PUF-Immobilized Bjerkandera adusta DSM 3375 as a Tool for Bioremediation of Creosote Oil Contaminated Soil.

Creosote oil, a byproduct of coal distillation, is primarily composed of aromatic compounds that are difficult to degrade, such as polycyclic aromatic hydrocarbons, phenolic compounds, and N-, S-, and O-heterocyclic compounds. Despite its toxicity and carcinogenicity, it is still often used to impregnate wood, which has a particularly negative impact on the condition of the soil in plants that impregnate wooden materials. Therefore, a rapid, effective, and eco-friendly technique for eliminating the creosote in this soil must be developed. The research focused on obtaining a preparation of Bjerkandera adusta DSM 3375 mycelium immobilized in polyurethane foam (PUF). It contained mold cells in the amount of 1.10 ± 0.09 g (DW)/g of the carrier. The obtained enzyme preparation was used in the bioremediation of soil contaminated with creosote (2% w/w). The results showed that applying the PUF-immobilized mycelium of B. adusta DSM 3375 over 5, 10, and 15 weeks of bioremediation, respectively, removed 19, 30, and 35% of creosote from the soil. After 15 weeks, a 73, 79, and 72% level of degradation of fluoranthene, pyrene, and fluorene, respectively, had occurred. The immobilized cells have the potential for large-scale study, since they can degrade creosote oil in soil.

Extensive chemical and bioassay analysis of polycyclic aromatic compounds in a creosote-contaminated superfund soil following steam enhanced extraction.

Polycyclic aromatic compounds (PACs) are organic compounds commonly found in contaminated soil. Previous studies have shown the removal of polycyclic aromatic hydrocarbons (PAHs) in creosote-contaminated soils during steam enhanced extraction (SEE). However, less is known about the removal of alkyl-PAHs and heterocyclic compounds, such as azaarenes, and oxygen- and sulfur-heterocyclic PACs (OPACs and PASHs, respectively). Further, the impact of SEE on the freely dissolved concentration of PACs in soil as well as the soil bioactivity pre- and post-SEE have yet to be addressed. To fulfil these research gaps, chemical and bioanalytical analysis of a creosote-contaminated soil, collected from a U.S. Superfund site, pre- and post-SEE were performed. The decrease of 64 PACs (5-100%) and increase in the concentrations of nine oxygenated-PAHs (OPAHs) (150%) during SEE, some of which are known to be toxic and can potentially contaminate ground water, were observed. The freely dissolved concentrations of PACs in soil were assessed using polyoxymethylene (POM) strips and the concentrations of 66 PACs decreased post-SEE (1-100%). Three in vitro reporter gene bioassays (DR-CALUX®, ERα-CALUX® and anti-AR CALUX®) were used to measure soil bioactivities pre- and post-SEE and all reporter gene bioassays measured soil bioactivity decreases post-SEE. Mass defect suspect screening tentatively identified 27 unique isomers of azaarenes and OPAC in the soil. As a remediation technique, SEE was found to remove alkyl-PAHs and heterocyclic PACs, reduce the concentrations of freely dissolved PACs, and decrease soil bioactivities.

Investigating the mycobiome of the Holcomb Creosote Superfund Site.

Even though many fungi are known to degrade a range of organic chemicals and may be advantageous for targeting hydrophobic chemicals with low bioavailability due to their ability to secrete extracellular enzymes, fungi are not commonly leveraged in the context of bioremediation. Here we sought to examine the fungal microbiome (mycobiome) at a model creosote polluted site to determine if fungi were prevalent under high PAH contamination conditions as well as to identify potential mycostimulation targets. Several significant positive associations were detected between OTUs and mid-to high-molecular weight PAHs. Several OTUs were closely related to taxa that have previously been identified in culture-based studies as PAH degraders. In particular, members belonging to the Ascomycota phylum were the most diverse at higher PAH concentrations suggesting this phylum may be promising biostimulation targets. There were nearly three times more positive correlations as compared to negative correlations, suggesting that creosote-tolerance is more common than creosote-sensitivity in the fungal community. Future work including shotgun metagenomic analysis would help confirm the presence of specific degradation genes. Overall this study suggests that mycobiome and bacterial microbiome analyses should be performed in parallel to devise the most optimal in situ biostimulation treatment strategies.

Bacteria involved in biodegradation of creosote PAH - A case study of long-term contaminated industrial area.

Polycyclic aromatic hydrocarbons (PAH) contained in creosote oil are particularly difficult to remove from the soil environment. Their hydrophobic character and low bioavailability to soil microorganisms affects their rate of biodegradation. This study was performed on samples of soil that were (for over forty years) subjected to contamination with creosote oil, and their metagenome and physicochemical properties were characterized. Moreover, the study was undertaken to evaluate the biodegradation of PAHs by autochthonous consortia as well as by selected bacteria strains isolated from long-term contaminated industrial soil. From among the isolated microorganisms, the most effective in biodegrading the contaminants were the strains Pseudomonas mendocina and Brevundimonas olei. They were able to degrade more than 60% of the total content of PAHs during a 28-day test. The biodegradation of these compounds using AT7 dispersant was enhanced only by Serratia marcescens strain. Moreover, the addition of AT7 improved the effectiveness of fluorene and acenaphthene biodegradation by Serratia marcescens 6-fold. Our results indicated that long-term contact with aromatic compounds induced the bacterial strains to use the PAHs as a source of carbon and energy. We observed that supplementation with surfactants does not increase the efficiency of hydrocarbon biodegradation.

Metataxonomic analyses reveal differences in aquifer bacterial community as a function of creosote contamination and its potential for contaminant remediation.

Metataxonomic approach was used to describe the bacterial community from a creosote-contaminated aquifer and to access the potential for in situ bioremediation of the polycyclic aromatic hydrocarbons (PAHs) by biostimulation. In general, the wells with higher PAH contamination had lower richness and diversity than others, using the Shannon and Simpson indices. By the principal coordinate analysis (PCoA) it was possible to observe the clustering of the bacterial community of most wells in response of the presence of PAH contamination. The significance analysis using edgeR package of the R program showed variation in the abundance of some Operational Taxonomic Units (OTUs) of contaminated wells compared to uncontaminated ones. Taxons enriched in the contaminated wells were correlated positively (p < 0.05) with the hydrocarbons, according to redundancy analysis (RDA). All these enriched taxa have been characterized as PAH degrading agents, such as the genus Comamonas, Geobacter, Hydrocarboniphaga, Anaerolinea and Desulfomonile. Additionally, it was possible to predict, with the PICRUSt program, a greater proportion of pathways and genes related to the degradation of PAHs in the wells with higher contamination levels. We conclude that the contaminants promoted the enrichment of several groups of degrading bacteria in the area, which strengthens the feasibility of applying biostimulation as an aquifer remediation strategy.

Characterization of polycyclic aromatic hydrocarbons in urban-rural integration area soil, North China: Spatial distribution, sources and potential human health risk assessment.

The promotion of urbanization has accelerated the development of small manufacturing workshops and brought serious environmental problems. In this study, spatial distribution, sources and potential health risk for polycyclic aromatic hydrocarbons (PAHs) in urban-rural integration area soil in North China (800 km2) were discussed. The average total concentration of 16 PAHs was 225 µg kg-1, and range from 25 to 15155 µg kg-1 (n = 250). According to the European soil quality standards, more than 70% of the samples don't reach the pollution level, while around the small workshop concentration area and non-ferrous metal smelter were more contaminated than other area. The spatial distribution of soil PAHs concentration shows that low molecular weight, medium molecular weight and high molecular weight is very similar to the distribution of total PAHs, indicating that is likely to be caused by point source pollution. The sources of PAHs were identified by positive matrix factorization. The main six sources in the region are coal and biomass combustion, creosote, coke tar, vehicle and oil, which is consistent with the local energy consumption structure. Finally, a deterministic assessment of the cancer risk showed that the range for children was 5.94 × 10-8 to 2.53 × 10-5, and adults it ranged from 2.11 × 10-8 to 9.01 × 10-6. There is not a carcinogenic risk value greater than 10-4 in the entire region, but potential carcinogenic risks persisted in some areas. We conclude that PAHs pollution of soil in the area is an issue that deserves urgent attention for the relevant departments.

Assessment of preservative migration from wood using a soil sachet method.

The ability of standard soils to capture heavy metals or polycyclic aromatic hydrocarbons (PAHs) from ammoniacal copper zinc arsenate (ACZA)- or creosote-treated wood, respectively, was assessed using pressure-treated posts immersed in a freshwater pond. The soil, in heat-sealed, permeable plastic mesh sachets, was able to intercept copper, zinc, arsenic, and PAHs migrating from the posts. Chemical levels were much higher immediately adjacent to the posts and declined with distance from the posts. Metals were consistently detected around ACZA-treated posts, while 10 of the 16 EPA priority pollutants were detected in at least one sachet embedded around creosote-treated posts at each sampling point. These results were consistent with traditional sediment sampling methods. The primary advantages of the sachets were their consistency in terms of soil characteristics and the ease with which they could be retrieved from the pond. Further studies are planned to better understand the role of soil characteristics in the sachets on the ability to capture migrating preservatives.

Extraction of PAHS from an aged creosote-polluted soil by cyclodextrins and rhamnolipids. Side effects on removal and availability of potentially toxic elements.

This study evaluated the effect of several cyclodextrins (CDs) and a rhamnolipid (RL) on the removal of polycyclic aromatic hydrocarbons (PAHs) from a co-contaminated soil which had received historically creosote and inorganic wood preservatives for almost 100 years, and the effect of such extractions on the potentially toxic elements (PTEs). The influence on such processes of an electrolyte (0.01 M Ca(NO3)2) was also studied. Up to 15.4% of the ∑16 PAHs were extracted using RL in the absence of the electrolyte as washing solution, but decreases until reaching 0.60% in the presence of Ca2+ due to RL precipitation and partial inactivation. Only up to 2% of the ∑16 PAHs was extracted with CDs (4-ring PAHs in higher concentrations), but the electrolyte had no effect on extraction. In relation to PTEs, CDs proved to be inefficient for their extraction, and even RL in the presence of the background electrolyte. But in the absence of electrolyte PTEs extraction by RL increased. Apart from that, the availability of Ni, Cr, and As, those more associated to Fe and Al soil surfaces, increased after extraction with RLs in the presence of Ca2+ (about 100% for Cr and Ni and 200% for As). Under these conditions Fe and Al availability increased two- and ten-fold, respectively, indicating that Fe-Al soil surfaces were altered. Therefore, the ionic strength and the cations present in the soil solution of soils have to be considered when RLs are used as extractants for remediation purposes.

Comprehensive composition of Creosote using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS).

Creosote is a distillation product of coal tar and is widely used as wood preservative for railway sleepers, utility poles and for other applications. Creosote can have potentially negative effects on the environment and many of the components are toxic. This study presents the analysis of a Creosote sample from a former wood impregnation plant located in the UK. The sample was analysed using two dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) and a database of compounds that could be detected was produced. The GCxGG-TOFMS was capable of detecting 1505 individual compounds, which is far more than previous estimates for the number of compounds present within Creosote. Post extraction derivatization using BTSFA with 1% TMCS was employed to increase the potential number of compounds detected with 255 derivatized compounds detected, 231 of which would not have been detected without prior derivatization. Selected derivatized compounds were quantified with limits of detection ranging from 0.6 mg/kg to 1.6 mg/kg from a concentrated dense non-aqueous phase liquid (DNAPL). This work presents the first published full analysis of a Creosote using GCxGC-TOFMS combined with derivatization.

Biosurfactant-enhanced bioremediation of aged polycyclic aromatic hydrocarbons (PAHs) in creosote contaminated soil.

The potential for biological treatment of an environment contaminated by complex petrochemical contaminants was evaluated using creosote contaminated soil in ex situ bio-slurry reactors. The efficacy of biosurfactant application and stimulation of in situ biosurfactant production was investigated. The biosurfactant produced was purified and characterised using Fourier transform infrared (FTIR) spectroscopy. Biosurfactant enhanced degradation of PAHs was 86.5% (with addition of biosurfactant) and 57% in controls with no biosurfactant and nutrient amendments after incubation for 45 days. A slight decrease in degradation rate observed in the simultaneous biosurfactant and nutrient, NH4NO3 and KH2PO4, supplemented microcosm can be attributed to preferential microbial consumption of the biosurfactant supplemented. The overall removal of PAHs was determined to be mass transport limited since the dissolution rate caused by the biosurfactant enhanced the bioavailability of the PAHs to the microorganisms. The consortium culture was predominated by the aromatic ring-cleaving species Bacillus stratosphericus, Bacillus subtilis, Bacillus megaterium, and Pseudomonas aeruginosa.

Pyrosequencing reveals the effect of mobilizing agents and lignocellulosic substrate amendment on microbial community composition in a real industrial PAH-polluted soil.

Bacterial and fungal biodiversity throughout different biostimulation and bioaugmentation treatments applied to an industrial creosote-polluted soil were analyzed by means of polyphasic approach in order to gain insight into the microbial community structure and dynamics. Pyrosequencing data obtained from initial creosote polluted soil (after a biopiling step) revealed that Alpha and Gammaproteobacteria were the most abundant bacterial groups, whereas Fusarium and Scedosporium were the main fungal genera in the contaminated soil. At the end of 60-days laboratory scale bioremediation assays, pyrosequencing and DGGE data showed that (i) major bacterial community shifts were caused by the type of mobilizing agent added to the soil and, to a lesser extent, by the addition of lignocellulosic substrate; and (ii) the presence of the non-ionic surfactant (Brij 30) hampered the proliferation of Actinobacteria (Mycobacteriaceae) and Bacteroidetes (Chitinophagaceae) and, in the absence of lignocellulosic substrate, also impeded polycyclic aromatic hydrocarbons (PAHs) degradation. The results show the importance of implementing bioremediation experiments combined with microbiome assessment to gain insight on the effect of crucial parameters (e.g. use of additives) over the potential functions of complex microbial communities harbored in polluted soils, essential for bioremediation success.

In vivo measurement, in vitro estimation and fugacity prediction of PAH bioavailability in post-remediated creosote-contaminated soil.

In this study, PAH bioavailability was assessed in creosote-contaminated soil following bioremediation in order to determine potential human health exposure to residual PAHs from incidental soil ingestion. Following 1,000 days of enhanced natural attenuation (ENA), a residual PAH concentration of 871 ± 8 mg kg(-1) (∑16 USEPA priority PAHs in the <250 µm soil particle size fraction) was present in the soil. However, when bioavailability was assessed to elucidate potential human exposure using an in vivo mouse model, the upper-bound estimates of PAH absolute bioavailability were in excess of 65% irrespective of the molecular weight of the PAH. These results indicate that a significant proportion of the residual PAH fraction following ENA may be available for absorption following soil ingestion. In contrast, when PAH bioavailability was estimated/predicted using an in vitro surrogate assay (FOREhST assay) and fugacity modelling, PAH bioavailability was up to 2000 times lower compared to measured in vivo values depending on the methodology used.

Creosote released from railway-ties recycled and the sanitary risks.

Through the history of railways, wooden crossties impregnated with potentially hazardous creosote tar, have been used for years. There are six major classes of compounds in the creosote: aromatic hydrocarbons; tar acids/phenolics; tar bases/nitrogen-containing heterocycles; aromatic amines; sulfur-containing heterocycles; and oxygen-containing heterocycles. The creosote molecules applied in railway crossties can be released in the environment and they can bioaccumulate in animals and vegetables. Some constituents (benzo(a)pyrene and phenolics like benzene) are considered as being carcinogenic which renders the entire complex of creosote to be classified as potentially carcinogenic. After several decades of use the railway-ties are been recycled for varies uses like fences, stakes for agriculture and fruit production or bank protection. In this paper are examined some environmental and sanitary risks from wood impregnated with creosote reported in the literature.

An integrated assessment of sediment remediation in a midwestern U.S. stream using sediment chemistry, water quality, bioassessment, and fish biomarkers.

A comprehensive biological, sediment, and water quality study of the lower Little Scioto River near Marion, Ohio, USA, was undertaken to evaluate the changes or improvements in biotic measurements following the removal of creosote-contaminated sediment. The study area covered 7.5 river miles (RMs), including a remediated section between RMs 6.0 and 6.8. Fish and macroinvertebrate assemblages, fish biomarkers (i.e., polycyclic aromatic hydrocarbon [PAH] metabolite levels in white sucker [Castostomus commersoni] and common carp [Cyprinus carpio] bile and DNA damage), sediment chemistry, and water quality were assessed at five locations relative to the primary source of historical PAH contamination-upstream (RM 9.2), adjacent (RM 6.5), and downstream (RMs 5.7, 4.4, and 2.7). Overall, the biomarker results were consistent with the sediment PAH results, showing a pattern of low levels of PAH bile metabolites and DNA damage at the upstream (reference or background location), as well as the remediated section, high levels at the two immediate downstream sites, and somewhat lower levels at the furthest downstream site. Results show that remediation was effective in reducing sediment contaminant concentrations and exposure of fish to PAHs and in improving fish assemblages (60% increase in index of biotic integrity scores) in remediated river sections. Additional remedial investigation and potentially further remediation is needed to improve the downstream benthic fish community, which is still heavily exposed to PAH contaminants.

A versatile cryo-focussing flow switching gas chromatography inlet for trace analysis of intractable compounds.

A wide variety of samples that can be analysed by gas chromatography do not lend themselves to the usual preparation of solvent extracts for split-splitless injections, and are best handled by purge and trap or equilibrium headspace sampling. A cryo-focussing, flow switching gas chromatography inlet system that handles different types of sample without the need for hardware changes has been prototyped. It provides excellent repeatability and linearity with liquid injections, purge and trap, and equilibrium headspace samples, in both split and splitless modes. The performance of the system was tested with sub-nanogram quantities of challenging analytes such as free carboxylic acids, alcohols, diols, phenols and aldehydes, and volatiles purged from contaminated soil, mammal faeces, a pesticide formulation, and a spice. Repeatability RSDs for peak areas were consistently below 11% and repeatabilities of retention times below 0.05%, independently of sample type (liquid or gas phase) and nature or quantity of compound. Regression coefficients of peak areas vs. quantity were typically ≥ 0.999 over two orders of magnitude ranges extending down to below 0.01 ng, also independently of sample and analyte. Limits of quantitation were robustly below 0.1-0.2 ng. Peak shapes and resolution are the same with use of the cryo-trap and flow switch as they are with conventional injections. Performance is robust to flow rate and, for most compounds, to trapping and desorption temperature. The cryo-trapping flow switching inlet's performance parameters match those of other sample introduction systems, and are achieved with sub-nanogram quantities of intractable analytes.

Self-sustaining smoldering combustion for NAPL remediation: laboratory evaluation of process sensitivity to key parameters.

Smoldering combustion has been introduced recently as a potential remediation strategy for soil contaminated by nonaqueous phase liquids (NAPLs). Published proof-of-concept experiments demonstrated that the process can be self-sustaining (i.e., requires energy input only to start the process) and achieve essentially complete remediation of the contaminated soil. Those initial experiments indicated that the process may be applicable across a broad range of NAPLs and soils. This work presents the results of a series of bench-scale experiments that examine in detail the sensitivity of the process to a range of key parameters, including contaminant concentration, water saturation, soil type, and air flow rates for two contaminants, coal tar and crude oil. Smoldering combustion was observed to be self-sustaining in the range 28,400 to 142,000 mg/kg for coal tar and in the range 31,200 to 104,000 mg/kg for crude oil, for the base case air flux. The process remained self-sustaining and achieved effective remediation across a range of initial water concentrations (0 to 177,000 mg/kg water) despite extended ignition times and decreased temperatures and velocities of the reaction front. The process also exhibited self-sustaining and effective remediation behavior across a range of fine to coarse sand grain sizes up to a threshold maximum value between 6 mm and 10 mm. Propagation velocity is observed to be highly dependent on air flux, and smoldering was observed to be self-sustaining down to an air Darcy flux of at least 0.5 cm/s for both contaminants. The extent of remediation in these cases was determined to be at least 99.5% and 99.9% for crude oil and coal tar, respectively. Moreover, no physical evidence of contamination was detected in the treatment zone for any case where a self-sustaining reaction was achieved. Lateral heat losses to the external environment were observed to significantly affect the smoldering process at the bench scale, suggesting that the field-scale lower bounds on concentration and air flux and upper bound on grain size were not achieved; larger scale experiments and field trials where lateral heat losses are much less significant are necessary to define these process limits for the purposes of field application. This work provides valuable design data for pilot field trials of both in situ and ex situ smoldering remediation applications.

A comparative toxicity assessment of materials used in aquatic construction.

Comparative toxicity testing was performed on selected materials that may be used in aquatic construction projects. The tests were conducted on the following materials: (1) untreated wood species (hemlock [Tsuga ssp], Western red cedar (Thuja plicata), red oak [Quercus rubra], Douglas fir [Pseudotsuga menziesii], red pine [Pinus resinosa], and tamarack [Larix ssp]); (2) plastic wood; (3) Ecothermo wood hemlock stakes treated with preservatives (e.g., chromated copper arsenate [CCA], creosote, alkaline copper quaternary [ACQ], zinc naphthenate, copper naphthenate, and Lifetime Wood Treatment); (4) epoxy-coated steel; (5) hot-rolled steel; (6) zinc-coated steel; and (7) concrete. Those materials were used in acute lethality tests with rainbow trout, Daphnia magna, Vibrio fischeri and threespine stickleback. The results indicated the following general ranking of the materials (from the lowest to highest LC(50) values); ACQ > creosote > zinc naphthenate > copper naphthenate > CCA (treated at 22.4 kg/m(3)) > concrete > red pine > western red cedar > red oak > zinc-coated steel > epoxy-coated steel > CCA (6.4 kg/m(3)). Furthermore, the toxicity results indicated that plastic wood, certain untreated wood species (hemlock, tamarack, Douglas fir, and red oak), hot-rolled steel, Ecothermo wood, and wood treated with Lifetime Wood Treatment were generally nontoxic to the test species.

Spatial uncoupling of biodegradation, soil respiration, and PAH concentration in a creosote contaminated soil.

Hotspots and coldspots of concentration and biodegradation of polycyclic aromatic hydrocarbons (PAHs) marginally overlapped at the 0.5-100 m scale in a creosote contaminated soil in southern Sweden, suggesting that concentration and biodegradation had little spatial co-variation. Biodegradation was substantial and its spatial variability considerable and highly irregular, but it had no spatial autocorrelation. The soil concentration of PAHs explained only 20-30% of the variance of their biodegradation. Soil respiration was spatially autocorrelated. The spatial uncoupling between biodegradation and soil respiration seemed to be governed by the aging of PAHs in the soil, since biodegradation of added 13C phenanthrene covaried with both soil respiration and microbial biomass. The latter two were also correlated with high concentrations of phospholipid fatty acids (PLFAs) that are common in gram-negative bacteria. However, several of the hotspots of biodegradation coincided with hotspots for the distribution of a PLFA indicative of fungal biomass.

Bioavailability of residual polycyclic aromatic hydrocarbons following enhanced natural attenuation of creosote-contaminated soil.

The impact of residual PAHs (2250 +/- 71 microg total PAHs g(-1)) following enhanced natural attenuation (ENA) of creosote-contaminated soil (7767 +/- 1286 microg total PAHs g(-1)) was assessed using a variety of ecological assays. Microtox results for aqueous soil extracts indicated that there was no significant difference in EC(50) values for uncontaminated, pre- and post-remediated soil. However, in studies conducted with Eisenia fetida, PAH bioaccumulation was reduced by up to 6.5-fold as a result of ENA. Similarly, Beta vulgaris L. biomass yields were increased 2.1-fold following ENA of creosote-contaminated soil. While earthworm and plant assays indicated that PAH bioavailability was reduced following ENA, the residual PAH fraction still exerted toxicological impacts on both receptors. Results from this study highlight that residual PAHs following ENA (presumably non-bioavailable to bioremediation) may still be bioavailable to important receptor organisms such as earthworms and plants.

Rebound of a coal tar creosote plume following partial source zone treatment with permanganate.

The long-term management of dissolved plumes originating from a coal tar creosote source is a technical challenge. For some sites stabilization of the source may be the best practical solution to decrease the contaminant mass loading to the plume and associated off-site migration. At the bench-scale, the deposition of manganese oxides, a permanganate reaction byproduct, has been shown to cause pore plugging and the formation of a manganese oxide layer adjacent to the non-aqueous phase liquid creosote which reduces post-treatment mass transfer and hence mass loading from the source. The objective of this study was to investigate the potential of partial permanganate treatment to reduce the ability of a coal tar creosote source zone to generate a multi-component plume at the pilot-scale over both the short-term (weeks to months) and the long-term (years) at a site where there is >10 years of comprehensive synoptic plume baseline data available. A series of preliminary bench-scale experiments were conducted to support this pilot-scale investigation. The results from the bench-scale experiments indicated that if sufficient mass removal of the reactive compounds is achieved then the effective solubility, aqueous concentration and rate of mass removal of the more abundant non-reactive coal tar creosote compounds such as biphenyl and dibenzofuran can be increased. Manganese oxide formation and deposition caused an order-of-magnitude decrease in hydraulic conductivity. Approximately 125 kg of permanganate were delivered into the pilot-scale source zone over 35 days, and based on mass balance estimates <10% of the initial reactive coal tar creosote mass in the source zone was oxidized. Mass discharge estimated at a down-gradient fence line indicated >35% reduction for all monitored compounds except for biphenyl, dibenzofuran and fluoranthene 150 days after treatment, which is consistent with the bench-scale experimental results. Pre- and post-treatment soil core data indicated a highly variable and random spatial distribution of mass within the source zone and provided no insight into the mass removed of any of the monitored species. The down-gradient plume was monitored approximately 1, 2 and 4 years following treatment. The data collected at 1 and 2 years post-treatment showed a decrease in mass discharge (10 to 60%) and/or total plume mass (0 to 55%); however, by 4 years post-treatment there was a rebound in both mass discharge and total plume mass for all monitored compounds to pre-treatment values or higher. The variability of the data collected was too large to resolve subtle changes in plume morphology, particularly near the source zone, that would provide insight into the impact of the formation and deposition of manganese oxides that occurred during treatment on mass transfer and/or flow by-passing. Overall, the results from this pilot-scale investigation indicate that there was a significant but short-term (months) reduction of mass emanating from the source zone as a result of permanganate treatment but there was no long-term (years) impact on the ability of this coal tar creosote source zone to generate a multi-component plume.