Aroclor misidentification in environmental samples: how do we communicate more effectively between the laboratory and the data user?

Disposal of carbonless copy paper (CCP) paper sludge during the 1960s contaminated a site in the USA with PCBs. Despite historic records of CCP sludge disposal and absence of evidence of any other disposal, a dispute arose among the parties over the source of the PCBs. Aroclor 1242 is well documented as the PCB mixture used in CCP, yet Aroclors 1242, 1248, 1254, and 1260 were reported by the analytical laboratory. How could the PCBs at a single, small site be reported as four different Aroclors? Some claimed that there had to be at least four Aroclors source inputs to the site. Disposal of four different Aroclors at this site would simply defy logic and the historic record. Weathering of the mixtures is part of the story. A larger issue is the conflict between the intent of the USEPA 8082 method to determine the total PCB content in environmental samples to facilitate environmental cleanup and disposal decisions within a regulatory context versus the data users' intent to identify the PCB sources. This inappropriate extension of the data leads to erroneous conclusions. To mitigate problems like this, laboratory analysis requests need to be matched to the intended data usage; conversely, the data must not be over-interpreted beyond the limits of the method. The PCB analysis community needs to develop a better articulation of the limits of Aroclor identification for the broader community that may naïvely assume that if the laboratory reports "Aroclor 1248," then someone must have placed Aroclor 1248 at the site. After all, when a laboratory reports "lead" or "chloroform," those identifications are never in question.

PCB dechlorination hotspots and reductive dehalogenase genes in sediments from a contaminated wastewater lagoon.

Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants that are distributed worldwide. Although industrial PCB production has stopped, legacy contamination can be traced to several different commercial mixtures (e.g., Aroclors in the USA). Despite their persistence, PCBs are subject to naturally occurring biodegradation processes, although the microbes and enzymes involved are poorly understood. The biodegradation potential of PCB-contaminated sediments in a wastewater lagoon located in Virginia (USA) was studied. Total PCB concentrations in sediments ranged from 6.34 to 12,700 mg/kg. PCB congener profiles in sediment sample were similar to Aroclor 1248; however, PCB congener profiles at several locations showed evidence of dechlorination. The sediment microbial community structure varied among samples but was dominated by Proteobacteria and Firmicutes. The relative abundance of putative dechlorinating Chloroflexi (including Dehalococcoides sp.) was 0.01-0.19% among the sediment samples, with Dehalococcoides sp. representing 0.6-14.8% of this group. Other possible PCB dechlorinators present included the Clostridia and the Geobacteraceae. A PCR survey for potential PCB reductive dehalogenase genes (RDases) yielded 11 sequences related to RDase genes in PCB-respiring Dehalococcoides mccartyi strain CG5 and PCB-dechlorinating D. mccartyi strain CBDB1. This is the first study to retrieve potential PCB RDase genes from unenriched PCB-contaminated sediments.

Growth and reproductive effects from dietary exposure to Aroclor 1268 in mink (Neovison vison), a surrogate model for marine mammals.

Polychlorinated biphenyls (PCBs) from the commercial mixture Aroclor 1268 were historically released into the Turtle-Brunswick River estuary (southeastern Georgia, USA) from industrial operations. Sum PCBs (ΣPCBs) in blubber samples from Turtle-Brunswick River estuary bottlenose dolphins (Tursiops truncatus) have been reported at concentrations more than 10-fold higher than those observed in dolphins from adjacent regional estuaries. Given that toxicity data specific to Aroclor 1268 and applicable to marine mammals are limited, predicting the toxic effects of Aroclor 1268 in dolphins is uncertain, particularly because of its unique congener profile and associated physiochemical characteristics compared with other PCB mixtures. American mink (Neovison vison) were chosen as a surrogate model for cetaceans to develop marine mammalian PCB toxicity benchmarks. Mink are a suitable surrogate species for cetaceans in toxicity studies because of similarities in diet and taxonomic class, and a characteristic sensitivity to PCBs provides a potential safety factor when using mink toxicology data for cross-species extrapolations. Effects of dietary exposure to Aroclor 1268 on reproduction, growth, and mortality in mink were compared with both a negative control and a positive control (3,3',4,4',5-pentachlorobiphenyl, PCB 126). Aroclor 1268 dietary ΣPCB concentrations ranged from 1.8 µg/g feed wet weight to 29 µg/g feed wet weight. Whelp success was unaffected by Aroclor 1268 exposure at any level. Treatment mean litter size, kit growth, and kit survival were adversely affected relative to the negative control at dietary ΣPCB concentrations of 10.6 µg/g feed wet weight and greater.

Enzyme induction and histopathology elucidate aryl hydrocarbon receptor-mediated versus non-aryl hydrocarbon receptor-mediated effects of Aroclor 1268 in American mink (Neovison vison).

Polychlorinated biphenyl (PCB) concentrations reported in preferred prey and blubber of bottlenose dolphins from the Turtle-Brunswick River estuary (Georgia, USA) suggest the potential for adverse effects. However, PCBs in Turtle-Brunswick River estuary dolphins are primarily derived from Aroclor 1268, and predicting toxic effects of Aroclor 1268 is uncertain because of the mixture's unique composition and associated physiochemical characteristics. These differences suggest that toxicity benchmarks for other PCB mixtures may not be relevant to dolphins exposed to Aroclor 1268. American mink (Neovison vison) were used as a surrogate model for cetaceans to characterize mechanisms of action associated with Aroclor 1268 exposure. Mink share similarities in phylogeny and life history with cetaceans and are characteristically sensitive to PCBs, making them an attractive surrogate species for marine mammals in ecotoxicity studies. Adult female mink and a subsequent F1 generation were exposed to Aroclor 1268 through diet, and effects on enzyme induction, histopathology, thyroid hormone regulation, hematology, organ weights, and body condition index were compared to a negative control and a 3,3',4,4',5-pentachlorobiphenyl (PCB 126)-positive control. Aroclor 1268 dietary exposure concentrations ranged from 1.8 µg/g wet weight to 29 µg/g wet weight. Anemia, hypothyroidism, and hepatomegaly were observed in mink exposed to Aroclor 1268 beyond various dietary thresholds. Cytochrome P450 induction and squamous epithelial proliferation jaw lesions were low in Aroclor 1268 treatments relative to the positive control. Differences in enzyme induction and the development of squamous epithelial proliferation jaw lesions between Aroclor 1268 treatments and the positive control, coupled with effects observed in Aroclor 1268 treatments not observed in the positive control, indicate that mechanisms additional to the aryl hydrocarbon receptor-mediated pathway are associated with Aroclor 1268 exposure.

Nano/bio treatment of polychlorinated biphenyls with evaluation of comparative toxicity.

The persistence of polychlorinated biphenyl (PCB) Aroclor 1248 in soils and sediments is a major concern because of its toxicity and presence at high concentrations. In this study, we developed an integrated remediation system for PCBs using chemical catalysis and biodegradation. The dechlorination of Aroclor 1248 was achieved by treatment with bimetallic nanoparticles Pd/nFe under anoxic conditions. Among the 32 PCB congeners of Aroclor 1248 examined, our process dechlorinated 99%, 92%, 84%, and 28% of tri-, tetra-, penta-, and hexachlorinated biphenyls, respectively. The resulting biphenyl was biodegraded rapidly by Burkholderia xenovorans LB400. Benzoic acid was detected as an intermediate during the biodegradation process. The toxicity of the residual PCBs after nano-bio treatment was evaluated in terms of toxic equivalent values which decreased from 33.8×10(-5)µgg(-1) to 9.5×10(-5)µgg(-1). The residual PCBs also had low cytotoxicity toward Escherichia coli as demonstrated by lower reactive oxygen species levels, lower glutathione peroxidase activity, and a reduced number of dead bacteria.

Evaluation of three activated carbons for combined adsorption and biodegradation of PCBs in aquatic sediment.

Three commercial granular activated carbons (GACs) were studied at laboratory scale with a view to the combined adsorption and biodegradation of PCBs in aquatic sediment. The three GACs, with contrasting physico-chemical characteristics, all show a high adsorption of PCBs and are thus capable of reducing aqueous pollutant concentrations. After a one-month incubation with 'Aroclor 1242'-spiked sediment, the three GACs were each colonized by a multispecies biofilm, although with different amounts of attached bacterial biomass and significantly distinct genetic bacterial communities; interestingly, the highest bacterial biomass was attached to the microporous vegetable GAC. The multispecies biofilms developed on the three GACs were all predominantly composed of Proteobacteria, especially the ß-, γ- and δ- subclasses, Chloroflexi and Acidobacteria, with genera previously found in environments containing PCBs or biphenyls, or able to perform cometabolic and direct PCB degradation. After an eight-month incubation under aerobic conditions, it was only the vegetable Picabiol GAC, with its low microporous volume, high total surface area and acidic property, that showed a significant (21%) reduction of tri- through penta-CB. Our results suggest that PCB bio-transformation by the bacterial community attached to the GAC is influenced by GAC's physico-chemical characteristics. Thus, a properly selected GAC could effectively be used to a) sequestrate and concentrate PCB from contaminated aquatic sediment and b) act as a support for efficient PCB degradation by an autochthonous bacterial biofilm.

Effects of activated carbon on reductive dechlorination of PCBs by organohalide respiring bacteria indigenous to sediments.

Polychlorinated biphenyls (PCBs) have accumulated in aquatic sediments due to their inherent chemical stability and their presence poses a risk due to their potential toxicity in humans and animals. Granular activated carbon (GAC) has been applied to PCB contaminated sediment sites to reduce the aqueous concentration by sequestration thus reducing the PCB exposure and toxicity to both benthic and aquatic organisms. However, it is not known how the reduction of PCB bioavailability by adsorption to GAC affects bacterial transformation of PCBs by indigenous organohalide respiring bacteria. In this study, the impact of GAC on anaerobic dechlorination by putative organohalide respiring bacteria indigenous to sediment from Baltimore Harbor was examined. It was shown that the average Cl/biphenyl after dehalogenation of Aroclor 1260 was similar between treatments with and without GAC amendment. However, GAC caused a substantial shift in the congener distribution whereby a smaller fraction of highly chlorinated congeners was more extensively dechlorinated to mono- through tri-chlorinated congeners compared to the formation of tri- through penta-chlorinated congeners in unamended sediment. The results combined with comparative sequence analysis of 16S rRNA gene sequences suggest that GAC caused a community shift to putative organohalide respiring phylotypes that coincided with more extensive dechlorination of ortho and unflanked chlorines. This shift in activity by GAC shown here for the first time has the potential to promote greater degradation in situ by promoting accumulation of less chlorinated congeners that are generally more susceptible to complete mineralization by aerobic PCB degrading bacteria.

Nanoscale zerovalent iron alters soil bacterial community structure and inhibits chloroaromatic biodegradation potential in Aroclor 1242-contaminated soil.

Nanoscale zerovalent iron (nZVI) has potential for the remediation of organochlorine-contaminated environments. Environmental safety concerns associated with in situ deployment of nZVI include potential negative impacts on indigenous microbes whose biodegradative functions could contribute to contaminant remediation. With respect to a two-step polychlorinated biphenyl remediation scenario comprising nZVI dechlorination followed by aerobic biodegradation, we examined the effect of polyacrylic acid (PAA)-coated nZVI (mean diameter = 12.5 nm) applied at 10 g nZVI kg(-1) to Aroclor-1242 contaminated and uncontaminated soil over 28 days. nZVI had a limited effect on Aroclor congener profiles, but, either directly or indirectly via changes to soil physico-chemical conditions (pH, Eh), nZVI addition caused perturbation to soil bacterial community composition, and reduced the activity of chloroaromatic mineralizing microorganisms. We conclude that nZVI addition has the potential to inhibit microbial functions that could be important for PCB remediation strategies combining nZVI treatment and biodegradation.

Treatment of Aroclor 1016 contaminated soil by hydrogen peroxide: laboratory column study.

The potential and feasibility of treating soil contaminated with electrical insulating oil, Aroclor 1016, containing polychlorinated biphenyls (PCBs) with stabilized hydrogen peroxide were evaluated using columns packed with soils of two different matrixes. The column experiments showed that PCBs degraded by the stabilized hydrogen peroxide treatment in both soil matrixes, although the efficacy of the treatment depended strongly on the soil characteristics. The removal of PCB-containing oil was higher in sandy silt soil than in sandy soil. While a higher iron content promoted hydrogen peroxide oxidation of the contaminant in sandy silt soil, lower permeability and higher organic matter content contributed to an oxidation decrease as a function of depth. Dehydrogenase activity measurements indicated no substantial changes in microbial activity during the treatment of both sandy and sandy silt soils, thus offering opportunities to apply the hydrogen peroxide treatment to the remediation of PCB-contaminated soil.

Polychlorinated biphenyls-containing electrical insulating oil contaminated soil treatment with calcium and magnesium peroxides.

Calcium and magnesium peroxides were applied for the treatment of soil contaminated by polychlorinated biphenyls-containing electrical insulating oil (Aroclor 1016). The removal of PCB-containing electrical insulating oil was achieved with the addition of either calcium peroxide or magnesium peroxide alone and dependent on dosages of the chemical. A 21-d treatment of 60% watered soil with the moderate addition (chemical/oil weight ratio of 0.005/1) of either calcium peroxide or magnesium peroxide resulted in nearly complete (96 ± 2%) oil removal, unsubstantial increase in soil pH and almost no changes in oxygen consumption and dehydrogenase activity, making it suitable for the soil decontamination.

Congener-based analysis of the weathering of PCB Aroclor 1242 in paper mill sludge.

Aroclor 1242 contains a high percentage of lightly chlorinated congeners, which makes it susceptible to congener profile alterations as a result of physical-chemical environmental weathering by water washing, evaporation, and volatilization. The analysis of the variability of congener profiles in paper sludge samples using PCA, mixing models, and correlation (R(2)) analysis, provided an integrated description of the behavior of Aroclor 1242 after its release in the environment. The results showed that the total PCB concentration decreased as the sample experienced weathering, with the congener profile of Aroclor 1242 shifting towards resembling heavier Aroclors as lighter congeners were lost. Mixing model analysis confirmed that a sample containing weathered Aroclor 1242 could easily be misidentified by laboratories as containing a mix of heavier Aroclors. The R(2) analysis showed that the profile of the congeners within a homologue group remained the same after weathering. This analysis showed that congeners that belong to the same level of chlorination behave similarly in such a manner that retains their overall profile when exposed to physical weathering.

Use of a polar ionic liquid as second column for the comprehensive two-dimensional GC separation of PCBs.

The orthogonality of three columns coupled in two series was studied for the congener specific comprehensive two-dimensional GC separation of polychlorinated biphenyls (PCBs). A non-polar capillary column coated with poly(5%-phenyl-95%-methyl)siloxane was used as the first ((1)D) column in both series. A polar capillary column coated with 70% cyanopropyl-polysilphenylene-siloxane or a capillary column coated with the ionic liquid 1,12-di(tripropylphosphonium)dodecane bis(trifluoromethane-sulfonyl)imide were used as the second ((2)D) columns. Nine multi-congener standard PCB solutions containing subsets of all native 209 PCBs, a mixture of 209 PCBs as well as Aroclor 1242 and 1260 formulations were used to study the orthogonality of both column series. Retention times of the corresponding PCB congeners on (1)D and (2)D columns were used to construct retention time dependences (apex plots) for assessing orthogonality of both columns coupled in series. For a visual assessment of the peak density of PCBs congeners on a retention plane, 2D images were compared. The degree of orthogonality of both column series was, along the visual assessment of distribution of PCBs on the retention plane, evaluated also by Pearson's correlation coefficient, which was found by correlation of retention times t(R,i,2D) and t(R,i,1D) of corresponding PCB congeners on both column series. It was demonstrated that the apolar+ionic liquid column series is almost orthogonal both for the 2D separation of PCBs present in Aroclor 1242 and 1260 formulations as well as for the separation of all of 209 PCBs. All toxic, dioxin-like PCBs, with the exception of PCB 118 that overlaps with PCB 106, were resolved by the apolar/ionic liquid series while on the apolar/polar column series three toxic PCBs overlapped (105+127, 81+148 and 118+106).

Feathers as bioindicators of PCB exposure in clapper rails.

In this study we used feathers to biomonitor exposure to the polychlorinated biphenyl (PCB) Aroclor 1268 congener mixture in clapper rails (Rallus longirostris). This species has been used as an indicator species of environmental damage for the LCP superfund site located in Brunswick, GA, USA which is contaminated with Aroclor 1268, a congener mixture that has been used in limited amounts elsewhere and therefore can be used as a contaminant marker. The Aroclor 1268 congener mixture, including congener profiles, were quantified in feathers using gas chromatography (GC). Concurrently, each sample was quantified for the total Aroclor 1268 congener mixture using an enzyme-linked immunosorbant assay (ELISA) and compared to the GC results to determine if ELISA was an efficient method for quantifying or qualifying PCBs in feathers. ELISA consistently quantified PCB loads over an order of magnitude lower than the GC. Based on sample replication, extraction recovery, and sample spike, it appears that GC is the more reliable method of detection and that ELISA methods may be more suitable for qualitative exposure assessment for this particular Aroclor. Moreover, since all clapper rails from the LCP site had the Aroclor 1268 congener mixture in their feathers, this experiment showed that birds were returning to the site to breed despite the adverse effects experienced by this population from the contamination revealed in previous studies. This study also supports the utility of feathers as a non-lethal mechanism by which to biomonitor PCBs in the environment.

Discovery of non-aroclor PCB (3,3'-dichlorobiphenyl) in Chicago air.

Air samples were collected in Chicago, Illinois in 2007, and 3,3'-dichlorobiphenyl (PCB11, CAS 2050-67-1) was detected and quantified using GC/MS/MS in 91% of 184 samples. To the best of our knowledge, this is the first published report of PCB11 in ambient air. This compound is ubiquitous in air throughout the city of Chicago. The annual mean concentration in air samples collected from November 2006 to November 2007 is 24 pg m(-3) (+/-24 pg m(-3) SD), although the seasonal variation is significant. The concentration of PCB11 is up to 15% of measured polychlorinated biphenyls (PCBs) in air but only up to 0.16% of commercial Aroclor mixtures that were banned from production in the 1970s. PCB11 is associated with pigments, paints, and resins and has been reported to be a dominant congener among PCBs detected in the wastewater effluent from paint production. The wide distribution of PCB11 in Chicago air is consistent with volatilization of this compound from painted surfaces although the actual source of PCB11 is unknown.

Dechlorination of individual congeners in aroclor 1248 as enhanced by chlorobenzoates, chlorophenols, and chlorobenzenes.

Previous investigations showed that three classes of haloaromatic compounds (HACs; chlorobenzoates, chlorophenols, and chlorobenzenes) enhanced the reductive dechlorination of Aroclor 1248, judging from the overall extent of reduction in Cl atoms on the biphenyl. In the present study, we further investigated the kind of polychlorinated biphenyl (PCB) congeners involved in the enhanced dechlorination by four isomers belonging to each class (2,3-, 2,5-, 2,3,5-, and 2,4,6-chlorobenzoates; 2,3-, 3,4-, 2,5-, and 2,3,6-chlorophenols; and 1,2-, 1,2,3-, 1,2,4-, and penta-chlorobenzenes). Although the PCB congeners involved in the enhanced dechlorination varied with the HACs, the enhancement primarily involved paradechlorination of the same congeners (2,3,4'-, 2,3,4,2'- plus 2,3,6,4'-, 2,5,3',4'- plus 2,4,5,2',6'-, and 2,3,6,2',4'- chlorobiphenyls), regardless of the HACs. These congeners are known to have low threshold concentrations for dechlorination. To a lesser extent, the enhancement also involved meta dechlorination of certain congeners with high threshold concentrations. There was no or less accumulation of 2,4,4'- and 2,5,4'-chlorobiphenyls as final products under HAC amendment. Although the dechlorination products varied, the accumulation of orthosubstituted congeners, 2-, 2,2'-, and 2,6-chlorobiphenyls, was significantly higher with the HACs, indicating a more complete dechlorination of the highly chlorinated congeners. Therefore, the present results suggest that the enhanced dechlorination under HAC enrichment is carried out through multiple pathways, some of which may be universal, regardless of the kind of HACs, whereas others may be HAC-specific.

Compound-specific chlorine isotope analysis of polychlorinated biphenyls isolated from Aroclor and Clophen technical mixtures.

Compound-specific chlorine isotope analysis (CSIA-Cl) is promising as a novel and powerful method for monitoring in situ degradation of organochlorines in the environment and for source fingerprinting purposes. In order to apply CSIA-Cl in field studies of polychlorinated biphenyls (PCBs), the chlorine isotopic composition (delta(37)Cl) of individual PCB congeners in source materials must be known. In the present study, we determined delta(37)Cl of 18 congeners isolated from three widely produced technical mixtures. All congeners provided delta(37)Cl ranging between -1.9 per thousand and -3.5 per thousand. Although the comparable products Aroclor 1242 (-2.0 per thousand to -2.5 per thousand) and Clophen A30 (-1.9 per thousand to -3.0 per thousand) were synthesized by different industries, they provided similar delta(37)Cl for the same type of congeners. On the contrary, the more chlorinated congeners present in Aroclor 1254 (-2.1 to -3.5 per thousand) were more (37)Cl depleted compared to Aroclor 1242 manufactured by the same company. Overall, delta(37)Cl of PCB congeners decreased by -0.26 per thousand for each additional chlorine atom.

Biodegradation of PCBs in two-phase partitioning bioreactors following solid extraction from soil.

This article demonstrates the feasibility of a novel process concept for the remediation of PCB contaminated soil. The proposed process consists of PCB extraction from soil using solid polymer beads, followed by biodegradation of the extracted PCBs in a solid-liquid two-phase partitioning bioreactor (TPPB), where PCBs are delivered from the polymer beads to the degrading organisms. The commercially available thermoplastic polymer Hytrel was used to extract Aroclor 1242 from contaminated artificial soil in bench scale experiments. Initial PCB contamination levels of 100 and 1,000 mg kg(-1) could be reduced to 32% +/- 1 to 41% +/- 7 of the initial value after 48 h mixing in the presence of a mobilizing agent at polymer-to-soil ratios of 1% (w/w) and 10% (w/w). The decrease of detectable PCBs in the soil was consistent with an increase of PCBs in the polymer beads. It was further shown that Aroclor 1242 could be delivered to the PCB degrading organism Burkholderia xenovorans LB400 in a solid-liquid TPPB via Hytrel beads. A total of 70 mg Aroclor 1242 could be degraded in a 1 L solid-liquid TPPB within 80 h of operation.

Development and characterization of stable sediment-free anaerobic bacterial enrichment cultures that dechlorinate aroclor 1260.

We have developed sediment-free anaerobic enrichment cultures that dechlorinate a broad spectrum of highly chlorinated polychlorinated biphenyls (PCBs). The cultures were developed from Aroclor 1260-contaminated sediment from the Housatonic River in Lenox, MA. Sediment slurries were primed with 2,6-dibromobiphenyl to stimulate Process N dechlorination (primarily meta dechlorination), and sediment was gradually removed by successive transfers (10%) to minimal medium. The cultures grow on pyruvate, butyrate, or acetate plus H(2). Gas chromatography-electron capture detector analysis demonstrated that the cultures extensively dechlorinate 50 to 500 mug/ml of Aroclor 1260 at 22 to 24 degrees C by Dechlorination Process N. Triplicate cultures of the eighth transfer without sediment dechlorinated 76% of the hexa- through nonachlorobiphenyls in Aroclor 1260 (250 mug/ml) to tri- through pentachlorobiphenyls in 110 days. At least 64 PCB congeners, all of which are chlorinated on both rings and 47 of which have six or more chlorines, were substrates for this dechlorination. To characterize the bacterial diversity in the enrichments, we used eubacterial primers to amplify and clone 16S rRNA genes from DNA extracted from cultures grown on acetate plus H(2). Restriction fragment length polymorphism analysis of 107 clones demonstrated the presence of Thauera-like Betaproteobacteria, Geobacter-like Deltaproteobacteria, Pseudomonas species, various Clostridiales, Bacteroidetes, Dehalococcoides of the Chloroflexi group, and unclassified Eubacteria. Our development of highly enriched, robust, stable, sediment-free cultures that extensively dechlorinate a highly chlorinated commercial PCB mixture is a major and unprecedented breakthrough in the field. It will enable intensive study of the organisms and genes responsible for a major PCB dechlorination process that occurs in the environment and could also lead to effective remediation applications.

Reductive dechlorination of polychlorinated biphenyls as affected by natural halogenated aromatic compounds.

We investigated the effects of halogenated aromatic compounds (HACs) including naturally occurring ones (L-thyroxine, 3-chloro-L-tyrosine, 5-chloroindole, 2-chlorophenol, 4-chlorophenol and chlorobenzene) on polychlorinated biphenyl (PCB) dechlorination in sediment cultures. A PCB-dechlorinating enrichment culture of sediment microorganisms from the St. Lawrence River was used as an initial inoculum. When the culture was inoculated into Aroclor 1248 sediments amended with each of the six HACs, the extent of dechlorination was not enhanced by amendment with HACs. The dechlorination patterns in the HAC-amended sediments were nearly identical to that of the HAC-free sediments except the 3-chloro-L-tyrosine-amended ones where no dechlorination activity was observed. When these sediment cultures were transferred into fresh sediments with the same HACs, the dechlorination specificities remained the same as those of the initial inoculations. Thus, in the present study, the substrate range of the highly selected enrichment culture could not be broadened by the HACs. It appears that HACs affect PCB dechlorination mainly through population selection rather than enzyme induction of single population.

Removal of PCB-DNAPL from a rough-walled fracture using alcohol/polymer flooding.

Phase behaviour experiments employing PCB (Aroclor 1242)/alcohol/water systems were conducted with ethanol (EtOH) and n-propanol (nPA). Both exhibited an affinity for the aqueous phase within the entire two-phase region. As much as 88% by volume (88% vol.) EtOH and 80% vol. nPA were necessary to achieve full miscibility of the PCB in the aqueous phase. DNAPL-water interfacial tension (IFT) was reduced from 38.9 dyn/cm to 4.7 dyn/cm and 2.4 dyn/cm with 80% vol. EtOH and 76% vol. nPA. The addition of alcohol brought about 41% and 54% reductions in DNAPL viscosity at maximal concentrations of EtOH and nPA. Density of the PCB-DNAPL was relatively unaffected by the presence of alcohol. A series of seven experiments were conducted where successive slugs of nPA and xanthan gum polymer solutions were injected into a fractured shale sample. A 30% vol. nPA solution injected under a hydraulic gradient of 0.36 allowed enhanced PCB removal primarily through reduction of IFT and resulted in 72% DNAPL recovery. Several pore volumes of alcohol solution were necessary to displace all the potentially mobile non-wetting phase since the high-viscosity DNAPL was mobilized at a lower flow rate than the overall fluid velocity, illustrating non-piston displacement. The injection of a 95% vol. nPA alcohol solution, theoretically at a sufficient concentration to produce fully miscible displacement of the residual DNAPL at equilibrium, resulted in non-equilibrium partitioning of the PCB into the flushing solution, likely due to the high fluid velocities in the fracture. The injection of 200 pore volumes of 95% vol. nPA solution resulted in 94% DNAPL recovery. Alcohol floods operated below the miscibility envelope appear to be a valuable source zone remedial alternative where the objective is to reduce DNAPL mobility to zero, but it should be noted that DNAPL mobility is increased during the application of the technology and steps may need to be taken to prevent unwanted vertical mobilization.