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Pentachlorophenol (PCP) is a highly toxic and carcinogenic compound with significant environmental impact, necessitating effective treatment technologies. This study evaluates PCP removal mechanisms, including adsorption and biodegradation, during the startup of a horizontal-flow anaerobic immobilized biomass reactor (HAIB), and examines the impact of PCP concentration on microbial diversity using denaturing gradient gel electrophoresis (DGGE). The primary mechanism for PCP removal in the HAIB was adsorption, effectively described by the Freundlich isotherm model. Adsorption efficiency ranged from 86 to 104% for PCP concentrations between 0.2 and 5.0 mg/L, and 46% to 64% for concentrations between 0.098 and 0.05 mg/L. Additionally, PCP degradation intermediates such as 2,3-DCP and 2,6-DCP were detected, indicating that biodegradation also occurred in the HAIB. Organic matter degradation averaged 81 ± 9%, and methane content in the biogas averaged 46 ± 9%, confirming the anaerobic process. No inhibition of microbial activity was observed due to PCP toxicity, even at a PCP load of 5 mg PCP/g STV per day. While the archaeal community showed only slight changes, with similarity coefficients ranging from 88 to 95%, the bacterial community was significantly affected by PCP, with similarity coefficients ranging from 18 to 50%. Bacterial groups were responsible for the initial PCP degradation, while the archaeal community was involved in metabolizing the resulting byproducts. The use of indigenous inoculum from the Santos-São Vicente estuary demonstrated its potential for effective PCP removal. Polyurethane foam proved to be an effective support material, enhancing the adsorption process and reducing PCP toxicity to the microbial consortium. This study provides valuable insights into PCP adsorption and biodegradation mechanisms in HAIB, highlighting the effectiveness of indigenous inoculum and polyurethane foam for PCP removal., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Organic and nanoparticle pollutants are the main environmental problems affecting marine species, which have received great attention. However, the combined effect of pollutants on marine life in the presence of predators needs to be clarified. In this study, the effects of pentachlorophenol (PCP) and titanium dioxide nanoparticles (nano-TiO 2 ) on the energy metabolism of mussels (Mytilus coruscus) in the presence of predators were assessed through cellular energy allocation (CEA) approach. Mussels were exposed to PCP (0, 1, and 10 μg/L), nano-TiO 2 (1 mg/L, 25 and 100 nm), and predators (Portunus trituberculatus presence/absence) for 14 days. Exposure to high concentrations of PCP (10 μg/L) with small particle size nano-TiO 2 (25 nm) decreased cellular energy stores (carbohydrates, lipids, and proteins) and increased cellular energy demand (measured as the activity of the mitochondrial electron transport system, ETS). During the first 7 days, energy was supplied mainly through the consumption of carbohydrates, while lipids are mobilized to participate after 7 days. The presence of predators caused a further decrease in energy stores. These findings demonstrate that PCP, nano-TiO 2 and predators have a negative impact on energy metabolism at the cellular level. Carbohydrates are not able to meet the metabolic demand, lipids need to be consumed, and energy metabolism was also mediated by the involvement of proteins. Overall, our results suggest that PCP, nano-TiO 2 and predators disrupt the cellular energy metabolism of mussels through reduced cellular energy allocation, small particles and predators drive mussels to exert energetic metabolic adjustments for detoxification reactions when toxic contaminants are present., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Anoxic aquifers suffer from energy limitations due to the unavailability of organic substrates, as dictated by hydrogen (H 2 ) for various electron-accepting processes. This deficiency often results in the accumulation of persistent organic pollutants, where bioremediation using organic compounds often leads to secondary contamination. This study involves the reductive dechlorination of pentachlorophenol (PCP) by dechlorinators that do not use H 2 directly, but rather through a reduced state of humin-a solid-phase humic substance-as the extracellular electron donor, which requires an organic donor such as formate, lactate, etc. This shortcoming was addressed by the development of an anaerobic mixed culture that was capable of reductively dechlorinating PCP using humin under autotrophic conditions induced by homoacetogenesis. Here, H 2 was used for carbon-dioxide fixation to acetate; the acetate produced was used for the reduction of humin; and consequently used for dechlorination through reduced humin. The 16SrRNA gene sequencing analysis showed Dehalobacter and Dehalobacterium as the possible dechlorinators, while Clostridium and Oxobacter were identified as the homoacetogens. Thus, this work contributes to the development of an anaerobic consortium that balanced H 2 dependency, where efficiency of humin reduction extends the applicability of anaerobic microbial remediation in aquifers through autotrophy, syntrophy, and reductive dechlorination., Competing Interests: The authors declare no conflicts of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Caspase proteases play an essential role in cell apoptosis and inflammation, thus matter greatly in animal development and other biological processes. As a ubiquitous environmental pollutant, pentachlorophenol (PCP) is considered to have adverse effects on animal apoptosis during embryonic development, yet the evidence that PCP interfere with caspase genes was seldom reported. To uncover the effects of PCP on caspases expression in early embryos of zebrafish, two concentrations of PCP (5 μg/L and 200 μg/L) were chosen and 14 types of caspase genes at two different developmental stages, 8 h post-fertilization (hpf) and 24 hpf were analyzed. Lower survival and hatching rates, distinct developmental delay and morphological deformities of head and tail were observed. PCP, especially in the high concentration, significantly altered the expressions of most caspase genes. At 8 hpf, PCP had the most significant inductive effects on gene casp8l2 with fold changes (FCs) of 6.87 at 5 μg/L and 4.48 at 200 μg/L, and casp6l1 (with FCs of 3.15/3.69), and inhibitory effects on caspa (with FCs of 0.93/0.53) and caspb (with FCs of 0.99/0.57). At 24 hpf, PCP had the most significant effects on casp6l2, casp9, and caspc. PCP exposure possibly disrupted intrinsic apoptosis pathway considering its effects on casp9 expression. In addition, most caspase genes exhibited higher levels at 24 hpf than 8 hpf except caspc. Our results suggested that PCP had different effects on varied caspase genes, which probably resulting in a profound impact on caspase proteins and apoptosis processes and, ultimately, developmental abnormality., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Humins have been reported to function as an electron mediator for microbial reducing reactions. However, the physicochemical properties and the functional moieties of humins from different natural sources have been poorly characterized. In this study, humins extracted from seven types of soil and from a river sediment were examined on the effect on microbial reductive dechlorination of pentachlorophenol (PCP) and characterized polyphasically. All humins facilitated microbial reductive dechlorination of PCP as electron mediators using formate as carbon source, with different dechlorination rates ranging from 0.99 to 7.63 (μmol Cl-) L(-1) d(-1). The highest rates were observed in humins with high carbon contents, extracted from Andisols containing allophone as major clay. Yields of the humins and the elemental compositions varied among sources. Fourier transform infrared analysis showed that all the humins exhibited similar spectra with different absorbance intensity; these data are indicative of their similar structures and identical classes of functional groups. The electron spin resonance spectra of humins prepared at different pH showed typical changes for the semiquinone-type radicals, suggestive of quinone moieties for the redox activity of the humins. Cyclic voltammetry analysis confirmed the presence of redox-active moieties in all the humins, with the estimated redox potentials in the range of -0.30 to -0.13 V (versus a standard hydrogen electrode), falling into the range of standard redox potential between the oxidation of formate as electron donor and the initial dechlorination of PCP as electron acceptor., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study has demonstrated the applicability of a simple technology such as the sequencing batch reactor (SBR), operated with suspended biomass, to the aerobic biodegradation of a highly toxic compound, the pentachlorophenol (PCP). An enrichment of a microbial consortium, originated from the biomass of an urban wastewater treatment plant, was performed and 70 days were sufficient to achieve removal efficiencies of ∼90% with the compound fed as only carbon and energy source Once completed the start-up period, the SBR was operated with the acclimatized biomass for 60 days at a feed concentration of PCP in the range of 10-20 mg L(-1). Improved performance was observed at increased influent concentration and the reached removal efficiency for the highest concentrations was stable at values≥90%. Kinetic and stoichiometric characterization of the acclimated biomass was performed with biodegradation tests carried out in the bioreactor during the reaction phase. The classical and a modified four-parameter forms of the Haldane equation were applied to model the substrate inhibited kinetics. Both models provided reliable predictions with high correlation coefficients (>0.99). The biomass characterization was completed with the evaluation of the growth yield coefficient, Y (0.075 on chemical oxygen demand base) and endogenous respiration rate, b (0.054 d(-1)). The aerobic SBR, operated in the metabolic mode with a mixed culture, showed superior performance in comparison to continuous systems applied in the same range of PCP influent loads and achieved removal rates are suitable for application.

This study proposes a new treatment method to decompose persistent chemicals such as pentachlorophenol (PCP) in water, utilizing hydrogen peroxide present in aquatic plants to proceed the biological Fenton reaction. PCP was not effectively removed by aquatic plants. However, by adding 2.8 mM of Fe(2+), there was a rapid removal of PCP while at the same time consumption of endogenous hydrogen peroxide occurred. It was observed the increase of chloride ions formation in water-confirming the complete degradation of PCP. These results demonstrated that PCP was oxidized through a biological Fenton reaction, and hydrogen peroxide in aquatic plants was a key endogenous substance in treatment of refractory toxic pollutants.

Horseradish peroxidase (HRP) is successfully in situ encapsulated into the poly(D,L-lactide-co-glycolide) (PLGA)/PEO-PPO-PEO (F108) electrospun fibrous membranes (EFMs) by emulsion electrospinning. The adsorption and degradation of pentachlorophenol (PCP) by HRP-EFMs are investigated. The experimental results show that the sorption kinetic of PCP on EFMs follows the pseudo-second-order model, and the sorption capacity is as high as 44.69 mg g(-1). The sorption mechanisms of EFMs for PCP can be explained by hydrogen bonding interactions, hydrophobic interactions and π-π bonding interactions. Profiting from the strong adsorption, the removal of PCP can be dramatically enhanced by the interaction of adsorbed PCP and HRP on the surface of EFMs. For PCP degradation, the optimal pH values for free HRP and immobilized HRP are 4 and 2-4, respectively. As pH>4.7, no adsorption and degradation are observed due to the deprotonation of PCP. The removal percentages reach 83% and 47% for immobilized HRP and free HRP, respectively, at 25 ± 1°C. The presence of humic acid can inhibit the activity of HRP and decreases the adsorption capacity of PCP because of competitive adsorption. The operational and storage stability of immobilized HRP are highly improved through emulsion electrospinning., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Complete mineralization of 50 µM of pentachlorophenol (PCP) was achieved anaerobically under continuous flow conditions using two columns connected in series with a hydraulic retention time of 14.2 days, showing the highest reported mineralization rate yet of 3.5 µM day(-1). The first column, when injected with a reductive PCP dechlorinating consortium, dechlorinated PCP to mainly phenol and traces of 3-chlorophenol (3-CP) using lactate supplied continuously as an electron donor. The second column, with an anaerobic phenol degrading consortium, decomposed phenol and 3-CP under iron-reducing conditions with substantial fermentative degradation of organic compounds. When 20 mM of lactate was introduced into the first column, the phenol degradation activity of the second column was lost in a short period of time, because the amorphous Fe(III) oxide (FeOOH) that had been packed in the column before use was depleted by lactate metabolites, such as acetate and propionate, flowing into the second column from the first column. The complete mineralization of PCP was maintained for a long period by reducing the lactate concentration to 4 mM, effectively extending the longevity of second-column activity with no depletion of FeOOH for more than 200 pore volumes (corresponding to 3,000 days). The carbon balance showed that 50 µM PCP and 4 mM lactate in the influent had transformed to CO(2) (81%) and CH(4) (3%) and had contributed to biomass growth (8%). A comparison of the microbial consortia introduced into the columns and those flowing out from the columns suggested that the introduced population did not flow out during the experiments, although the microbial composition of the phenol column was considered to be affected by the inflow of microbes from the PCP dechlorination column. These results suggest that a sequential combination of reductive dechlorinating and anaerobic oxidizing consortia is useful for anaerobic remediation of chlorinated aromatic compounds in a microbial permeable reactive barrier., (© 2010 Wiley Periodicals, Inc.)

Toxicological studies in sentinel organisms frequently use biomarkers to assess biological effect. Development of "omic" technologies has enhanced biomarker discovery at the molecular level, providing signatures unique to toxicant mode-of-action (MOA). However, these signatures often lack relevance to organismal responses, such as growth or reproduction, limiting their value for environmental monitoring. Our primary objective was to discover metabolic signatures in chemically exposed organisms that can predict physiological toxicity. Marine mussels (Mytilus edulis) were exposed for 7 days to 12 and 50 microg/l copper and 50 and 350 microg/l pentachlorophenol (PCP), toxicants with unique MOAs. Physiological responses comprised an established measure of organism energetic fitness, scope for growth (SFG). Metabolic fingerprints were measured in the same individuals using nuclear magnetic resonance-based metabolomics. Metabolic signatures predictive of SFG were sought using optimal variable selection strategies and multivariate regression and then tested upon independently field-sampled mussels from rural and industrialized sites. Copper and PCP induced rational metabolic and physiological changes. Measured and predicted SFG were highly correlated for copper (r(2) = 0.55, P = 2.82 x 10(-7)) and PCP (r(2) = 0.66, P = 3.20 x 10(-6)). Predictive metabolites included methionine and arginine/phosphoarginine for copper and allantoin, valine, and methionine for PCP. When tested on field-sampled animals, metabolic signatures predicted considerably reduced fitness of mussels from the contaminated (SFG = 6.0 J/h/g) versus rural (SFG = 15.2 J/h/g) site. We report the first successful discovery of metabolic signatures in chemically exposed environmental organisms that inform on molecular MOA and that can predict physiological toxicity. This could have far-reaching implications for monitoring impacts on environmental health.

Two PCP-degrading bacterial strains, Bacillus cereus (ITRC-S6) and Serratia marcescens (ITRC-S7) were used for the treatment of pulp and paper mill effluent at conditions; 1.0% glucose and 0.5% peptone at 30 +/- 1 degrees C at 120 rpm for 168 h of incubation. These two bacterial strains effectively reduced colour (45-52%), lignin (30-42%), BOD (40-70%), COD (50-60%), total phenol (32-40%) and PCP (85-90%) within 168 h of incubation. However, the highest reduction in colour (62%), lignin (54%), BOD (70%), COD (90%), total phenol (90%) and PCP (100%) was recorded by mixed culture treatment. The bacterial mechanism for the degradation of pulp and paper mill effluent may be explained by an increase in the cells biomass using added co-substrates resulting liberation of significant amount of chloride due to bacterial dechlorination of chlorolignins and chlorophenols this showed reduction in colour, lignin and toxicity in the effluent. Further, GC-MS analysis of ethyl acetate-extractable compounds from treated pulp paper mill effluent reinforces the bacterium capability for the degradation of lignin and pentachlorophenol, as many aromatic compounds such as 2-chlorophenol, 2, 4, 6-trichlorophenol and tetrachlorohydroquinone, 6-chlorohydroxyquinol and tetrachlorohydroquinone detected which were not present in the untreated effluent.

This study focuses on the use of non-viable Aspergillus niger biomass, for the biosorption of pentachlorophenol (PCP) from aqueous solutions. Various forms of the biomass-autoclaved and chemically conditioned, were tested for their potential in the removal of PCP from aqueous solutions. It was found that PCP removal was pH dependent; PCP removal decreased with the increase in pH for all type of biomass, except for cetyltrimethylammonium bromide (CTAB) biomass. For CTAB biomass, a near complete removal of PCP was observed at all pHs. Therefore, CTAB biomass was used in further studies. PCP removal was rapid, with an equilibrium time of 2h. The rate of adsorption kinetics was well described by a pseudo-second order model. Isotherm models of the type one and two parameter models were found to fit the isotherm data. PCP biosorption was found to be exothermic in nature; the amount of PCP sorbed decreased with an increase in temperature. Desorption was carried out using deionized water, dilute HCl and dilute NaOH, and it was found that most of the PCP was irreversibly bound to the biomass. The addition of inorganic salts did not affect the removal of PCP from aqueous solutions. Among the surface functional groups present on the biomass, carboxyl, amide and hydroxyl groups seem to have played a role in PCP biosorption. It was concluded that CTAB treated biomass was an excellent adsorbent for the removal of PCP from aqueous solutions.

Pentachlorophenol (PCP) has been used as a wood preservative for more than 100 years. The extensive use of PCP has widely contaminated soil and groundwater. PCP is toxic to living organisms. The main objective of this research was to inoculate the pure PCP-degrading bacterium strain Sphingomonas chlorophenolica PCP-1, isolated from PCP-contaminated soils, into PCP-contaminated groundwater for remediation purposes. The factors that influenced the bioremediation were explored with batch experiments using the inoculated immobilized and suspended cells as inoculation. A biological treatment system inoculated with immobilized cells was set up to estimate the microbial capability to degrade PCP. The results indicated that the suspended and immobilized cells could be inoculated into PCP-contaminated groundwater without adding other supplementary nitrogen and phosphate sources in batch conditions. Moreover, PCP decomposition was accompanied with released Cl- and decreasing pH value. The optimum HRT in the bioreactor system was 12.6h. PCP removal in the bioreactor remained stable and PCP removal efficiency was higher than 92% at this phase. Furthermore, PCP concentration in the biotreatment system effluent remained undetectable. It is possible to bioremediate PCP-contaminated groundwater using immobilized S. chlorophenolica PCP-1 cells in a bioreactor system. The proposed biological treatment system could be maintained for at least for 2 months.

The fungal biomass of Penicillium chrysogenum was used as raw materials to prepare the sorbent, and polyethylenimine (PEI) was grafted onto the biomass surface in a two-step reaction. The best sorbent was obtained through the optimization experiments. As the PEI-modified biomass was found to possess zero zeta-potential at pH 10.2, the biosorbent is favorable for the removal of anionic pentachlorophenol (PCP), 2,4-dichlorophenoxyacetic acid (2,4-D) and perfluorooctane sulphonate (PFOS) potassium in water. The sorption isotherms of the biomass for three pollutants were well described by Langmuir equation, with a maximum sorption at 342.9 mg PCP, 234.1 mg 2,4-D and 1725.6 mg PFOS per g biomass. The thermodynamic parameters calculated show that the sorption for three pollutants was spontaneous, and the sorption for 2,4-D and PFOS were endothermic, while the sorption for PCP was exothermic.

The potential of C(60)-nanoparticles (Buckminster fullerenes) as contaminant carriers in aqueous systems was studied in a series of toxicity tests with algae (Pseudokirchneriella subcapitata) and crustaceans (Daphnia magna). Four common environmental contaminants (atrazine, methyl parathion, pentachlorophenol (PCP), and phenanthrene) were used as model compounds, representing different physico-chemical properties and toxic modes of action. The aggregates of nano-C(60) formed over 2 months of stirring in water were mixed with model compounds 5 days prior to testing. Uptake and excretion of phenanthrene in 4-days-old D. magna was studied with and without addition of C(60) in aqueous suspensions. It was found that 85% of the added phenanthrene sorbed to C(60)-aggregates >200 nm whereas about 10% sorption was found for atrazine, methyl parathion, and pentachlorophenol. In algal tests, the presence of C(60)-aggregates increased the toxicity of phenanthrene with 60% and decreased toxicity of PCP about 1.9 times. Addition of C(60)-aggregates reduced the toxicity of PCP with 25% in tests with D. magna, whereas a more than 10 times increase in toxicity was observed for phenanthrene when results were expressed as water phase concentrations. Thus, results from both toxicity tests show that phenanthrene sorbed to C(60)-aggregates is available for the organisms. For atrazine and methyl parathion no statistically significant differences in toxicities could be observed in algal and daphnid tests as a result of the presence of C(60)-aggregates. In bioaccumulation studies with phenanthrene in D. magna it was found that the uptake of phenanthrene was faster when C(60) was present in suspension and that a 1.7 times higher steady-state concentration was reached in the animals. However, a very fast clearance took place when animals were transferred to clean water resulting in no accumulation of phenanthrene. This study is the first to demonstrate the influence of C(60)-aggregates on aquatic toxicity and bioaccumulation of other environmentally relevant contaminants. The data provided underline that not only the inherent toxicity of manufactured nanoparticles, but also interactions with other compounds and characterisation of nanoparticles in aqueous suspension are of importance for risk assessment of nanomaterials.

The effect of low operating temperature and pollutant concentration on the performance of five anaerobic hybrid reactors was investigated. Stable and efficient long-term (>400 days) treatment of a cold (6-13 degrees C), volatile fatty acid (VFA)-based, wastewater was achieved at applied organic loading rates (OLRs) of 5 kg chemical oxygen demand (COD) m(-3) d(-1) with COD removal efficiencies c. 84% at 6 degrees C (sludge loading rate (SLR) 1.04-1.46 kg COD kg [VSS](-1) d(-1)). VFA-based wastewaters, containing up to 14 g pentachlorophenol (PCP) m(-3) d(-1) or 155 g toluene m(-3) d(-1) were successfully treated at applied OLRs of 5-7 kg COD m(-3) d(-1). Despite transient declines in reactor performance in response to increasing toxicant loading rates, stable operation (COD removal efficiencies > 90%) and satisfactory toxicant removal efficiencies (>88%) were demonstrated by the systems.

Pentachlorophenol (PCP) concentrations were determined in 55 samples of fish, shrimp, crabs, frogs and turtles collected in Jiangsu Province and 55 freshwater shrimp samples collected from the Huiming Fish Market, Nanjing, China between 2003 and 2004. PCP concentrations ranged from less than the method detection limit (MDL: 0.5 microg/kg ww) to 61 microg/kg ww, with a mean of 5.2 microg/kg ww in 55 samples collected across Jiangsu Province and a mean of 0.5 microg/kg ww for freshwater shrimp collected from the Huiming Fish Market. Concentrations of PCP in common carp (Carassius auratus) were significantly greater than concentrations of PCP in other species from all of the areas studied. Grass carp (Ctenopharyngodon idella) contained the second greatest concentrations and crustacean species contained the least concentrations. Concentrations of PCP were greater in samples collected from Southern Jiangsu than those collected from other areas of Jiangsu Province. Concentrations of PCP in the freshwater shrimp (Macrobrachium nipponense) from the Huiming Fish Market were greater in March and September than those collected in June and December. Based on the allowable daily intake (ADI) set by the US National Academy of Science, current concentrations of PCP measured in aquatic products from Jiangsu Province presented minimus health risks to humans.

This paper reports the toxic effects of pentachlorophenol (PCP) on duckweed, Lemna polyrhiza. The 8-day IC(50) of PCP to L. polyrhiza was 8.08 mg/L. At 0.2 and 0.5 mg/L, PCP inhibited L. polyrhiza chloroplast activity. At low PCP exposures, chloroplast activity was more sensitive than chlorophyll content of L. polyrhiza. At 0.2 and 0.5mg/L, PCP stimulated L. polyrhiza nitrate reductase activity. At 0.2 and 0.5mg/L PCP, duckweed peroxidase activity was 78.3% and 91.0% of the control test, respectively. The bioaccumulation factors (BCFs) of PCP in L. polyrhiza were 79 and 62 at 0.2 and 0.5mg/L PCP, respectively. This is the first study of the effect of PCP on peroxidase activity, nitrate reductase activity, and chloroplast activity of L. polyrhiza. The BCFs of PCP in L. polyrhiza are also for reported the first time.

The influence of the nonionic surfactant Tween 80 on pentachlorophenol (PCP) oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration (CMC). Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.

The solubilization of pentachlorophenol (PCP) by beta-cyclodextrin (beta-CD) and three of its most used derivatives, methyl-beta-cyclodextrin (MCD), hydroxypropyl-beta-cyclodextrin (HPCD) and carboxymethyl-beta-cyclodextrin (CMCD), has been investigated. The formation of soluble inclusion complexes between PCP and cyclodextrin (CDs) increases the aqueous solubility of PCP. Due to the ionizable nature of PCP, the effects of pH and ionic strength on the equilibrium complexation were evaluated. All CDs were found to form 1:1 inclusion complexes. Equilibrium constants calculated from solubility enhancement experiments revealed that the stability of the complexes was dependent on the polarity of the compound, on the ionic strength and on the cyclodextrin type. In general, weaker equilibrium constants were observed for PCP with beta-CD than with MCD or CMCD. For all CDs, the complexation or the solubilization efficiency of PCP (weak acid) depended on pH and ionic strength. Moreover, we observed that the solubility of the beta-CD/PCP complex was lower than that of the beta-CD molecule and dependent on the ionic strength of the solution. Although the equilibrium constant of PCP/CD complex was found to be higher at pH 3 than at pH 7 in water, extraction of PCP from porous media by a CD solution at neutral pH would be achievable due to the higher PCP aqueous solubility in neutral/basic media.

Pentachlorophenol (PCP) has been used in the past as a pesticide, herbicide, antifungal agent, bactericide, and wood preservative. Thus, PCP is among the most ubiquitous chlorinated compounds found in groundwater contamination. A former pesticide manufacturing plant located in southern Taiwan has been identified as a PCP spill site. In this study, groundwater samples collected from the PCP site were analyzed to assess the occurrence of natural PCP biodegradation. Microcosm experiments were conducted to (1) evaluate the feasibility of biodegrading PCP by indigenous microbial consortia under aerobic and cometabolic conditions, and (2) determine the potential of enhancing PCP biodegradation using cane molasses and biological sludge cake as the substitute primary substrates under cometabolic conditions. The inocula used in this microcosm study were aquifer sediments collected from the PCP site and activated sludges collected from the municipal and industrial wastewater treatment plants. Results from this field investigation indicate that the natural biodegradation of PCP is occurring and causing the decrease in PCP concentration. Microcosm results show that the indigenous microorganisms can biodegrade PCP under both aerobic and aerobic cometabolism conditions. A PCP-degrading bacterium was isolated from the collected aquifer sediments and identified as Pseudomonas mendocina NSYSU via some biochemical tests and further conformation of DNA sequencing. In batch cultures, P. mendocina NSYSU used PCP as its sole source of carbon and energy. The isolated bacterium, P. mendocina NSYSU, was capable of completely degrading PCP as indicated by the increase in biomass formation with the decrease in PCP concentrations occurred in the carbon-free medium simultaneously. Results indicate that the in situ or on-site aerobic bioremediation using indigenous microorganisms or inoculated bacteria would be a feasible technology to clean up the studied PCP-contaminated site. Results from this study will be useful in designing a scale-up in situ or on-site PCP bioremediation system (e.g., on-site bioreactor) for field application.

Pentachlorophenol (PCP) has been widely used as a wood preservative since 1980s. Although it has been banned worldwide, residues of PCP are still commonly found. The spent compost of oyster mushroom Pleurotus pulmonarius (SMC) which was a degraded paddy straw-based substrate, contained 25% chitin. Five percentage of the SMC could remove 89.0 +/- 0.4% of 100 mg PCPl(-1) within 2 days at room temperature predominantly by biodegradation. The maximum removal capacity was 15.5 +/- 1.0 mg g(-1) SMC. The sorption kinetics of PCP by SMC can be described by the Freundlich monolayer model with a theoretical sorption capacity similar to that found for chitin. A PCP-degradative bacterium was isolated from the SMC. Yet, biodegradation was predominantly contributed by the immobilized ligninolytic enzymes secreted by the mushroom to the SMC. Degradation of PCP involves dechlorination, methylation, carboxylation and ring cleavage as verified by GC-MSD and ion chromatography. Thus, the SMC has a potential for treating PCP-contaminated water.

Acute static bioassays were performed using three freshwater invertebrate species (the oligochaete Lumbriculus variegatus, the fingernail clam Sphaerium corneum and the larvae Chironomus riparius) exposed separately to a variety of 14C radiolabelled contaminants. The aim of this work was to investigate if the chemicals remained as parent compounds after the treatments. Chemicals used were 2,4-dichlorophenol; 2,4,5-trichlorophenol; pentachlorophenol; pyrene; Fenpropidin, and Trifluralin. Homogenates of the whole body tissue of each organism were prepared and total radioactivity was measured. Contaminants were then extracted into organic solvents and analysed by high-pressure liquid chromatography techniques. Chromatograms showed that most of the substances extracted were present as parent compounds in S. corneum and in L. variegatus. In contrast, for C. riparius a low proportion of the chemicals was recovered as parent compounds. These results suggest that different metabolic processes could take place in the different species.

Bioremedial treatment to remove low level organic contamination to regulatory standards has met with limited success. In this study source water from a contaminated surficial aquifer at a former wood treatment facility was used to evaluate the potential for indigenous microorganisms to degrade low level (< 1.0 mg) pentachlorophenol (PCP) to a regulatory drinking water standard of 0.001 mg/L. PCP degradation was evaluated in series of batch reactors in a two phase study to (a) determine the rate and extent of PCP removal and (b) evaluate the impact of nutrient amendment (N and P) on removal rate. All reactors with the exception of the abiotic control demonstrated PCP removal to a level < 0.002 mg/L within a maximum period of 32 d with and without nutrient amendment. A regression analysis of reactive phosphate (ortho-P) concentration versus removal rate produced an R2 of 0.94 (p = 0.006) indicating a significant correlation between the level of available phosphate and PCP degradation rate. Selective bacterial enumeration (for PCP degrading bacteria) revealed PCP-degrading bacteria increased in abundance prior to and in conjunction with the degradation phase to a density of between 10(3) to 10(4) CFU/ml. Isolates were also analyzed for total fatty acids using Fatty Acid Methyl Ester (FAME) methodology and the results indicated that PCP degrading bacteria were present in the aquifer and consisted of predominately fluorescent, oxidase positive Pseudomonas species. Overall, data indicate that autochthonous microbes are capable of removing low level PCP (< 1.0 mg/L) to approach if not reach the regulatory standard of 0.001 mg/L with the addition of oxygen, with or without nutrient amendment. Results of this research can be applied to full-scale implementation of in-situ or ex-situ bioremediation of groundwater at former wood treatment facilities.

Chlorophenol-degrading bacteria from a long-term polluted groundwater aquifer were characterized. All isolates degraded 2,4,6-trichlorophenol and 2,3,4,6-tetrachlorophenol at concentrations detected in the contaminated groundwater (< 10 mg 1(-1)). Pentachlorophenol was degraded by three isolates when present alone. In two gram-positive isolates, 2,3,4,6-tetrachlorophenol was required as an inducer for the degradation of pentachlorophenol. The gram-positive isolates were sensitive to pentachlorophenol, with an IC50 value of 5 mg/l. Isolates belonging to the Cytophaga/Flexibacter/Bacteroides phylum had IC50 values of 25 and 63 mg/l. Isolates belonging to alpha-, beta- and gamma-Proteobacteria generally tolerated the highest pentachlorophenol concentrations (> 100 mg/l). Polychlorophenol-degrading capacity was found in strains of Nocardioides, Pseudomonas, Ralstonia, Flavobacterium, and Caulobacter previously not known to degrade polychlorophenols. In addition, six polychlorophenol-degrading sphingomonads were found.

A fluidized-bed reactor (FBR) was used to enrich an aerobic chlorophenol-degrading microbial culture. Long-term continuous-flow operation with low effluent concentrations selected oligotrophic microorganisms producing good-quality effluent for pentachlorophenol(PCP)-contaminated water. PCP biodegradation kinetics was studied using this FBR enrichment culture. The results from FBR batch experiments were modeled using a modified Haldane equation, which resulted in the following kinetic constants: qmax = 0.41 mg PCP mg protein-1 day-1, Ks = 16 micrograms l-1, Ki = 5.3 mg l-1, and n = 3.5. These results show that the culture has a high affinity for PCP but is also inhibited by relatively low PCP concentrations (above 1.1 mg PCP l-1). This enrichment culture was maintained over 1 year of continuous-flow operation with PCP as the sole source of carbon and energy. During continuous-flow operation, effluent concentrations below 2 micrograms l-1 were achieved at 268 min hydraulic retention time (tHR) and 2.5 mg PCP l-1 feed concentration. An increase in loading rate by decreasing tHR did not significantly deteriorate the effluent quality until a tHR decrease from 30 min to 21 min resulted in process failure. Recovery from process failure was slow. Decreasing the feed PCP concentration and increasing tHR resulted in an improved process recovery.

The strictly anaerobic, pentachlorophenol (PCP) degrading bacterium DCB-2 was immobilized in an Upflow Anaerobic Sludge Blanket (UASB) reactor containing sterile granules. PCP and lactate were fed to the reactor and the concentration of chlorophenols in the effluent were monitored for 641 days. PCP was found to be degraded and transformed into 3,4,5-trichlorophenol in the reactor where DCB-2 introduced PPCP was still transformed to 3,4,5-trichlorophenol when the hydraulic retention time was decreased to six hours which was much lower than the generation time of DCB-2 insuring no free living cells in the reactor. This indicated that DCB-2 was immobilized in the granular layer. A control reactor that contained only sterile granules did not dechlorinate PCP indicating that the performance in the inoculated reactor was only due to the introduced bacteria. Immobilization of DCB-2 in the granules was further demonstrated by adding an antibody raised against DCB-2 to sliced granules. Bacteria thus visualized formed a net structure inside the granules. No DCB-2 bacteria could be found in granules from the control reactor. When lactate was omitted from the influent, the reactor still dechlorinated PCP in accordance with our findings that lactate was not used by DCB-2. This suggested that the reducing equivalents for reductive dechlorination were derived from the granules themselves. The reactor performance was 120 mumol.l reactor-1.day-1, comparable to the best described performance of a UASB-reactor and to aerobic reactors. Our study demonstrates that granules can be constructed which possess specific abilities such as a dechlorinating activity and at the same time be high performing. This result have implications for eco-engineering of granules for anaerobic treatment of contaminated waters.

Anaerobic granules degrading pentachlorophenol (PCP) with specific PCP removal activity up to 14.6 mg/g of volatile suspended solids per day were developed in a laboratory-scale anaerobic upflow sludge blanket reactor at 28 degrees C, by using a mixture of acetate, propionate, butyrate, and methanol as the carbon source. The reactor was able to treat synthetic wastewater containing 40 to 60 mg of PCP per liter at a volumetric loading rate of up to 90 mg/liter of reactor volume per day, with a hydraulic retention time of 10.8 to 15 h. PCP removal of more than 99% was achieved. Results of adsorption of PCP by granular biomass indicated that the PCP removal by the granules was due to biodegradation rather than adsorption. A radiotracer assay demonstrated that the PCP-degrading granules mineralized [14C]PCP to 14CH4 and 14CO2. Toxicity test results indicated that syntrophic propionate degraders and acetate-utilizing methanogens were more sensitive to PCP than syntrophic butyrate degraders. The PCP-degrading granules also exhibited a higher tolerance to the inhibition caused by PCP for methane production and degradation of acetate, propionate, and butyrate, compared with anaerobic granules unadapted to PCP.

Freshwater and seawater acclimated (FWA and SWA) killifish (Oryzias latipes) were exposed to pentachlorophenol (PCP) for 3-10 days. Uptake and clearance rates of FWA and SWA killifish were determined. The estimated bioaccumulation factors (BCF) of PCP for FWA and SWA killifish were 1680 and 370, respectively. The smaller uptake rate and faster clearance rate resulted in the lower BCF for SWA killifish. Fresh- and seawater killifish excreted the PCP metabolites, the glucuronide and sulfate conjugates of PCP; the major metabolite of freshwater killifish was PCP sulfate; for seawater acclimated fish, it was PCP glucuronide. The greater excretion of PCP glucuronide by seawater killifish may be responsible for the rapid elimination of PCP. PCP accumulation in killifish decreased with higher pH levels in both freshwater and seawater environments, but these differences were less than the effect of salinity. The results indicate that salinity can affect the accumulation and elimination of environmental pollutants in killifish.

Shake flask studies examined the rate and extent of biodegradation of pentachlorophenol (PCP) and 42 components of coal-tar creosote present in contaminated groundwater recovered from the American Creosote Works Superfund site, Pensacola, Fla. The ability of indigenous soil microorganisms to remove these contaminants from aqueous solutions was determined by gas chromatographic analysis of organic extracts of biotreated groundwater. Changes in potential environmental and human health hazards associated with the biodegradation of this material were determined at intervals by Microtox assays and fish toxicity and teratogenicity tests. After 14 days of incubation at 30 degrees C, indigenous microorganisms effectively removed 100, 99, 94, 88, and 87% of measured phenolic and lower-molecular-weight polycyclic aromatic hydrocarbons (PAHs) and S-heterocyclic, N-heterocyclic, and O-heterocyclic constituents of creosote, respectively. However, only 53% of the higher-molecular-weight PAHs were degraded; PCP was not removed. Despite the removal of a majority of the organic contaminants through biotreatment, only a slight decrease in the toxicity and teratogenicity of biotreated groundwater was observed. Data suggest that toxicity and teratogenicity are associated with compounds difficult to treat biologically and that one may not necessarily rely on indigenous microorganisms to effectively remove these compounds in a reasonable time span; to this end, alternative or supplemental approaches may be necessary. Similar measures of the toxicity and teratogenicity of treated material may offer a simple, yet important, guide to bioremediation effectiveness.

The microbial degradation of a number of 14C-labeled, recalcitrant, aromatic pollutants, including trichloroguaiacol and di-, tri-, and pentachlorophenol, was investigated in aquatic model systems in the laboratory. Natural, mixed cultures of microorganisms in the water from a brown-water lake with a high content of humic compounds mineralized all of the tested substances to a higher degree than did microorganisms in the water from a clear-water lake. Dichlorophenol was the most rapidly degraded pollutant.

The steady-state growth of a Flavobacterium strain known to utilize pentachlorophenol (PCP) was examined when cellobiose and PCP simultaneously limited its growth rate in continuous culture. A concentration of 600 mg of PCP per liter in influent medium could be continuously degraded without affecting steady-state growth. We measured specific rates of PCP carbon degradation as high as 0.15 +/- 0.01 g (dry weight) of C per h at a growth rate of 0.045 h-1. Comparable specific rates of PCP degradation were obtained and maintained by PCP-adapted, natural consortia of epilithic microorganisms. The consortium results suggest that a fixed-film bioreactor containing a PCP-adapted natural microbial population could be used to treat PCP-contaminated water.

The 2nd year of a 2-year study of the fate of pentachlorophenol in outdoor artificial streams focused on details of microbial degradation by a combination of in situ and laboratory measurements. Replicate streams were dosed continuously at pentachlorophenol concentrations of 0, 48, and 144 micrograms/L, respectively, for an 88-d period during the summer of 1983. Pentachlorophenol was degraded both aerobically and anaerobically. Aerobic degradation was more rapid than anaerobic degradation. Mineralization of pentachlorophenol was concommitant with pentachlorophenol disappearance under aerobic conditions, but lagged behind loss of the parent molecule under anaerobic conditions. Biodegradation in the streams, or in specific stream compartments such as the sediment or water column, was characterized by an adaptation period (3-5 weeks for the stream as a whole, and reproducible from the previous year), which was inversely dependent on the concentration of pentachlorophenol and microbial biomass. The adaptation in the streams could be attributed to the time necessary for selective enrichment of an initially low population of pentachlorophenol degraders on surface compartments. The extent of biodegradation in the streams (percent loss of initial concentration of pentachlorophenol) increased with increasing pentachlorophenol input, which was explicable by an increase in the pentachlorophenol degrader population with increasing pentachlorophenol concentration. The sediment zone most significant to overall pentachlorophenol biodegradation was the top 0.5- to 1-cm layer as shown by pentachlorophenol migration rates and depth profiles of degrader density within the sediment. Pentachlorophenol profiles in sediment cores taken during and after the adaptation period for degradation showed that diffusion of pentachlorophenol into the sediment was rate limiting to degradation in this compartment.(ABSTRACT TRUNCATED AT 250 WORDS)

Roach (Rutilus rutilus) were exposed, along with their appropriate controls, to a simulated bleached kraft mill effluent (KME-Sa + CP) first for 38 days at a concentration of 0.035 X LC50 and then for 14 days at 0.07 X LC50. During the experiment, their tolerances to KME-Sa + CP were tested five times by measuring the 48-hr LC50 values. In addition, the growth of roach was monitored. At the end of the exposure, accumulation of [14C]pentachlorophenol in various parts of the fish (total PCP in water 15.6 micrograms/liter) was measured. When the fish were preexposed to KME-Sa + CP, the acute tolerance of this mixture in roach increased by 30-39%, but the response was abolished in 31 days. Fish growth remained unchanged during the experiment. Measurement of PCP accumulation revealed no difference in the absorption rate, but under steady-state conditions the degree of bioconcentration was 16% lower (P less than 0.02) in preexposed roach than in their unexposed controls. This difference was entirely accounted for in the head and visceral parts of the fish. Even when no final changes were noted in tolerance and growth rate of the fish, the authors suggest that the significantly lowered body burden implied acclimatizatory compensation under subchronic exposure of this xenobiotic.

Outdoor artificial streams were treated continuously with pentachlorophenol (PCP) for 88 days during the summer of 1983. The contributions of different stream compartments (microbial habitats) to microbial degradation of PCP were determined in a stream treated with 144 micrograms of PCP per liter. The 488-m long stream was composed of mud-bottomed pools alternating with gravel riffles. PCP loss in the stream attributable to microbial degradation after an adaptation period was in the range of 55 to 74%. Contributions to PCP loss were determined for rock surface (epilithic), macrophyte surface (epiphytic), sedimentary, and water column communities by measuring rates of PCP disappearance in stream water, containing ambient concentrations of PCP, in contact with representative compartmental samples. The specific capability, in units of micrograms of PCP per hour per square meter of stream cross-sectional area (macrophytes at maximum plant density, water column at mean depth, upper 10-cm layer of gravel), followed the order rock surface much greater than macrophytes greater than sediment approximately equal to water column. The compartmental contribution to total stream losses in units of grams per hour followed the same order, although the differences were smaller. The rate of PCP disappearance in the water column above sediment cores followed the order oxygen-rich greater than oxygen-poor approximately equal to anaerobic greater than sorption-only conditions. The large difference in specific capability between the rock surface and sediment compartments could be attributed to oxygen deficiency (because of chemical and biological oxygen demand) in the sediments. Free-floating and particle-attached organisms in the water column were important to PCP biodegradation.