Assessing the Transport of Pharmaceutical Compounds in a Layered Aquifer Discharging to a Stream.

A groundwater plume containing high concentrations of pharmaceutical compounds, mainly sulfonamides, barbiturates, and ethyl urethane, in addition to chlorinated ethenes and benzene was investigated. The contamination originating from a former pharmaceutical industry discharges into a multilayered aquifer system and a downgradient stream. In this study, geological and hydrogeological data were integrated into a numerical flow model to examine identified trends using statistical approaches, including principal component analysis and hierarchal cluster analysis. A joint interpretation of the groundwater flow paths and contaminant concentrations in the different compartments (i.e., groundwater and hyporheic zone) provided insight on the transport processes of the different contaminant plumes to the stream. The analysis of historical groundwater concentrations of pharmaceutical compounds at the site suggested these compounds are slowly degrading. The pharmaceutical compounds migrate in both a deep semiconfined aquifer, as well as in the shallow unconfined aquifer, and enter the stream along a 2-km stretch. This contrasted with the chlorinated ethenes, which mainly discharge to the stream as a focused plume from the unconfined aquifer. The integrated approach developed here, combining groundwater flow modeling and statistical analyses of the contaminant concentration data collected in groundwater and the hyporheic zone, lead to an improved understanding of the observed distribution of contaminants in the unconfined and semiconfined aquifers, and thus to their discharge to the stream. This approach is particularly relevant for large and long-lasting contaminant sources and plumes, such as abandoned landfills and industrial production sites, where field investigations may be very expensive.

A simple contaminant fate and transport modelling tool for management and risk assessment of groundwater pollution from contaminated sites.

Contaminated sites pose a significant threat to groundwater resources. The resources that can be allocated by water regulators for site investigation and cleanup are limited compared to the large number of contaminated sites. Numerical transport models of individual sites require large amounts of data and are labor intensive to set up, and thus they are likely to be too expensive to be useful in the management of thousands of contaminated sites. Therefore, simple tools based on analytical solutions of contaminant transport models are widely used to assess (at an early stage) whether a site might pose a threat to groundwater. We present a tool consisting of five different models, representing common geological settings, contaminant pathways, and transport processes. The tool employs a simplified approach for preliminary, conservative, fast and inexpensive estimation of the contamination levels of aquifers. This is useful for risk assessment applications or to select and prioritize the sites, which should be targeted for further investigation. The tool is based on steady-state semi-analytical models simulating different contaminant transport scenarios from the source to downstream groundwater, and includes both unsaturated and saturated transport processes. The models combine existing analytical solutions from the literature for vertical (from the source to the top of the aquifer) and horizontal (within the aquifer) transport. The effect of net recharge causing a downward migration and an increase of vertical dispersion and dilution of the plume is also considered. Finally, we illustrate the application of the tool for a preliminary assessment of two contaminated sites in Denmark and compare the model results with field data. The comparison shows that a first preliminary assessment with conservative, and often non-site specific parameter selection, is qualitatively consistent with broad trends in observations and provides a conservative estimate of contamination.

Delay in catchment nitrogen load to streams following restrictions on fertilizer application.

A MIKE SHE hydrological-solute transport model including nitrate reduction is employed to evaluate the delayed response in nitrogen loads in catchment streams following the implementation of nitrogen mitigation measures since the 1980s. The nitrate transport lag times between the root zone and the streams for the period 1950-2011 were simulated for two catchments in Denmark and compared with observational data. Results include nitrogen concentration and mass discharge to streams. By automated baseflow separation, stream discharge was separated into baseflow and drain flow components, and the nitrogen concentration and mass discharge in baseflow and drain flow were determined. This provided insight on the development of stream nitrogen loads, with a short average lag time in drain flow and a long average lag time in baseflow. The long term effect of nitrogen mitigation measures was determined, with results showing that there is a 15 years long delay in the appearance of peak nitrogen loads in streams. This means that real time stream monitoring data cannot be used alone to assess the effect of nitrogen mitigation measures.

Characterization of chlorinated solvent contamination in limestone using innovative FLUTe® technologies in combination with other methods in a line of evidence approach.

Characterization of dense non-aqueous phase liquid (DNAPL) source zones in limestone aquifers/bedrock is essential to develop accurate site-specific conceptual models and perform risk assessment. Here innovative field methods were combined to improve determination of source zone architecture, hydrogeology and contaminant distribution. The FACT™ is a new technology and it was applied and tested at a contaminated site with a limestone aquifer, together with a number of existing methods including wire-line coring with core subsampling, FLUTe® transmissivity profiling and multilevel water sampling. Laboratory sorption studies were combined with a model of contaminant uptake on the FACT™ for data interpretation. Limestone aquifers were found particularly difficult to sample with existing methods because of core loss, particularly from soft zones in contact with chert beds. Water FLUTe™ multilevel groundwater sampling (under two flow conditions) and FACT™ sampling and analysis combined with FLUTe® transmissivity profiling and modeling were used to provide a line of evidence for the presence of DNAPL, dissolved and sorbed phase contamination in the limestone fractures and matrix. The combined methods were able to provide detailed vertical profiles of DNAPL and contaminant distributions, water flows and fracture zones in the aquifer and are therefore a powerful tool for site investigation. For the limestone aquifer the results indicate horizontal spreading in the upper crushed zone, vertical migration through fractures in the bryozoan limestone down to about 16-18m depth with some horizontal migrations along horizontal fractures within the limestone. Documentation of the DNAPL source in the limestone aquifer was significantly improved by the use of FACT™ and Water FLUTe™ data.

A Bayesian belief network approach for assessing uncertainty in conceptual site models at contaminated sites.

A key component in risk assessment of contaminated sites is in the formulation of a conceptual site model (CSM). A CSM is a simplified representation of reality and forms the basis for the mathematical modeling of contaminant fate and transport at the site. The CSM should therefore identify the most important site-specific features and processes that may affect the contaminant transport behavior at the site. However, the development of a CSM will always be associated with uncertainties due to limited data and lack of understanding of the site conditions. CSM uncertainty is often found to be a major source of model error and it should therefore be accounted for when evaluating uncertainties in risk assessments. We present a Bayesian belief network (BBN) approach for constructing CSMs and assessing their uncertainty at contaminated sites. BBNs are graphical probabilistic models that are effective for integrating quantitative and qualitative information, and thus can strengthen decisions when empirical data are lacking. The proposed BBN approach facilitates a systematic construction of multiple CSMs, and then determines the belief in each CSM using a variety of data types and/or expert opinion at different knowledge levels. The developed BBNs combine data from desktop studies and initial site investigations with expert opinion to assess which of the CSMs are more likely to reflect the actual site conditions. The method is demonstrated on a Danish field site, contaminated with chlorinated ethenes. Four different CSMs are developed by combining two contaminant source zone interpretations (presence or absence of a separate phase contamination) and two geological interpretations (fractured or unfractured clay till). The beliefs in each of the CSMs are assessed sequentially based on data from three investigation stages (a screening investigation, a more detailed investigation, and an expert consultation) to demonstrate that the belief can be updated as more information becomes available.

Sources, occurrence and predicted aquatic impact of legacy and contemporary pesticides in streams.

We couple current findings of pesticides in surface and groundwater to the history of pesticide usage, focusing on the potential contribution of legacy pesticides to the predicted ecotoxicological impact on benthic macroinvertebrates in headwater streams. Results suggest that groundwater, in addition to precipitation and surface runoff, is an important source of pesticides (particularly legacy herbicides) entering surface water. In addition to current-use active ingredients, legacy pesticides, metabolites and impurities are important for explaining the estimated total toxicity attributable to pesticides. Sediment-bound insecticides were identified as the primary source for predicted ecotoxicity. Our results support recent studies indicating that highly sorbing chemicals contribute and even drive impacts on aquatic ecosystems. They further indicate that groundwater contaminated by legacy and contemporary pesticides may impact adjoining streams. Stream observations of soluble and sediment-bound pesticides are valuable for understanding the long-term fate of pesticides in aquifers, and should be included in stream monitoring programs.

Modeling the Factors Impacting Pesticide Concentrations in Groundwater Wells.

This study examines the effect of pumping, hydrogeology, and pesticide characteristics on pesticide concentrations in production wells using a reactive transport model in two conceptual hydrogeologic systems; a layered aquifer with and without a stream present. The pumping rate can significantly affect the pesticide breakthrough time and maximum concentration at the well. The effect of the pumping rate on the pesticide concentration depends on the hydrogeology of the aquifer; in a layered aquifer, a high pumping rate resulted in a considerably different breakthrough than a low pumping rate, while in an aquifer with a stream the effect of the pumping rate was insignificant. Pesticide application history and properties have also a great impact on the effect of the pumping rate on the concentration at the well. The findings of the study show that variable pumping rates can generate temporal variability in the concentration at the well, which helps understanding the results of groundwater monitoring programs. The results are used to provide guidance on the design of pumping and regulatory changes for the long-term supply of safe groundwater. The fate of selected pesticides is examined, for example, if the application of bentazone in a region with a layered aquifer stops today, the concentration at the well can continue to increase for 20 years if a low pumping rate is applied. This study concludes that because of the rapid response of the pesticide concentration at the drinking water well due to changes in pumping, wellhead management is important for managing pesticide concentrations.

Evaluating alternate biokinetic models for trace pollutant cometabolism.

Mathematical models of cometabolic biodegradation kinetics can improve our understanding of the relevant microbial reactions and allow us to design in situ or in-reactor applications of cometabolic bioremediation. A variety of models are available, but their ability to describe experimental data has not been systematically evaluated for a variety of operational/experimental conditions. Here five different models were considered: first-order; Michaelis-Menten; reductant; competition; and combined models. The models were assessed on their ability to fit data from simulated batch experiments covering a realistic range of experimental conditions. The simulated observations were generated by using the most complex model structure and parameters based on the literature, with added experimental error. Three criteria were used to evaluate model fit: ability to fit the simulated experimental data, identifiability of parameters using a colinearity analysis, and suitability of the model size and complexity using the Bayesian and Akaike Information criteria. Results show that no single model fits data well for a range of experimental conditions. The reductant model achieved best results, but required very different parameter sets to simulate each experiment. Parameter nonuniqueness was likely to be due to the parameter correlation. These results suggest that the cometabolic models must be further developed if they are to reliably simulate experimental and operational data.

Dilution and volatilization of groundwater contaminant discharges in streams.

An analytical solution to describe dilution and volatilization of a continuous groundwater contaminant plume into streams is developed for risk assessment. The location of groundwater plume discharge into the stream (discharge through the side versus bottom of the stream) and different distributions of the contaminant plume concentration (Gaussian, homogeneous or heterogeneous distribution) are considered. The model considering the plume discharged through the bank of the river, with a uniform concentration distribution was the most appropriate for risk assessment due to its simplicity and limited data requirements. The dilution and volatilization model is able to predict the entire concentration field, and thus the mixing zone, maximum concentration and fully mixed concentration in the stream. It can also be used to identify groundwater discharge zones from in-stream concentration measurement. The solution was successfully applied to published field data obtained in a large and a small Danish stream and provided valuable information on the risk posed by the groundwater contaminant plumes. The results provided by the dilution and volatilization model are very different to those obtained with existing point source models, with a distributed source leading to a larger mixing length and different concentration field. The dilution model can also provide recommendations for sampling locations and the size of impact zones in streams. This is of interest for regulators, for example when developing guidelines for the implementation of the European Water Framework Directive.

A new settling velocity model to describe secondary sedimentation.

Secondary settling tanks (SSTs) are the most hydraulically sensitive unit operations in biological wastewater treatment plants. The maximum permissible inflow to the plant depends on the efficiency of SSTs in separating and thickening the activated sludge. The flow conditions and solids distribution in SSTs can be predicted using computational fluid dynamics (CFD) tools. Despite extensive studies on the compression settling behaviour of activated sludge and the development of advanced settling velocity models for use in SST simulations, these models are not often used, due to the challenges associated with their calibration. In this study, we developed a new settling velocity model, including hindered, transient and compression settling, and showed that it can be calibrated to data from a simple, novel settling column experimental set-up using the Bayesian optimization method DREAM(ZS). In addition, correlations between the Herschel-Bulkley rheological model parameters and sludge concentration were identified with data from batch rheological experiments. A 2-D axisymmetric CFD model of a circular SST containing the new settling velocity and rheological model was validated with full-scale measurements. Finally, it was shown that the representation of compression settling in the CFD model can significantly influence the prediction of sludge distribution in the SSTs under dry- and wet-weather flow conditions.

Risk-based prioritization of ground water threatening point sources at catchment and regional scales.

Contaminated sites threaten ground water resources all over the world. The available resources for investigation and remediation are limited compared to the scope of the problem, so prioritization is crucial to ensure that resources are allocated to the sites posing the greatest risk. A flexible framework has been developed to enable a systematic and transparent risk assessment and prioritization of contaminant point sources, considering the local, catchment, or regional scales (Danish EPA, 2011, 2012). The framework has been tested in several catchments in Denmark with different challenges and needs, and two of these are presented. Based on the lessons learned, the Danish EPA has prepared a handbook to guide the user through the steps in a risk-based prioritization (Danish EPA, 2012). It provides guidance on prioritization both in an administratively defined area such as a Danish Region, and within the bounds of a specified ground water catchment. The handbook presents several approaches in order to prevent the prioritization from foundering because of a lack of data or an inappropriate level of complexity. The developed prioritization tools, possible graphical presentation and use of the results are presented using the case studies as examples. The methodology was developed by a broad industry group including the Danish EPA, the Danish Regions, the Danish Nature Agency, the Technical University of Denmark, and consultants - and the framework has been widely accepted by the professional community in Denmark. The concepts are quite general and can be applied in other countries facing similar challenges.

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

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

Does microbial centimeter-scale heterogeneity impact MCPA degradation in and leaching from a loamy agricultural soil?

The potential for pesticide degradation varies greatly at the centimeter-scale in agricultural soil. Three dimensional numerical simulations were conducted to evaluate how such small-scale spatial heterogeneity may affect the leaching of the biodegradable pesticide 2-methyl-4-chlorophenoxyacetic acid (MCPA) in the upper meter of a variably-saturated, loamy soil profile. To incorporate realistic spatial variation in degradation potential, we used data from a site where 420 mineralization curves over 5 depths have been measured. Monod kinetics was fitted to the individual curves to derive initial degrader biomass values, which were incorporated in a reactive transport model to simulate heterogeneous biodegradation. Six scenarios were set up using COMSOL Multiphysics to evaluate the difference between models having different degrader biomass distributions (homogeneous, heterogeneous, or no biomass) and either matrix flow or preferential flow through a soil matrix with a wormhole. MCPA leached, within 250 days, below 1m only when degrader biomass was absent and preferential flow occurred. Both biodegradation in the plow layer and the microbially active lining of the wormhole contributed to reducing MCPA-leaching below 1m. The spatial distribution of initial degrader biomass within each soil matrix layer, however, had little effect on the overall MCPA-leaching.

The impact of bioaugmentation on dechlorination kinetics and on microbial dechlorinating communities in subsurface clay till.

A molecular study on how the abundance of the dechlorinating culture KB-1 affects dechlorination rates in clay till is presented. DNA extracts showed changes in abundance of specific dechlorinators as well as their functional genes. Independently of the KB-1 added, the microbial dechlorinator abundance increased to the same level in all treatments. In the non-bioaugmented microcosms the reductive dehalogenase gene bvcA increased in abundance, but when KB-1 was added the related vcrA gene increased while bvcA genes did not increase. Modeling showed higher vinyl-chloride dechlorination rates and shorter time for complete dechlorination to ethene with higher initial concentration of KB-1 culture, while cis-dichloroethene dechlorination rates were not affected by KB-1 concentrations. This study provides high resolution abundance profiles of Dehalococcoides spp. (DHC) and functional genes, highlights the ecological behavior of KB-1 in clay till, and reinforces the importance of using multiple functional genes as biomarkers for reductive dechlorination.

The gompertz function can coherently describe microbial mineralization of growth-sustaining pesticides.

Mineralization of (14)C-labeled tracers is a common way of studying the environmental fate of xenobiotics, but it can be difficult to extract relevant kinetic parameters from such experiments since complex kinetic functions or several kinetic functions may be needed to adequately describe large data sets. In this study, we suggest using a two-parameter, sigmoid Gompertz function for parametrizing mineralization curves. The function was applied to a data set of 252 normalized mineralization curves that represented the potential for degradation of the herbicide MCPA in three horizons of an agricultural soil. The Gompertz function fitted most of the normalized curves, and trends in the data set could be visualized by a scatter plot of the two Gompertz parameters (rate constant and time delay). For agricultural topsoil, we also tested the effect of the MCPA concentration on the mineralization kinetics. Reduced initial concentrations lead to shortened lag-phases, probably due to reduced need for bacterial growth. The effect of substrate concentration could be predicted by simply changing the time delay of the Gompertz curves. This delay could to some extent also simulate concentration effects for 2,4-D mineralization in agricultural soil and aquifer sediment and 2,6-dichlorobenzamide mineralization in single-species, mineral medium.

Discharge of landfill leachate to streambed sediments impacts the mineralization potential of phenoxy acid herbicides depending on the initial abundance of tfdA gene classes.

To understand the role of abundance of tfdA gene classes belonging to ß- and γ-proteobacteria on phenoxy acid herbicide degradation, streambed sediments were sampled around three seepage meters (SMs) installed in a landfill-impacted groundwater-surface water interface. Highest herbicide mass discharge to SM3, and lower herbicide mass discharges to SM1 and SM2 were determined due to groundwater discharge rates and herbicide concentrations. SM1-sediment with the lowest abundance of tfdA gene classes had the slowest mineralization, whereas SM2- and SM3-sediments with more abundant tfdA genes had faster mineralization. The observed difference in mineralization rates between discharge zones was simulated by a Monod-based kinetic model, which confirmed the role of abundance of tfdA gene classes. This study suggests presence of specific degraders adapted to slow growth rate and high yield strategy due to long-term herbicide exposure; and thus groundwater-surface water interface could act as a natural biological filter and protect stream water quality.

A conceptual model linking functional gene expression and reductive dechlorination rates of chlorinated ethenes in clay rich groundwater sediment.

We used current knowledge of cellular processes involved in reductive dechlorination to develop a conceptual model to describe the regulatory system of dechlorination at the cell level; the model links bacterial growth and substrate consumption to the abundance of messenger RNA of functional genes involved in the dechlorination process. The applicability of the model was tested on a treatability study of biostimulated and bioaugmented microcosms. Using quantitative real time PCR, high-resolution expression profiles of the functional reductive dehalogenase genes bvcA and vcrA were obtained during two consecutive dechlorination events of trichlorethene, cis-dichlorethene and vinyl chloride. Up-regulation of the bvcA (for the biostimulated microcosms) and vcrA (for the bioaugmented microcosms) gene expression fitted well with high rates of dechlorination of vinyl chloride, while no known transcripts could be measured during trichloroethene and cis-dichlorethene dechlorination. Maximum concentrations of 2.1 and 1.7 transcripts per gene of the bvcA and vcrA genes, respectively, were measured at the same time points as maximum dechlorination rates were observed. The developed model compared well with the experimental data for both biostimulated and bioaugmented microcosms under non-steady state conditions and was supported by results from a recently published study under steady state conditions.

Review of reactive kinetic models describing reductive dechlorination of chlorinated ethenes in soil and groundwater.

Reductive dechlorination is a major degradation pathway of chlorinated ethenes in anaerobic subsurface environments, and reactive kinetic models describing the degradation process are needed in fate and transport models of these contaminants. However, reductive dechlorination is a complex biological process, where many microbial populations including dechlorinating, fermentative, methanogenic, iron and sulfate reducing, interact. In this article the modeling approaches and the experimental data needed to calibrate them are reviewed, classified, and discussed. Model approaches considered include first order kinetics, Monod kinetics to describe sequential reductive dechlorination and bacterial growth, and metabolic models which simulate fermentation and redox processes interacting with reductive dechlorination processes. The review shows that the estimated kinetic parameters reported vary over a wide range, and that experimental microbial data are scarce. Very few studies have been performed evaluating the influence of sulfate and iron reduction, and contradictory conclusions on the interaction of redox processes with reductive dechlorination have been reported. The modeling approaches for metabolic reductive dechlorination employing different descriptions of the interaction between redox and dechlorination processes and competition for hydrogen are classified. The current concepts lead to different results, suggesting a need for further investigations on the interactions between the microbial communities performing dechlorination and redox processes, including the establishment of biomarkers quantifying dechlorination, and on geochemical characterization. Finally, the relevance of laboratory data and the development of practical modeling tools for field applications are discussed.

A catchment scale evaluation of multiple stressor effects in headwater streams.

Mitigation activities to improve water quality and quantity in streams as well as stream management and restoration efforts are conducted in the European Union aiming to improve the chemical, physical and ecological status of streams. Headwater streams are often characterised by impairment of hydromorphological, chemical, and ecological conditions due to multiple anthropogenic impacts. However, they are generally disregarded as water bodies for mitigation activities in the European Water Framework Directive despite their importance for supporting a higher ecological quality in higher order streams. We studied 11 headwater streams in the Hove catchment in the Copenhagen region. All sites had substantial physical habitat and water quality impairments due to anthropogenic influence (intensive agriculture, urban settlements, contaminated sites and low base-flow due to water abstraction activities in the catchment). We aimed to identify the dominating anthropogenic stressors at the catchment scale causing ecological impairment of benthic macroinvertebrate communities and provide a rank-order of importance that could help in prioritising mitigation activities. We identified numerous chemical and hydromorphological impacts of which several were probably causing major ecological impairments, but we were unable to provide a robust rank-ordering of importance suggesting that targeted mitigation efforts on single anthropogenic stressors in the catchment are unlikely to have substantial effects on the ecological quality in these streams. The SPEcies At Risk (SPEAR) index explained most of the variability in the macroinvertebrate community structure, and notably, SPEAR index scores were often very low (<10% SPEAR abundance). An extensive re-sampling of a subset of the streams provided evidence that especially insecticides were probably essential contributors to the overall ecological impairment of these streams. Our results suggest that headwater streams should be considered in future management and mitigation plans. Catchment-based management is necessary because several anthropogenic stressors exceeded problematic thresholds, suggesting that more holistic approaches should be preferred.

ZVI-Clay remediation of a chlorinated solvent source zone, Skuldelev, Denmark: 2. Groundwater contaminant mass discharge reduction.

The impact of source mass depletion on the down-gradient contaminant mass discharge was monitored for a 19-month period as a part of a field demonstration of the ZVI-Clay soil mixing remediation technology. Groundwater samples were collected from conventional monitoring wells (120 samples) and a dense network of multilevel samplers (640 samples). The hydraulic gradient and conductivity were determined. Depletion of the contaminant source is described in the companion paper (Fjordbøge et al., 2012). Field data showed four distinct phases for PCE mass discharge: (1) baseline conditions, (2) initial rapid reduction, (3) temporary increase, and (4) slow long-term reduction. Numerical modeling was utilized to develop a conceptual understanding of the four phases and to identify the governing processes. The initial rapid reduction of mass discharge was a result of the changed hydraulic properties in the source zone after soil mixing. The subsequent phases depended on the changed accessibility of the contaminant mass after mixing, the rate of source depletion, and the concentration gradient at the boundaries of the mixed source zone. Overall, ZVI-Clay soil mixing resulted in a significant down-gradient contaminant mass discharge reduction (76%) for the parent compound (PCE), while the overall reduction of chlorinated ethenes was smaller (21%).