the next two years, based on allografts succeeded by genetically modified human tissue, without the need to pass through a xenograft stage.

Influence of alginate characteristics on the properties of multi-component microcapsules.

A variety of sodium alginates, differing in molar mass and structural composition, have been evaluated in the preparation of multi-component microbeads and microcapsules. Bead formation occurred by gelation with calcium chloride. Capsules were produced by reacting the pre-formed beads with the oligocation poly(methylene-co-guanidine). Despite the equiponderous (1:1) mixing with a second polyanion, sodium cellulose sulphate, the influence of the alginate properties remains evident. Specifically, the effect of the chemical composition was found to be more significant than that of the molar mass for both the mechanical and transport properties. Furthermore, for alginates of 73% alpha-l-guluronic acid content less shrinking was observed compared to the 38% guluronic materials. This results in the case of the same encapsulator settings in larger microsphere diameters and thicker membranes accompanied by enhanced mechanical resistance though, also, in a higher permeability for the high-G capsules. However, subsequent coating with lower molar mass alginate allows one to adjust the permeability over a broad range, suitable for cell encapsulation and immunoprotection, without compromising the durability.

Monitoring oxidation of chlorinated ethenes by permanganate in groundwater using stable isotopes: laboratory and field studies.

Permanganate injection is increasingly applied for in situ destruction of chlorinated ethenes in groundwater. This laboratory and field study demonstrates the roles that carbon isotope analysis can play in the assessment of oxidation of trichloroethene (TCE) by permanganate. In laboratory experiments a strong carbon isotope fractionation was observed during oxidation of TCE with similar isotopic enrichment factors (-25.1 to -26.8 per thousand) for initial KMnO4 concentrations between 67 and 1,250 mg/L. At the field site, a single permanganate injection episode was conducted in a sandy aquifer contaminated with TCE as dense nonaqueous liquid (DNAPL). After injection, enriched delta13C values of up to +204% and elevated Cl- concentrations were observed at distances of up to 4 m from the injection point. Farther away, the Cl- increased without any change in delta13C of TCE suggesting that Cl- was not produced locally but migrated to the sampling point Except for the closest sampling location to the injection point, the delta13C rebounded to the initial 613C again, likely due to dissolution of DNAPL Isotope mass balance calculations made it possible to identify zones where TCE oxidation continued to occur during the rebound phase. The study indicates that delta13C values can be used to assess the dynamics between TCE oxidation and dissolution and to locate zones of oxidation of chlorinated ethenes that cannot be identified from the Cl- distribution alone.

Characterization of microcapsules: recommended methods based on round-robin testing.

Alginate beads, as well as microcapsules based on alginate, cellulose sulphate and polymethylene-co-guanidine, were produced at diameters of 0.4, 1.0 and 1.5 mm. These standard materials were tested, by independent laboratories, in regards to water activity, bead or capsule size, mechanical resistance and transport behaviour. The water activity and mechanical resistance were observed to increase with bead and capsule size. Transport properties (ingress) were assessed using a variety of low molar mass and macromolecular probes. It was observed that the penetration of Vitamin B12 increased with bead diameter, as did dextran penetration. However, for the membrane-containing microcapsules, larger membrane thickness, observed for the larger capsules, retarded ingress. The authors, who are part of a European working group, recommend that permeability be assessed either using a large range of probes or a broad molar mass standard, with measurements at one or two molar masses insufficient to simulate the behaviour in application. Mechanical compression is seen as a good means to estimate elasticity and rupture of beads and capsules, with the sensitivity of the force transducer, which can vary from microN to tens of N, required to be tuned to the anticipated bead or capsule strength. Overall, with the exception of the mechanical properties, the precision in the inter-laboratory testing was good. Furthermore, the various methods of assessing transport properties agreed, in ranking, for the beads and capsules characterized, with gels having smaller radii being less permeable. For microcapsules, the permeation across the membrane dominates the ingress, and thicker membranes have lower permeability.