Understanding the dynamics of enhanced light non-aqueous phase liquids (LNAPL) remediation at a polluted site: Insights from hydrogeophysical findings and chemical evidence.

This study intricately unfolds a pioneering methodology for remediating contaminants in a persistent light non-aqueous phase liquids (LNAPL)-contaminated site. The remediation strategy seamlessly integrates enhanced desorption and in-situ chemical oxidation (ISCO), orchestrating the injection of PetroCleanze® (a desorbent) and RegenOx® (an oxidizer) through meticulously designed wells. These injections, based on detailed geological and hydrogeological assessments, aim at mobilizing residual contaminants for subsequent extraction. Real-time subsurface dynamics are investigated through geophysical monitoring, employing electrical resistivity tomography (ERT) to trace reagent migration pathways via their effect on bulk electrical conductivity. The integration of groundwater sampling data aims at providing additional insights into the transformations of contaminants in the spatiotemporal context. Vivid two-dimensional time-lapse ERT sections showcase the evolution of resistivity anomalies, providing high-resolution evidence of the heterogeneity, dispersion pathways of desorbent and oxidant, and residual LNAPL mobilization. Hydrochemical analyses complement this, revealing effective mobilization processes with increasing aqueous concentrations of total petroleum hydrocarbons (TPH) over time. Speciation analysis unveils the intricate interplay of desorption and oxidation, portraying the dynamic fractionation of hydrocarbon components. The hydrogeophysical and data-driven framework not only delivers qualitative and quantitative insights into reagent and contaminant distribution but also enhances understanding of spatial and temporal physio-chemical changes during the remediation process. Time-lapse ERT visually narrates the reagent's journey through time, while chemical analyses depict the unfolding processes of desorption and oxidation across space and time. The coupling of hydrogeophysical and chemical findings pictures the transformations of pollutants following the sequence of product injection and the push and pull activities, capturing the removal of mobilized contaminants through hydraulic barrier wells. This enhanced understanding proves instrumental towards optimizing and tailoring remediation efforts, especially in heterogeneous environmental settings. This study establishes a new standard for a sophisticated and innovative contaminant remediation approach, advancing environmental practices through the harmonized analysis of geophysical and chemical data.

A data-driven modeling approach for the sustainable remediation of persistent arsenic (As) groundwater contamination in a fractured rock aquifer through a groundwater recirculation well (IEG-GCW®).

Persistent arsenic (As) pollution sources from anthropogenic activities pose a serious threat to groundwater quality. This work aims to illustrate the application of an innovative remediation technology to remove As from a heavily contaminated fractured aquifer at a historically polluted industrial site. Groundwater circulation well (GCW) technology was tested to significantly increase and accelerate the mobilization and removal of As in the source area. The GCW extracts and re-injects groundwater at different depths of a vertical circulation well. By pumping out and reinjecting in different screen sections of the well, the resulting vertical hydraulic gradients create recirculation cells and affect and mobilize trapped contaminants that cannot be influenced by traditional pumping systems. The first 45-m deep IEG-GCW® system was installed in 2020, equipped with 4 screen sections at different depths and with an above-ground As removal system by oxidation and filtration on Macrolite (Enki). A geomodeling approach supports both remediation and multi-source data interpretation. The first months of operation demonstrate the hydraulic effectiveness of the IEG-GCW® system in the fractured rock aquifer and the ability to significantly enhance As removal compared to conventional pumping wells currently feeding a centralized treatment system. The recirculation flow rate amounts to about 2 m3/h. Water pumped and treated by the GCW system is reintroduced with As concentrations reduced by an average of 20%-60%. During the pilot test, the recirculating system removed 23 kg As whilst the entire central pump-and-treat (P&T) system removed 129 kg, although it treated 100 times more water volume. The P&T plant removed 259 mg As per m3 of pumped and treated groundwater while the GCW removed 4814 mg As per m3 of the treated groundwater. The results offer the opportunity for a more environmentally sustainable remediation approach by actively attacking the contamination source rather than containing the plume.

Remediation of chlorinated aliphatic hydrocarbons (CAHs) contaminated site coupling groundwater recirculation well (IEG-GCW®) with a peripheral injection of soluble nutrient supplement (IEG-C-MIX) via multilevel-injection wells (IEG-MIW).

An innovative Groundwater Circulation Well (GCW) process was configured, installed, and tested for optimizing the distribution of a soluble nutrient supplement in a heterogeneous aquifer for reductive dehalogenation. This generated an in-situ bioreactor for the enhanced treatment of chlorinated aliphatic hydrocarbons (CAHs). At a site in Barcelona, Spain, trichloroethylene (TCE) concentration was found in the source area to a maximum value of up to 170 mg/L, while the degradation products like 1,2-dichloroethylene (1,2-DCE) and vinyl chloride (VC) were detected in significantly lower concentrations or were even absent. The novel system combined a vertical recirculation well (IEG-GCW®) and four multilevel injection wells (IEG-MIWs) to introduce the carbon solution into the aquifer. A 12 m deep IEG-GCW® equipped with 2 screened sections were located in the center of the 4 IEG-MIWs. The GCW induced flow moves the groundwater in an ellipsoidal recirculation cell to spread the supplements from the central GCW and from the peripheral MIWs in the aquifer body. Two multilevel sampling wells (IEG-MLSWs®) in the radius of influence (ROI) monitor the remediation process to capture hydrochemical variations along the vertical aquifer sections. A multi-source model harmonizes geological and hydrochemical information during different remediation stages, guiding the adaptation of the remediation strategy to physicochemical conditions and unmasking the decontamination mechanics induced by the remedial actions. Hydrochemical monitoring of MLWS and the stable carbon isotopic signature of cis-1,2-DCE and VC show the mobilization of secondary contamination sources triggered by recirculation during remediation, the stimulation of microbiological activity following nutrient supplement via GCW and MIWs, and the strong decrease of CAHs concentrations at different aquifer levels. Evidence from the first application at the field scale reveals a significant increase in the chloroethane biodegradation rate and short-term effectiveness of the innovative remediation strategy. GCW-MIWs synergy represents a promising strategy to degrade CAHs in a shorter period through the combination of a controllable hydraulic system, effective nutrient distribution, and the monitoring of the remediation process.

A field-scale remediation of residual light non-aqueous phase liquid (LNAPL): chemical enhancers for pump and treat.

The remediation of petroleum-contaminated soil and groundwater is a challenging task. The petroleum hydrocarbons have a long persistence in both the vadose zone and in the aquifer and potentially represent secondary and residual sources of contamination. This is particularly evident in the presence of residual free-phase. Pump-and-treat is the most common hydrocarbon decontamination strategy. Besides, it acts primarily on the water dissolved phase and reduces concentrations of contaminants to an asymptotic trend. This study presents a case of enhanced light non-aqueous phase liquid (LNAPL) remediation monitored using noninvasive techniques. A pilot-scale field experiment was conducted through the injection of reagents into the subsoil to stimulate the desorption and the oxidation of residual hydrocarbons. Geophysical and groundwater monitoring during pilot testing controlled the effectiveness of the intervention, both in terms of product diffusion capacity and in terms of effective reduction of pollutant concentrations. In particular, non-invasive monitoring of the reagent migration and its capability to reach the target areas is a major add-on to the remediation technique. Most of the organic contaminants were decomposed, mobilized, and subsequently removed using physical recovery techniques. A considerable mass of contaminant was recovered resulting in the reduction of concentrations in the intervention areas.

Delineation of hydrocarbon contaminants with multi-frequency complex conductivity imaging.

The characterization of contaminated sites is a serious issue that requires a number of techniques to be deployed in the field to reconstruct the geometry, hydraulic properties and state of contamination of the shallow subsurface, often at the hundreds of meter scale with metric resolution. Among the techniques that have been proposed to complement direct investigations (composed of drilling, sampling, and laboratory characterization) are geophysical methods, which can provide extensive spatial coverage both laterally and at depth with the required resolution. However, geophysical methods only measure physical properties that are indirectly related to contamination, and their correlation may be difficult to ascertain without direct ground truth. In this study, we present a successful example where the results of complex conductivity measurements conducted in an imaging framework are compared with direct evidence of subsoil contamination at a jet fuel impacted site. Thus, proving that a combination of direct and indirect investigations can be successfully used to image a site in its complex (potentially 3D) structure in order to build a reliable conceptual model of the site.

Bioelectrochemical treatment of groundwater containing BTEX in a continuous-flow system: Substrate interactions, microbial community analysis, and impact of sulfate as a co-contaminant.

Microbial electrochemical technologies (MET) are increasingly being considered for in situ remediation of contaminated groundwater. However, their application potential for the simultaneous treatment of complex mixtures of organic and inorganic contaminants, has been only marginally explored. Here we have analyzed the performance of the 'bioelectric well', a previously developed bioelectrochemical reactor configuration, in the treatment of benzene, toluene, ethyl-benzene and xylenes (BTEX) mixtures. Although to different extents, all BTEX were found to be degraded in the bioelectrochemical system, operated using a continuous-flow of groundwater at a hydraulic retention time of 8.8 h, with the graphite anode potentiostatically controlled at +0.200 V vs. the standard hydrogen electrode. In the case of toluene and ethyl-benzene, biodegradation was further confirmed by the GC-MS identification of fumarate-addition metabolites, previously shown to be involved in the activation of these contaminants under anaerobic conditions. Degradation rates were higher for toluene (31.3 ±â€¯1.5 mg/L d) and lower for benzene (6.1 ±â€¯0.3 mg/L d), ethyl-benzene (3.3 ±â€¯0.1 mg/L d), and xylenes (4.5 ±â€¯0.2 mg/L d). BTEX degradation was linked to electric current generation, with coulombic efficiencies falling in the range 53-69%, although methanogenesis also contributed to contaminant degradation. Remarkably, the system also allowed removal of sulfate simultaneously with toluene. Sulfate removal was likely driven by the hydrogen abiotically generated at the cathode. Taken as a whole, these findings highlight the remarkable potential of this innovative reactor configuration for application in a variety of contamination scenarios.

Contaminant back-diffusion from low-permeability layers as affected by groundwater velocity: A laboratory investigation by box model and image analysis.

Low-permeability lenses represent potential sources of long-term release when filled from contaminant solute through direct contact with dissolved plumes. The redistribution of contaminant from low to high permeability aquifer zones (Back-Diffusion) was studied. Redistribution causes a long plume tail, commonly regarded as one of the main obstacles to effective groundwater remediation. Laboratory tests were performed to reproduce the redistribution process and to investigate the effect of pumping water on the remediation time of these contaminated low-permeability lenses. The test section used is representative of clay/silt lenses (k≈1∗10-10m/s/k≈1∗10-7m/s) in a sand aquifer (k≈1∗10-3m/s). Hence, an image analysis procedure was used to estimate the diffusive flux of contaminant released by these low-permeability zones. The proposed technique was validated performing a mass balance of a lens saturated by a known quantity of tracer. For each test, performed using a different groundwater velocity, the diffusive fluxes of contaminant released by lenses were compared and the remediation times of the low-permeability zones calculated. For each lens, the obtained remediation timeframes were used to define an analytical relation vs groundwater velocity and the coefficients of these relations were matched to grain size of the low-permeability lenses. Results show that an increase of the velocity field is not useful to diminish the total depletion times as the process mainly diffusive. This is significant when the remediation approach relies on pumping technology.

Monitoring alkylphenols in water using the polar organic chemical integrative sampler (POCIS): Determining sampling rates via the extraction of PES membranes and Oasis beads.

Polar organic chemical integrative samplers (POCIS) have previously been used to monitor alkylphenol (AP) contamination in water and produced water. However, only the sorbent receiving phase of the POCIS (Oasis beads) is traditionally analyzed, thus limiting the use of POCIS for monitoring a range of APs with varying hydrophobicity. Here a "pharmaceutical" POCIS was calibrated in the laboratory using a static renewal setup for APs (from 2-ethylphenol to 4-n-nonylphenol) with varying hydrophobicity (log Kow between 2.47 and 5.76). The POCIS sampler was calibrated over its 28 day integrative regime and sampling rates (Rs) were determined. Uptake was shown to be a function of AP hydrophobicity where compounds with log Kow < 4 were preferentially accumulated in Oasis beads, and compounds with log Kow > 5 were preferentially accumulated in the PES membranes. A lag phase (over a 24 h period) before uptake in to the PES membranes occurred was evident. This work demonstrates that the analysis of both POCIS phases is vital in order to correctly determine environmentally relevant concentrations owing to the fact that for APs with log Kow ≤ 4 uptake, to the PES membranes and the Oasis beads, involves different processes compared to APs with log Kow ≥ 4. The extraction of both the POCIS matrices is thus recommended in order to assess the concentration of hydrophobic APs (log Kow ≥ 4), as well as hydrophilic APs, most effectively.

Characterizing Biochar as Alternative Sorbent for Oil Spill Remediation.

Biochar (BC) was characterized as a new carbonaceous material for the adsorption of toluene from water. The tested BC was produced from pine wood gasification, and its sorption ability was compared with that of more common carbonaceous materials such as activated carbon (AC). Both materials were characterized in terms of textural features and sorption abilities by kinetic and equilibrium tests. AC and BC showed high toluene removal from water. Kinetic tests demonstrated that BC is characterized by faster toluene removal than AC is. Textural features demonstrated that the porosity of AC is double that of BC. Nevertheless, equilibrium tests demonstrated that the sorption ability of BC is comparable with that of AC, so the materials' porosity is not the only parameter that drives toluene adsorption. The specific adsorption ability (mg sorbed m-2 of surface) of the BC is higher than that of AC: toluene is more highly sorbed onto the biochar surface. Biochar is furthermore obtained from biomaterial thermally treated for making energy; this also makes the use of BC economically and environmentally convenient compared with AC, which, as a manufactured material, must be obtained in selected conditions for this type of application.

Polyhydroxyalkanoate as a slow-release carbon source for in situ bioremediation of contaminated aquifers: From laboratory investigation to pilot-scale testing in the field.

A pilot-scale study aiming to evaluate the potential use of poly-3-hydroxy-butyrate (PHB) as an electron donor source for in situ bioremediation of chlorinated hydrocarbons in groundwater was conducted. Compared with commercially available electron donors, PHB offers a restricted fermentation pathway (i.e., through acetic acid and molecular hydrogen) by avoiding the formation of any residual carbon that could potentially spoil groundwater quality. The pilot study was carried out at an industrial site in Italy, heavily contaminated by different chlorinated aliphatic hydrocarbons (CAHs). Prior to field testing, PHB was experimentally verified as a suitable electron donor for biological reductive dechlorination processes at the investigated site by microcosm studies carried out on site aquifer material and measuring the quantitative transformation of detected CAHs to ethene. Owing to the complex geological characteristics of the aquifer, the use of a groundwater circulation well (GCW) was identified as a potential strategy to enable effective delivery and distribution of electron donors in less permeable layers and to mobilise contaminants. A 3-screened, 30-m-deep GCW coupled with an external treatment unit was installed at the site. The effect of PHB fermentation products on the in situ reductive dechlorination processes were evaluated by quantitative real-time polymerase chain reaction (qPCR). The results from the first 4 months of operation clearly demonstrated that the PHB fermentation products were effectively delivered to the aquifer and positively influenced the biological dechlorination activity. Indeed, an increased abundance of Dehalococcoides mccartyi (up to 6.6 fold) and reduced CAH concentrations at the installed monitoring wells were observed.

Bioelectrochemical approach for reductive and oxidative dechlorination of chlorinated aliphatic hydrocarbons (CAHs).

A sequential reductive-oxidative treatment was developed in this study in a continuous-flow bioelectrochemical reactor to address bioremediation of groundwater contaminated by trichloroethene (TCE) and less-chlorinated but still harmful intermediates, such as vinyl chloride. In order to optimize the anodic compartment, whereby the oxygen-driven microbial oxidation of TCE-daughter products occurs, abiotic batch experiments were performed with various anode materials poised at +1.20 V vs. SHE (i.e., graphite rods and titanium mesh anode coated with mixed metal oxides (MMO)) and setups (i.e., electrodes embedded within a bed of silica beads or graphite granule). The MMO anode displayed higher efficiency (>90%) for oxygen generation compared to the graphite electrodes. Additionally, the graphite bed presence adversely affects oxygen generation, likely due to the oxygen scavenging. This effect was completely eliminated by replacing the graphite granules with silica beads. The anodic setups were thereafter verified in a mentioned reactor at an applied TCE loading rate of approximately 20 µM d-1 and a hydraulic retention time of 1.4 d in each compartment. The cathode consisted of a bed of graphite granules and was potentiostatically controlled at -0.65 V vs. SHE. The best reactor performance in terms of removal efficiency (i.e., >97%), removal rate (i.e., 121.8 ± 2.7 µeq L-1 d-1), and the residual concentration (i.e., 5.03 ± 0.63 µeq L-1) of chlorinated contaminants was achieved with the MMO anode placed in a silica bed. Ecotoxicity tests performed with algae confirmed these results by showing progressive toxicity reduction from inlet to cathodic and anodic effluent using this reactor configuration.

Image analysis procedure for studying Back-Diffusion phenomena from low-permeability layers in laboratory tests.

In this study, the long-term tailing derived from the storage process of contaminants in low-permeability zones is investigated. The release from these areas in the groundwater can be considered a long-term source that often undermines remediation efforts. An Image Analysis technique is used to analyze the process and evaluate the concentrations of a tracer at different points of the test section. Furthermore, the diffusive flux from the low-permeability lenses is determined. To validate the proposed technique, the results are compared with samples, and the diffusive fluxes resulting from the low-permeability zones of the reconstructed aquifer are compared with a theoretical approach.

Polyhydroxyalkanoate (PHB) as a slow-release electron donor for advanced in situ bioremediation of chlorinated solvent-contaminated aquifers.

During the last two decades permeable reactive barriers (PRBs) established as robust alternatives to traditional pump & treat approaches for groundwater remediation. Zero-valent iron (ZVI) is currently the most frequently employed reactive media, especially for treating plumes polluted by chlorinated hydrocarbons. However PRB-ZVI technology is affected by some problems such as the long-term performance decrease, loss of porosity and no applicability to some important compounds, such as 1,2-dichloroetane (1,2-DCA). In this study we wanted to investigate whether the coupling of ZVI with a long-lasting slow-release substrate (i.e. poly-hydroxybutyrate, PHB) could be a strategy to enhance the degradation performance of ZVI barriers towards chlorinated ethanes especially stimulating biological reductive dechlorination downgradient the PRB. Results here presented clearly demonstrate the feasibility of the proposed approach and the possibility that a biodegradable polymer, usually produced for different commercial sectors, could be advantageously used in the groundwater remediation market.

Use of a reactive transport model to describe reductive dechlorination (RD) as a remediation design tool: application at a CAH-contaminated site.

In this paper, a numerical model is presented that is capable of describing the complex set of biochemical processes that occur in chlorinated aliphatic hydrocarbon (CAH)-contaminated groundwater when an exogenous electron donor is added. The reactive pattern is based on the degradation pathways of both chlorinated ethanes and ethenes, and it includes electron donor production (H2 and acetate) from the fermentation of an organic substrate as well as rate-limiting processes related to electron acceptor competition. Coupling of the kinetic model to a convection-dispersion module is described. The calibration phase was carried out using data obtained at a real CAH-contaminated site in the north of Italy. Model simulations of different application scenarios are presented to draw general conclusions on the effectiveness of reductive dechlorination (RD) as a possible cleanup strategy. Early outcomes indicate that cleanup targets can only be achieved if source longevity is reduced. Therefore, metabolic RD is expected to produce beneficial effects because it is known to induce bioenhanced degradation and transformation of CAHs.

Improved electrical wiring of microbes: anthraquinone-modified electrodes for biosensing of chlorinated hydrocarbons.

The present study reports the development of a novel bioelectrochemical sensor for trichloroethene (TCE), a common subsurface contaminant, based on the measurement of the electrical current resulting from the microbially catalysed reduction of TCE at anthraquinone (AQ)-modified electrodes. Firstly, we describe the development and electrochemical characterisation of AQ-modified electrodes, prepared via spontaneous or electrochemical reduction of AQ diazonium derivatives. Finally, the proof-of-principle of the bioelectrochemical sensor for TCE was evaluated, using a TCE-dechlorinating microbial culture as the biosensing element. The response of the bioelectrochemical sensor was measured either as the peak current in cyclic voltammetry or the steady-state current in chronoamperometry; in both cases, it was found to be proportional to TCE concentrations in the range 0-100 µmol/L. On the other hand, the microorganisms in contact with the electrode surface caused severe fouling problems which drastically reduced the life-time of the sensor.

Laboratory investigation of DNAPL migration in porous media.

Laboratory experiments have been carried out with and without groundwater flow in a two-dimensional laboratory-scale tank to assess the influence of layered media and hydraulic gradient on DNAPL infiltration and redistribution processes. Hydrofluoroether has been used as DNAPL and glass beads have been utilized as porous medium. An image analysis procedure has been used to determine saturation distribution during infiltration and redistribution processes. This method allows quantitative time dependent full fields mapping of the DNAPL saturation, as well as the monitoring of DNAPL saturation variation. By means of performed experiments important information were obtained about the migration and redistribution process, the infiltration and migration velocity, the characteristics of migration body. The experimental results show that the hydraulic gradient promotes the infiltration process, increasing the infiltration rate. It hampers DNAPL spread and fingering bringing to a reduction of residual DNAPL and it also promotes the DNAPL redistribution, and it reduces the amount remaining at residual saturation. Furthermore the hydraulic gradient promotes downward and down-gradient migration. DNAPL migration in the direction of water flow, can be considered important due to significant errors in the location of sources in the case of high gradients and high aquifer thicknesses, and for high water flow velocities, such as those which can be expected during pumping actions in water supply or in remediation activities.

Characterization and distribution of petroleum hydrocarbons and heavy metals in groundwater from three Italian tank farms.

The present paper highlights the utility of petroleum chemical fingerprinting in investigating known or suspected tank farm releases. A detailed characterization of groundwater was carried out in three tank farms located in north, central and south Italy. Eighteen parent polycyclic aromatic hydrocarbons (naphthalene through coronene), n-alkanes (n-C(10) through n-C(36)), isoprenoids pristane and phytane, vanadium, nickel and lead were determined. Distribution profiles and diagnostic ratios of specific fuel constituents were studied in order to identify contamination sources. Data analysis shows that in the study sites multiple pollutant sources affecting the tank farms and the surrounding industrial areas are present. Both high concentrations of contaminants coming from fuel releases and noticeable concentrations of biogenic compounds were found. A detailed data analysis suggests the origin and the level of pollution of the three sites. The results demonstrate that threshold concentration approach is not always sufficient and it is necessary to carry out studies of contaminant distribution and their diagnostic ratios in order to perform a successful forensic investigation.

Anaerobic bioremediation of groundwater containing a mixture of 1,1,2,2-tetrachloroethane and chloroethenes.

This study investigated the biotransformation pathways of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) in the presence of chloroethenes (i.e. tetrachloroethene, PCE; trichloroethene, TCE) in anaerobic microcosms constructed with subsurface soil and groundwater from a contaminated site. When amended with yeast extract, lactate, butyrate, or H2 and acetate, 1,1,2,2-TeCA was initially dechlorinated via both hydrogenolysis to 1,1,2-trichloroethane (1,1,2-TCA) (major pathway) and dichloroelimination to dichloroethenes (DCEs) (minor pathway), with both reactions occurring under sulfidogenic conditions. In the presence of only H2, the hydrogenolysis of 1,1,2,2-TeCA to 1,1,2-TCA apparently required the presence of acetate to occur. Once formed, 1,1,2-TCA was degraded predominantly via dichloroelimination to vinyl chloride (VC). Ultimately, chloroethanes were converted to chloroethenes (mainly VC and DCEs) which persisted in the microcosms for very long periods along with PCE and TCE originally present in the groundwater. Hydrogenolysis of chloroethenes occurred only after highly reducing methanogenic conditions were established. However, substantial conversion to ethene (ETH) was observed only in microcosms amended with yeast extract (200 mg/l), suggesting that groundwater lacked some nutritional factors which were likely provided to dechlorinating microorganisms by this complex organic substrate. Bioaugmentation with an H2-utilizing PCE-dechlorinating Dehalococcoides spp. -containing culture resulted in the conversion of 1,1,2,2-TeCA, PCE and TCE to ETH and VC. No chloroethanes accumulated during degradation suggesting that 1,1,2,2-TeCA was degraded through initial dichloroelimination into DCEs and then typical hydrogenolysis into ETH and VC.

Comparative study of methanol, butyrate, and hydrogen as electron donors for long-term dechlorination of tetrachloroethene in mixed anerobic cultures.

This study examined the ability of different electron donors (i.e., hydrogen, methanol, butyrate, and yeast extract) to sustain long-term (500 days) reductive dechlorination of tetrachloroethene (PCE) in anerobic fill-and-draw bioreactors operated at 3:1 donor:PCE ratio (defined on a total-oxidation basis for the donor). Initially (i.e., until approximately day 80), the H(2)-fed bioreactor showed the best ability to completely dechlorinate the dosed PCE (0.5 mmol/L) to ethene whereas, in the presence of methanol, butyric acid or no electron donor added (but low-level yeast extract), dechlorination was limited by the fermentation of the organic substrates and in turn by H(2) availability. As the study progressed, the H(2)-fed reactor experienced a diminishing ability to dechlorinate, while more stable dechlorinating activity was maintained in the reactors that were fed organic donors. The initial diminished ability of the H(2)-fed reactor to dechlorinate (after about 100 days), could be partially explained in terms of increased competition for H(2) between dechlorinators and methanogens, whereas other factors such as growth-factor limitation and/or accumulation of toxic and/or inhibitory metabolites were shown to play a role for longer incubation periods (over 500 days). In spite of decreasing activity with time, the H(2)-fed reactor proved to be the most effective in PCE dechlorination: after about 500 days, more than 65% of the added PCE was dechlorinated to ethene in the H(2)-fed reactor, versus 36%, 22%, and <1% in the methanol-fed, butyrate-fed, and control reactors, respectively.