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The presence of chlorophenols in water poses a significant threat to human health and the environment. In response to this issue, a study was undertaken to evaluate the catalytic capabilities of chlorinated Heme towards common chlorophenols present in water, such as 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. The study employed the B3LYP method, a sophisticated computational technique within density functional theory, to investigate the molecular interactions and transformations involved. It scrutinized structural parameters, Wiberg Bond Indices, which offer insights into the strength and nature of chemical bonds, along with spectroscopic data including infrared vibrational spectra, ultraviolet-visible absorption spectra, and molecular fluorescence spectra. Furthermore, the research analyzed molecular binding energies and orbital energy levels before and after the formation of complexes between Heme and the targeted chlorophenols. The findings indicate that Heme displays a notable activation characteristic towards these chlorophenols. This suggests that Heme could act as an effective catalyst in the degradation of chlorophenols in water, presenting a novel approach to water purification. The theoretical insights derived from this study are invaluable, potentially guiding the development of more efficient catalytic systems for treating chlorophenol-contaminated water, thereby reducing the environmental and health risks associated with these hazardous compounds., (© 2024. The Author(s).)

A simple method for purifying water using household items has been developed. The solution containing an environmental pollutant was added to the PET bottle. The lid of the PET bottle was closed, and the bottle was then placed with the lid down in a freezer for 9 h. The pourer of the PET bottle was surrounded by shredded paper scraps as a lagging material. Before the solution was completely frozen, the sample was removed from the freezer. The unfrozen portion (liquid) was sampled. The pollutant was concentrated in the liquid. The remaining frozen portion was completely thawed. As results, the concentration of the pollutant (Congo Red, Cr (VI), Pb (II), pentachlorophenol, fluoride, nitrate, or phosphate) in the thawed liquid was decreased by more than 90% compared with the initial concentration (0.10 mM). PRACTITIONER POINTS: A pollutant in a water sample can be removed by freezing a portion of the solution using a PET bottle, shredder scrap, and household freezer. Fluorine and hexavalent chromium can be removed from water to levels that meet water quality standards. The present method can efficiently remove a wide range of contaminants from water, including azo dyes, heavy metals, and pentachlorophenol., (© 2024 Water Environment Federation.)

Although the use of ferrate (VI), an emerging green oxidant, has been widely investigated to remove organic pollutants in water, its ability to remediate contaminated soils has been scarcely evaluated. Here, we explore the use of ferrate (VI) to degrade a polychlorinated persistent compound, the pentachlorophenol (PCP), in aqueous solution and in an aged contaminated soil under batch, water-saturated and water-unsaturated flow conditions. The first results showed the prominent efficiency of ferrate (VI) over conventional oxidants (e.g. H 2 O 2 and persulfate) in both matrices and at different oxidant doses. In aqueous solution, more than 80% of PCP was degraded by ferrate (VI) while complete removal was observed in soil under batch conditions. In column experiments, PCP removal by ferrate (VI) remained efficient but dependent on the flow rate and water saturation. Maximum PCP removal (95%) in columns was observed under water saturated conditions when ferrate (VI) (0.2 g g -1 of soil) was injected at a low flow rate (i.e. 0.025 mL min -1 ). This study has strong implications in the development of new sustainable processes based on ferrate (VI) for the remediation of different environmental compartments., Competing Interests: Declaration of competing interests 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 © 2020 Elsevier Ltd. All rights reserved.)

Antibody-Drug Conjugates (ADCs) consist of antibodies attached to cytotoxic small molecules or biological agents (i.e., payloads) through chemical linkers which may be cleavable or non-cleavable. The development of new ADCs is challenging, particularly the process of attaching the linker-payload construct to the antibody (i.e., the conjugation process). One of the major problems associated with conjugation is high hydrophobicity of the payload which can lead to low yields of the ADC through aggregation and/or lower than desired Drug-Antibody Ratios (DARs). We report here a UPLC-based assay that can be used to study the physicochemical properties of ADC payloads at an early stage of development, and to provide information on whether the hydrophilic-hydrophobic balance is suitable for conjugation or further physicochemical optimization is required. The assay is relatively simple to establish and should be of use to those working in the ADC area., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: IP has share options and PJMJ, KMR and DET have founding stock in Femtogenix Ltd, the company supplying one of the experimental ADC payloads evaluated in this study. IP and PJMJ are fully employed by Femtogenix Ltd, and KMR and DET have consultancies with the company. PJMJ, KMR and DET are named inventors on patents filed and owned by the company., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Electron transfer capacities (ETC) of humic-like acids (HLA) and their effects on dechlorination are dependent on their redox-active properties. Aging and minerals can affect the chemical compositions and structures of HLA. However, the underlying mechanism and the impacts on the dechlorination capacities of HLA are poorly understood. We investigated how redox properties change in association with the intrinsic chemical natures and exterior minerals of the HLA extracted from landfilled solid wastes. Furthermore, the ETC of the landfill-derived HLA could be strengthened by increasing landfill age and demineralization, thereby facilitating the dechlorination of pentachlorophenol (PCP). The HLA molecules started to polymerize aromatic macromolecules during landfilling, leading to an increase in ETC and dechlorination capacities. Macromolecular HLA were dissociated to smaller molecules and exposed more aromatic and carboxyl groups when separated from minerals, which enhanced the ETC and the dechlorination abilities of the HLA. Microbial-mediated dechlorination was an effective way to degrade PCP, and almost 80% of the PCP was transformed after 40 days of demineralized HLA and Shewanella oneidensis MR-1 incubation. The demineralization and aging further facilitated the microbial-mediated PCP dechlorination. The findings provide a scientific base for improving in-situ bioremediation of chlorinated compound-contaminated soils using freshly synthesized HLA., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study explores the zero-valent iron (ZVI) dechlorination of pentachlorophenol (PCP) and its dependence on the dissolved oxygen (O 2 ), presence/formation of iron oxides, and presence of nickel metal on the ZVI surface. Compared to the anoxic system, PCP dechlorination was slower in the presence of O 2 , which is a potential competitive electron acceptor. Despite O 2 presence, Ni 0 deposited on the ZVI surfaces catalyzed the hydrogenation reactions and enhanced the PCP dechlorination by Ni-coated ZVI bimetal (Nic/Fe). The presence of O 2 led to the formation of passivating oxides (maghemite, hematite, lepidocrocite, ferrihydrite) on the ZVI and Nic/Fe bimetallic surfaces. These passive oxides resulted in greater PCP incorporation (sorption, co-precipitation, and/or physical entrapment with the oxides) and decreased PCP dechlorination in the oxic systems compared to the anoxic systems. As received ZVI comprised of a wustite film, and in the presence of O 2 , only ≈ 17% PCP dechlorination observed after 25 days of exposure with tetrachlorophenol being detected as the end product. Wustite remained as the predominant oxide on as received ZVI during the 25 days of reaction with PCP under oxic and anoxic conditions. ZVI acid-pretreatment resulted in the replacement of wustite with magnetite and enhanced PCP degradation (e.g. ≈ 52% of the initial PCP dechlorinated after 25 days under oxic condition) with accumulation of mixtures of tetra-, tri-, and dichlorophenols. When the acid-washed ZVI was rinsed in NiSO 4 /H 2 SO 4 solution, Ni 0 deposited on the ZVI surface and all the wustite were replaced with magnetite. After 25 days of exposure to the Nic/Fe, ≈ 78% and 97% PCP dechlorination occurred under oxic and anoxic conditions, respectively, producing predominantly phenol. Wustite and magnetite are respectively electrically insulating and conducting oxides and influenced the dechlorination and H 2 production. In conclusion, this study clearly demonstrates that the dissolved oxygen present in the aqueous solution decreases the PCP dechlorination and increases the PCP incorporation when using ZVI and Nic/Fe bimetallic systems. The findings provide novel insights towards deciphering and optimizing the performance of complex ZVI and bimetallic systems for PCP dechlorination in the presence of O 2 .

In the present study, ascorbic acid (AA) induced persulfate activation was investigated for the further exploration of organic pollutants oxidation by persulfate. We interestingly found that AA showed a significant catalytic activity to persulfate. Under neutral pH and room temperature condition, about 71.3% of pentachlorophenol (PCP, 10 mg L -1 ) was decomposed in 180 min with 40 mmol L -1 persulfate and 1.0 mmol L -1 AA, while only 15.4% and 3.2% of PCP was removed by alone persulfate and AA respectively. The result of EPR spectra identified sulfate radical (SO 4 •- ) and hydroxyl radical (OH) were generated during the reaction between persulfate and AA. Quenching experiments confirmed that both SO 4 - and OH contributed to the decomposition of PCP. With the addition of AA augmented from 0 to 1 mmol L -1 , the PCP degradation ratio continuously increased. However, excess AA could consume the generated reactive oxygen species (ROSs) that led to the inhibition of PCP degradation. Meanwhile, the PCP degradation by persulfate-AA was strongly pH dependent. The PCP degradation rate was declined as the initial pH increased from 3.5 to 10.5. At pH above 12.5, the base activation began to predominate over AA activation of persulfate. Furthermore, it was observed that the AA inducing persulfate activation was related to the extent of AA ionization, while C 6 H 8 O 6 promoted the highest persulfate activation for the PCP degradation, and C 6 H 6 O 6 2- induced the lowest persulfate activation. This study indicates the high potential of AA induced persulfate activation for treatment of organochlorine contaminated water., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Pentachlorophenol (PCP) is a class 2B human carcinogen that is used as an insecticide, herbicide, and wood preservative. PCP is rapidly absorbed and enters the blood where it can interact with erythrocytes. We have examined the effect of PCP on human erythrocytes. Treatment of erythrocytes with PCP increased the intracellular generation of reactive oxygen and nitrogen species. It also increased lipid and protein oxidation accompanied by decrease in glutathione levels and total sulfhydryl content. The activities of all major antioxidant enzymes were altered. The antioxidant power was significantly impaired resulting in lower free radical quenching and metal reducing ability of the PCP-treated cells. PCP exposure also inhibited the activities of enzymes of glycolysis and pentose phosphate shunt, the two pathways of glucose metabolism in erythrocytes. Heme degradation was enhanced leading to the release of free iron. Incubation of erythrocytes with PCP caused significant cell lysis suggesting plasma membrane damage which was also evident from inhibition of bound enzymes. Scanning electron microscopy of erythrocytes confirmed these biochemical results and showed that PCP treatment converted the normal biconcave discoids to echinocytes and other irregularly shaped cells. Thus, PCP induces oxidative and nitrosative stress in erythrocytes, alters the enzymatic and nonenzymatic antioxidant defense systems, inhibits glucose metabolism, and causes significant modifications in cellular morphology.

Compost-derived humic acids (HAs) as cheap soil conditioners have potential to facilitate pentachlorophenol (PCP) bio-dechlorination but lack proof and studies. To clarify this, PCP bio-dechlorination mediated by compost-derived HAs under Fe(III) reduction conditions was investigated. Reverse phase high-performance liquid chromatography and high-performance size exclusion chromatography were employed to identify the functional components within compost-derived HAs. Our results showed that compost-derived HAs facilitated the bio-dechlorination of PCP under Fe(III) reduction conditions, and four kinds of byproducts were detected during the process. The relatively hydrophilic and high molecular weight (MW) components within compost-derived HAs presented significant associations with the concentration of byproducts from bio-dechlorination of PCP in Fe 2 O 3 reduction conditions. In contrast, the hydrophobic and low MW components were the main functional components for PCP bio-dechlorination in Fe 3 O 4 reduction environment. These findings clarified the effects of polarity and MW of compost-derived HAs on PCP bio-dechlorination, giving clues to optimize composting technology to utilize compost products for in situ contamination remediation of paddy soil.

The development of new catalysts from abundant raw materials, generating attractive photocatalytic activity, constitutes a real challenge in the context of sustainable development concerns. In this setting, a dolomite was treated at 800 °C (D800) and then chemically modified by Ca(NO 3 ) 2 (CaD800) using a simple procedure. The resulting materials were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy (EDS), solid state UV spectroscopy, and used as catalysts of pentachlorophenol (PCP) degradation in aqueous solutions under UV light irradiation. The treatment of dolomite at 800 °C enabled a full decarbonation of CaMg(CO 3 ) 2 , with formation of CaO, Ca(OH) 2 , and MgO. Additional CaO was generated after chemical treatment as revealed by EDS analysis; the Ca/Mg ratio increased from 1.29 (D800) to 1.44 for CaD800. This CaO in aqueous medium hydrates by giving Ca(OH) 2 . CaD800 was found to be the best photocatalyst with a PCP degradation rate of 95% after only 1 h of treatment, for a CaD800/D800 degradation rate constant ratio of 1.58. In this regard, we investigated the Fourier transform infrared spectra of CaD800, PCP, and CaD800 loaded with PCP after degradation. We thus evidenced the involvement of Ca(OH) 2 in the PCP degradation process. Catalytic activity was discussed through the contribution of OH radicals and electrodonation.

Our previous study showed that tetrachlorobenzoquinone (TCBQ) mediated the activation of Nod-like receptor protein 3 (NLRP3) inflammasome, which involves K + efflux, reactive oxygen species (ROS) production, and mitochondrial DNA damage. In addition, TCBQ down-regulates NLRP3 ubiquitination and promotes the activation of NLRP3 inflammasome. However, the induction of NLRP3 inflammasome by atypical pathways has not yet been characterized. Using human umbilical vein endothelial cells (HUVEC), we discovered that TCBQ activates caspase 1/4/5 and cleaves gasdermin D (GSDMD) into N-terminal and C-terminal cleavage products. In parallel, TCBQ also activates receptor interacting protein kinase 3 (RIPK3)/mixed lineage kinase domain-like protein (MLKL) signaling pathways. The N-terminal fragments of GSDMD and MLKL translocate from cytoplasm to cell membrane and form oligomers and membrane pores on the cell membrane. The formation of membrane pores not only promotes the extracellular secretion of interleukin 1 beta (IL-1β) but also affects cellular ion homeostasis, in particular promotes K + outflow, which further activates NLRP3 inflammasome and aggravates cellular inflammation. These results indicated that GSDMD and MLKL play important roles in TCBQ-induced endothelial pro-inflammatory responses, which may point to potential therapeutic approaches for TCBQ-mediated toxicity.

Humin (HM) has been reported to function as an external electron mediator (EEM) in various microbial reducing reactions. In this study, the effect of isolation methods on EEM functionality and the chemical/electrochemical structures of HM were examined based on the correlation between dechlorination rates in the anaerobic HM-dependent pentachlorophenol (PCP)-dechlorinating consortium and the chemical/electrochemical structures of HM. A lack of PCP dechlorination activity suggested no EEM function in the HM samples prepared as a soluble fraction in dimethyl sulfoxide and sulfuric acid (which did not contain any electric capacitance). Other HM samples exhibited EEM functionality as shown by the dechlorination activity ranging from 0.55 to 3.48 (µmol Cl - ) L -1 d -1 . The comparison of dechlorination activity with chemical structural characteristics suggested that HM with EEM functionalities had predominantly aliphatic and carbohydrate carbons with the partial structures C=O, O=C⁻N, and O=C⁻O. EEM functionality positively correlated with the proportion of O=C⁻N and O=C⁻O, suggesting an association between peptidoglycan structure and EEM functionality. The lack of detection of a quinone structure in one HM sample with EEM functionality and a negative correlation with aromatic or C=C carbon suggested that the mechanism containing quinone structures is a minor component for the functionality of EEM.

Complete biodegradation and mineralization of pentachlorophenol (PCP), a priority pollutant in water, is challenging for water treatment. In this study, a hydrogen (H 2 )-based membrane biofilm reactor (MBfR) was applied to treat PCP, along with nitrate and sulfate, which often coexist in contaminated groundwater. Throughout 120-days of continuous operation, almost 100% of up to 10 mg/L PCP was removed with minimal intermediate accumulation and in parallel with complete denitrification of 20 mg-N/L nitrate. PCP initially was reductively dechlorinated to phenol, which was then mineralized to CO 2 through pathways that began with aerobic activation via monooxygenation by Xanthobacter and anaerobic activation via carboxylation by Azospira and Thauera. Sulfur cycling induced by SO 4 2- reduction affected the microbial community: The dominant bacteria became sulfate-reducers Desulfomicrobium, sulfur-oxidizers Sulfuritalea and Flavobacterium. This study provides insights and a promising technology for bioremediation of water contaminated with PCP, nitrate, and sulfate., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The sorption of trace organic pollutants at solid/liquid interfaces is one of the most important processes that influence their fate and behaviours in the aquatic environment. Sorption is affected by coexisting contaminants. The process and extent to which coexisting heavy metals affect the sorption of organochlorine pesticides (OCPs), especially acid radical anion heavy metals, are still unclear. Here, the effects of the species, concentrations, and speciation of the heavy metals Cu, Pb, and Cr, and the metalloid As on the sorption of pentachlorophenol (PCP), as a model OCP, by river biofilms were investigated through batch experiments. The results show that the presence of Cu, Pb, Cr, and As decreased the maximum sorption quantity of PCP onto the biofilms by 67.7, 9.2, 58.4, and 14.4%, respectively. The inhibitory effect of heavy metals on sorption decreased as the initial concentration ratios of heavy metals to PCP increased. In addition, the impact of heavy metals on PCP sorption was attributed to differences in heavy metal speciation. Cu and Pb commonly existed as divalent cations, but Cr and As existed as anionic acid radicals under the experimental conditions. The inhibitory effects of heavy metals on PCP sorption by biofilms were enhanced as the cation valence state increased, while the effects were weakened as the anionic acid radical valence state increased. Although all four heavy metals had inhibitory effects on PCP sorption by biofilms, there were distinct differences in the mechanisms causing these effects.

Composite surface soil samples were collected at 0, 25, and 50 cm from the base of 12 utility poles on the Kenai National Wildlife Refuge in Alaska, to assess the extent to which pentachlorophenol, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo furans may have leached from pentachlorophenol-treated poles. Six pairs of utility poles were included, consisting of an "old" pole manufactured in 1959 or 1963, a "new" pole manufactured within the past 20 years, and a suitable background soil sample from the same vicinity. Old poles had greater concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) near the pole base and at 25 cm than "new" poles did. For all 12 poles combined, the mean pentachlorophenol levels in soil were 1810, 157, and 17.8 ppm dry weight (d.w.) near the pole bases, at 25 and 50 cm from the poles, respectively, while the mean total TEQ levels in soil were 15,200, 5170, and 1510 parts per trillion d.w. at those distances. Surface soil levels of pentachlorophenol and TCDD-TEQs exceeded both human health and ecological risk-based screening levels. The design and results of this study were similar to another project in Montreal, Quebec in Canada. Together the results are cause for concern, indicating that millions of similarly treated utility poles in North America may be point sources of pentachlorophenol and dioxins/furans to soil.

The dechlorination of chlorinated organic pollutants by zero valent iron (ZVI) is an important water treatment process with a complex dependence on many variables. This complexity means that there are reported inconsistencies in terms of dechlorination with ZVI and the effect of ZVI acid treatment, which are significant and are as yet unexplained. This study aims to decipher some of this complexity by combining Raman spectroscopy with gas chromatography-mass spectrometry (GC-MS) to investigate the influence of the mineralogy of the iron oxide phases on the surface of ZVI on the reductive dechlorination of pentachlorophenol (PCP). Two electrolytic iron samples (ZVI-T and ZVI-H) were found to have quite different PCP dechlorination reactivity in batch reactors under anoxic conditions. Raman analysis of the "as-received" ZVI-T indicated the iron was mainly covered with the ferrous oxide (FeO) wustite, which is non-conducting and led to a low rate of PCP dechlorination. In contrast, the dominant oxide on the "as-received" ZVI-H was magnetite which is conducting and, compared to ZVI-T, the ZVI-H rate of PCP dechlorination was four times faster. Treating the ZVI-H sample with 1 N H 2 SO 4 made small change to the composition of the oxide layers and also minute change to the rate of PCP dechlorination. However, treating the ZVI-T sample with H 2 SO 4 led to the loss of wustite so that magnetite became the dominant oxide and the rate of PCP dechlorination increased to that of the ZVI-H material. In conclusion, this study clearly shows that iron oxide mineralogy can be a contributing factor to apparent inconsistencies in the literature related to ZVI performance towards dechlorination and the effect of acid treatment on ZVI reactivity.

Organic micropollutants, in particular those of anthropogenic origin, may have a toxic influence on water organisms. Photochemical oxidation processes are one of the most effective methods of decomposition of a wide range of those compounds. During the oxidation process a large number of different by-products are generated, which can still be biologically active. The development of analytical techniques, including the reduction of the detection limit to several fg/L, allows the identification of even trace concentrations of compounds. The paper presents the determination of pentachlorophenol and benzo(a)pyrene degradation pathways during the process of heterogeneous photocatalysis carried out in the presence of titanium dioxide. The gas chromatography-mass spectrometry (GC-MS) analysis of post-processing samples indicated the formation of different by-products of the parent micropollutants. Moreover, the toxicity assessment demonstrates for both tested micropollutants an increase in the toxicity within the whole time of the UV irradiation process run.

Study was undertaken to determine the effect of hydrostatic pressure on the sorption of pentachlorophenol (PCP). The experiment was conducted at atmospheric pressure (1000 hPa) and at increased pressure (6000 hPa) simulating conditions at the water depth of 50 m. The sorption of PCP was examined in an artificial environment (microcosm) consisting of the marine water and the bottom sediments from a Polish harbor and the southern Baltic Sea. The first part of the experiment comprised the determination of PCP sorption parameters in the microcosms and parameters of the sediments (organic matter content, conductivity) and of the overlying water (pH, ion concentration) at 1000 hPa. The second part of the experiment was conducted at 6000 hPa inside the hyperbaric chamber. The hyperbaric exposure affected parameters of the harbor sediments and the overlying water but had little influence on the concentration of PCP in the microcosms containing the southern Baltic Sea sediments. Considering the specific characteristics of the harbor sediments, it can be assumed that the impact of hydrostatic pressure on the sorption process of PCP at 50-m depth appears to be negligible.

Potassium permanganate (KMnO 4 ) has been an effective technology for the in situ chemical oxidation (ISCO) of many organic compounds including chlorinated alkanes and alkenes, but it has rarely been applied for oxidizing aromatic organochlorines. This study confirms the ability of permanganate to oxidize an aromatic chlorinated compound, pentachlorophenol (PCP), in an efficient manner at neutral pH. The rate of the reaction between KMnO 4 and PCP was calculated and the results indicated that the reaction between PCP and permanganate is relatively fast with a second-order rate constant k″ ∼ 30 M -1  s -1 . Besides the kinetic aspect, the authors identified the main reaction by-products, and proposed a possible reaction mechanism scheme. The general pathway shows the formation of chlorinated intermediates, and ultimately, the complete mineralization to chloride, water, and CO 2 confirmed by total organic carbon and chloride measurement in solution. Flow-through column experiments, consisting of flushing a PCP-contaminated sandy or natural soil with oxidant, showed the good ability of permanganate to eliminate the pollutant. After 24 h of treatment, 77% and 56% of PCP abatement were obtained for sandy and natural soil, respectively. These findings show the high potential of permanganate for the in situ remediation of aromatic organochlorine contaminated soils.

Various properties of soil affect the partition of organic contaminants within, and conversely, the properties of the organic contaminants also directly affect their partition behavior in soil. Therefore, understanding the effects of various properties of soil on the partition of organic contaminants favors subsequent assessment and provides soil remediation methods for policymakers. This study selected pentachlorophenol (PCP), a common hydrophobic ionizable organic compound in contaminated sites worldwide, as the target contaminant. The effects of pH, organic matter, and the combination of both, on PCP adsorption/desorption behavior in soil were investigated. Phosphoric acid and potassium hydroxide were used as buffer solutions to modify the soil pH by the batch and column extraction methods. A common retail organic fertilizer and fulvic acid were selected as additives to manipulate the soil organic content. Modifying the pH of the soil samples revealed that acidic soil exhibited a greater PCP adsorption rate than alkaline soil. The amount of PCP desorption increased regardless of pH of the in situ contaminated soil. The adsorption of PCP increased with increasing amount of organic additive. However, addition of fulvic acid yielded different results compared to the addition of organic fertilizer. Specifically, the organic fertilizer could not compete with the in situ contaminated soil in PCP adsorption, whereas fulvic acids increased the PCP dissolution to facilitate adsorbing contaminant adsorption. The combined effect of pH modification and organic matter addition provides additional PCP adsorption sites; therefore, adding the organic fertilizer to decrease the soil pH elevated the PCP adsorption rates of the laterite, alluvial, and in situ contaminated soil samples. The study results revealed that both pH and organic matter content are crucial to PCP adsorption/desorption in soil. Therefore, the effects of soil pH and organic matter should be considered in facilitating PCP treatment for soil remediation.

The ubiquitous distribution of halogenated aromatic compounds (XAr) coupled with their carcinogenicity has raised public concerns on their potential risks to both human health and the ecosystem. Recently, advanced oxidation processes (AOPs) have been considered as an "environmentally-friendly" technology for the remediation and destruction of such recalcitrant and highly toxic XAr. During our study on the mechanism of metal-independent production of hydroxyl radicals (OH) by halogenated quinones and H 2 O 2 , we found, unexpectedly, that an unprecedented OH-dependent two-step intrinsic chemiluminescene (CL) can be produced by H 2 O 2 and tetrachloro-p-benzoquinone, the major carcinogenic metabolite of the widely used wood preservative pentachlorophenol. Further investigations showed that, in all OH-generating systems, CL can also be produced not only by pentachlorophenol and all other halogenated phenols, but also by all XAr tested. A systematic structure-activity relationship study for all 19 chlorophenolic congeners showed that the CL increased with an increasing number of Cl-substitution in general. More importantly, a relatively good correlation was observed between the formation of quinoid/semiquinone radical intermediates and CL generation. Based on these results, we propose that OH-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual CL production; and a rapid, sensitive, simple, and effective CL method was developed not only to detect and quantify trace amount of XAr, but also to provide useful information for predicting the toxicity or monitoring real-time degradation kinetics of XAr. These findings may have broad chemical, environmental and biological implications for future studies on halogenated aromatic persistent organic pollutants., (Copyright © 2017. Published by Elsevier B.V.)

A three-dimensional quantitative structure activity relationship (3D-QSAR) model is built by using a comparative molecular similarity indices analysis (CoMSIA) technique with an experimentally determined logarithm of bioconcentration factors (logBCFs) for 36 phenols in fish. Meanwhile, with the pentachlorophenol (PCP) molecule as target molecules, contributions of the molecular fields indicate that the electrostatic fields are the main influences on the bioconcentration of the PCP molecule. Based on the analytical results of CoMSIA contour map of PCP and PCP molecular docking with SOD protease (PDB ID: 4A7T), the R 6 substituent positions of PCP were modified to give seven new modified PCP molecules with low bioconcentration in this paper. The energy barrier calculation of the new modified PCP molecular reaction pathways can infer the order of the substitution reaction s as -SCl > -CH 2 Cl > -COCl > -CCl 3  > -CH=CH 2  > -NO 2  > -SH. These calculations, combined with anaerobic biodegradation, ecotoxic effect, and mobility of new modified PCP molecules, enable a new environmentally friendly compound when the Cl at the R 6 position of PCP was replaced with -COCl substituent with low bioconcentration (reduced by 32.89%), ecotoxic effect basically unchanged (increased by 1.37%), anaerobic biodegradation increased (increased by 24.81%), and mobility basically unchanged (reduced by 0.94%) to be designed.

Phenanthrene (Phe) and pentachlorophenol (PCP) are classified as persistent organic pollutants and represent serious concern for the environment as they are toxic and ubiquitous. Biochar based remediation is an emerging technology used in water and soil contamination. In this study we used poplar (BP) and conifer (BC) biochars to remediate water and soil contaminated by Phe and PCP. BP and BC were able to remove completely either Phe or PCP from contaminated water within one to three days. When biochar was confined in a porous membrane, BC and BP maintained their sorption efficiency for several remediation cycles. However, in these conditions BC allowed faster Phe removal. In soil remediation experiments, addition of two biochar rates, i.e. 2.5 and 5 mg g -1 , strongly reduced Phe extractability (up to 2.7% of the initially added Phe with the larger BC dose). This was similar to the behavior observed when compost was applied in order to verify the role of soil organic matter in the fate of both contaminants. PCP extractability was reduced only up to 75% (in average) in all samples including those with compost amendment. Only larger amount of biochar (20 and 50 mg g -1 ) allowed reduction of the extractable PCP and nullified phytotoxicity of the contaminant., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The transformation of phosphorus added to the soil environment has been proven to be influenced by the Fe biochemical process, which thereby may affect the transformation of organic chlorinated contaminants. However, the amount of related literatures regarding this topic is limited. This study aimed to determine the effects of phosphorus addition on pentachlorophenol (PCP) anaerobic transformation, iron reduction, and paddy soil microbial community structure. Results showed that the transformation of phosphorus, iron, and PCP were closely related to the microorganisms. Moreover, phosphorus addition significantly influenced PCP transformation and iron reduction, which promoted and inhibited these processes at low and high concentrations, respectively. Both the maximum reaction rate of PCP transformation and the maximum Fe(II) amount produced were obtained at 1 mmol/L phosphorus concentration. Among the various phosphorus species, dissolved P and NaOH-P considerably changed, whereas only slight changes were observed for the remaining phosphorus species. Microbial community structure analysis demonstrated that adding low concentration of phosphorus promoted the growth of Clostridium bowmanii, Clostridium hungatei, and Clostridium intestinale and Pseudomonas veronii. By contrast, high-concentration phosphorus inhibited growth of these microorganisms, similar to the curves of PCP transformation and iron reduction. These observations indicated that Clostridium and P. veronii, especially Clostridium, played a vital role in the transformation of related substances in the system. All these findings may serve as a reference for the complicated reactions among the multiple components of soils.

An anaerobic soil slurry incubation experiment was conducted by controlling different Fe/S mole ratios (1/3, 1/2, 1/1, 2/1, 3/1, 8/1 and the control without sulfate) through the addition of sodium sulfate, to investigate the effect of sulfate and iron reduction on the reductive dechlorination of pentachlorophenol (PCP). Two sequential incubation periods were carried out with the stage I incubation conducted under a low electron donor concentration (0.5 mM lactate) and stage II incubation conducted under increased electron donor supply with lactate at 20 mM. During stage I, the production of Fe(II) occurred markedly while sulfate reduction and PCP dechlorination rate were low, with the highest dechlorination rates of PCP only 11.0% among all treatments at the end of stage I incubation. During stage II, both PCP dechlorination and sulfate reduction were greatly enhanced in all treatments, while the concentration of Fe(II) changed slightly. The rate of PCP dechlorination decreased (from 87.7% to 34.2%) with the increase of sulfate concentration (from Fe/S mole ratio of 8/1 to 1/3). Our study suggested that the presence of a certain amount of sulfate might facilitate PCP dechlorination in the range of Fe/S mole ratios greater than 1 when compared with the control without SO 4 2- . With the investigation of the dechlorination of PCP under the Fe-S-PCP coexisting condition with different Fe/S mole ratios, our study may provide improved strategy for optimizing the remediation of flooded soils and sediments polluted by PCP., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The remediation of dioxin-contaminated soil of a specific coastal area previously employed for the manufacture of pentachlorophenol (PCP) in southern Taiwan's Tainan City has attracted much attention of researchers there. This work addresses the possibility of providing an effective and environmentally friendly option for removing PCDD/Fs from soil in that field. Soil screening/sieving was first conducted to assess particle distribution. Fine sand was observed to be the major component of the soil, accounting for more than 60% of the total mass. A combination of ultrasonification and mechanical double-blade agitation was used to facilitate the washing of the soil using the biosurfactant anaerobic compost tea. More than 85 and 95% of total removal efficiencies were achieved for moderately and highly contaminated soils after 6 and 10 washing cycles, respectively, under ambient temperature, a soil/liquid ratio 1:2.5, 700 rpm, and over a relatively short duration. These results were achieved through the collision and penetration effects of this combined treatment as well as PCDD/F partitioning between the particles and anaerobic compost tea. This study represents the first to report the use of anaerobic compost tea solvent to wash soil highly contaminated by dioxin. It was concluded that anaerobic compost tea, rich in non-toxic bio-surfactants (e.g., alcohols, humic acids), can be used to improve bioavailability and bioactivity of the soil making bio-attenuation and full remediation more efficient.

The performance and removal mechanisms of a hybrid constructed wetland (HCW) followed by a willow planted filter (WPF) were evaluated for the treatment of a leachate contaminated by wood pole preservatives (pentachlorophenol (PCP) and chromated copper arsenate) to reach the storm sewer discharge limits. The HCW aimed to dechlorinate the PCP and polychlorodibenzo-p-dioxins/polychlorodibenzofuran (PCDD/F) and to remove metals by adsorption and precipitation. The HCW was efficient in removing PCP (>98.6%), oil, arsenic (99.4%), chromium (>99.2%), copper (>99.6%%) and iron (29%) to under their discharge limits, but it was unable to reach those of Mn and PCDD/F, with residual concentrations of 0.11 mg Mn/L and 0.32 pg TEQ/L. Iron and manganese could be removed but were subsequently released by the HCW due to low redox conditions. No dechlorination of PCDD/F was observed since its chlorination profile remained the same in the different sections of the HCW. Adsorption was the most probable removal mechanism of PCDD/F. The WPF was able to remove some residual contamination, but it released Mn at a gradually decreasing rate. Total evapotranspiration of the leachate by a larger fertilized WPF and the construction of an underground retention basin are proposed to prevent any discharge of PCDD/F traces in the environment.

Pentachlorophenol (PCP), an extensively used pesticide and biocide, is of critical environmental concern due to its toxicity and recalcitrance to degradation. In this study, the effect of PCP on induction of transcription factors, cytochrome P450 (CYP450) genes, and the antioxidative enzyme system were investigated in the quail liver. A total of 60 (4- to 6-week-old) male quails (Coturnix japonica) were administered 0, 0.05, 0.5, and 5 mg/kg/d PCP orally for 42 d. Following exposure, both absolute and relative liver weights were significantly lower than those of the control. Using gas chromatography-mass spectrometry, PCP accumulation was, from highest to lowest, kidney > liver > muscle for all exposure groups. The expressions of CYP1A5, CYP1B1, CYP2C18, nuclear translocator 1 (ARNT1), and aryl hydrocarbon receptor 1 (AHR1) were induced after PCP treatment, and increases were found in the activities of hepatic superoxide dismutase (SOD) and catalase (CAT), and the content of hepatic malondialdehyde (MDA). In addition, exposure to PCP induced an increase in liver 8-hydroxydeoxyguanosine (8-OHdG) and significantly elevated ethoxyresorufin O-deethylase (EROD), methoxyresorufin O-demethylase (MROD), and 7-ethoxycoumarin-O-deethylase (ECOD) activity, but decreased that of glutathione peroxidase (GSH-Px), benzyloxyresorufin O-debenzylase (BROD), pentoxyresorufin O-depentylase (PROD), and erythromycin N-demethylase (END). No significant responses were observed for benzyloxy-trifluoromethyl-coumarin (BFC). The protein level of liver nuclear factor κB (NF-κB) was higher, whereas that of nuclear factor E2-related factor 2 (Nrf2) was lower for exposed quail. These results suggest that PCP affects quail oxidative stress by modulating CYP450 enzymes and nuclear transcription factors., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Atmospheric transport is the major route for global distribution of semi-volatile compounds such as halogenated aromatics as well as their major exposure route for humans. Their major atmospheric removal process is oxidation by hydroxyl radicals. There is very little information on the reaction mechanism or reaction-path dynamics of atmospheric degradation of halogenated benzenes. Furthermore, the measured reaction rate constants are missing for the range of environmentally relevant temperatures, i.e. 230-330 K. A series of recent theoretical studies have provided those valuable missing information for fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene. Their comparative analysis has provided additional and more general insight into the mechanism of those important tropospheric degradation processes as well as into the mobility, transport and atmospheric fate of halogenated aromatic systems. It was demonstrated for the first time that the addition of hydroxyl radicals to monohalogenated as well as to perhalogenated benzenes proceeds indirectly, via a prereaction complex and its formation and dynamics have been characterized including the respective transition-state. However, in fluorobenzene and chlorobenzene reactions hydroxyl radical hydrogen is pointing approximately to the center of the aromatic ring while in the case of hexafluorobenzene and hexachlorobenzene, unexpectedly, the oxygen is directed towards the center of the aromatic ring. The reliable rate constants are now available for all environmentally relevant temperatures for the tropospheric oxidation of fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene while pentachlorophenol, a well-known organic micropollutant, seems to be a major stable product of tropospheric oxidation of hexachlorobenzene. Their calculated tropospheric lifetimes show that fluorobenzene and chlorobenzene are easily removed from the atmosphere and do not have long-range transport potential while hexafluorobenzene seems to be a potential POP chemical and hexachlorobenzene is clearly a typical persistent organic pollutant.

Pentachlorophenol (PCP) is a persistent pollutant which has been widely used as a pesticide and a wood preservative. As PCP is toxic and is present in significant quantities in the environment, there is considerable interest in elimination of PCP from waters. One of the promising methods is the application of ferrate. Ferrate is an oxidant and coagulant. It can be applied as a multi-purpose chemical for water and wastewater treatment as it degrades a wide range of environmental pollutants. Moreover, ferrate is considered a green oxidant and disinfectant. This study focuses on the kinetics of PCP degradation by ferrate under different pH conditions. The formation of degradation products is also considered. The second-order rate constants of the PCP reaction with ferrate increased from 23 M -1 s -1 to 4,948 M -1 s -1 with a decrease in pH from 9 to 6. At neutral pH the degradation was fast, indicating that ferrate could be used for rapid removal of PCP. The total degradation of PCP was confirmed by comparing the initial PCP molarity with the molarity of chloride ions released. We conclude no harmful products are formed during ferrate treatment as all PCP chlorine was released as chloride. Specifically, no polychlorinated dibenzo-p-dioxins and dibenzofurans were detected.

Chlorophenols are highly toxic, environmentally-persistent compounds which have been classified as probable human carcinogens by the United States Environmental Protection Agency. Due to the high toxicity of these compounds, it is necessary to treat water and soils with concentrations of chlorophenols above the detection limit set by regulatory agencies. The aim of this work is to demonstrate the capabilities of using ball-milled magnesium for the dechlorination of PCP. Comparison of dechlorination processes were performed in an attempt to determine the most effective system for degradation of PCP to phenol. Three systems with powerful capabilities of treatment were studied: ball-milled zero-valent magnesium (ZVMg), ball-milled zero-valent magnesium carbon (ZVMg/C), and ball-milled zero-valent magnesium with palladium (ZVMg/Pd). In addition to measuring PCP disappearance, all byproducts were identified and quantified for each degradation system. The results of these studies indicate that all three of the systems degrade PCP within 30 min. The most rapid and complete PCP dechlorination is achieved using ball-milled Mg/Pd and a matrix consisting of at least 0.02 g Mg0/mL ethanol, and 10 μL acetic acid/mL ethanol, in which case 20 ng/μL of PCP was dechlorinated to chlorophenols in approximately 15 min with complete dechlorination achieved in six days. Carbon mass balances of 90.16% for Mg, 94.76% (Mg/C) and 97.05% (Mg/Pd) verify dechlorination was responsible for declining concentrations of PCP. The reactions of PCP degradation and phenol formation were found to follow pseudo-first order kinetics for all systems. Further work will consist of optimization and development of field-scale applications., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Three-dimensional quantitative structure-activity relationship (3D-QSAR) models were established by comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA). Experimental toxicity data in Poecilia reticulata (pLC 50 ) and physico-chemical properties for 12 polychlorinated phenols were used as dependent and as independent variables, respectively. Among the 12 polychlorinated phenols, nine were randomly selected and used as a training set to construct the 3D-QSAR models through the SYBYL-X software to predict the pLC 50 values of the remaining 8 polychlorinated phenols congeners, and the other three polychlorinated phenols were used as a test set to evaluate the 3D-QSAR models (the training set and test set were arranged randomly, shuffled 60 times). Pentachlorophenol (PCP), which is the most toxic among the 20 polychlorinated phenols used in this experiment, was selected as an example for modification using contour maps produced using the established 3D-QSAR models. The aim was to decrease its toxicity and bioconcentration, increase its biodegradation, and maintain or better its effectiveness as a pesticide. The 3D-QSAR models were robust and had good predictive abilities with cross-validation correlation coefficients (q 2 ) of 0.858-0.992 (>0.5), correlation coefficients (r 2 ) of 0.966-1.000 (>0.9), and standard errors of prediction (SEP) of 0.004-0.159. CoMFA showed that the toxicity of the polychlorinated phenols arose mainly from electrostatic (42.7-66.7%) and steric (33.3-7.3%) contributions. By comparison, CoMSIA showed that the toxicity of polychlorinated phenols was dominated by electrostatic (57.5-76.9%) and hydrophobic (19.8-25.7%) contributions, with lesser contributions from the steric (0.7-1.0%) hydrogen bond donor (0.1-20.3%), and hydrogen bond acceptor (0-0.9%). 3D-QSAR electrostatic contour maps were used to modify PCP and design 11 new compounds with lower toxicity. The effectiveness of each of these molecules as a pesticide was verified using a 3D-QSAR model for polychlorinated phenol toxicity against Tetrahymena pyriformis. Four of these compounds, with -Br, -I, -OH and -NH 2 groups in place of chlorine at the 3-position on PCP, were all at least as effective as PCP against T. Pyriformis. The first-order rate constants (K b ) of these four compounds were predicted using a 3D-QSAR model for polychlorinated phenol degradation, which showed they were more biodegradable than PCP. Furthermore, a 3D-QSAR model for polychlorinated phenols bioconcentration in fish (containing Poecilia reticulata, Oncorhynchus mykiss, Pimephales promelas and Oryzias latipes) showed that there was no significant difference between the bioconcentration factors of the four new compounds and that of PCP. The results obtained are hoped to provide a new route for lowering the POPs characteristics of those polychlorinated phenol homologues and derivatives in use., (Copyright © 2016 Elsevier Inc. All rights reserved.)

The present study investigated the effects on reproductive and interrenal system by pentachlorophenol (PCP) using in silico and in vivo assays. Molecular docking results indicated interacting potency of PCP with steroid receptors (ERα, ERβ, AR, GR) but not Cytochrome P450 enzymes (CYPs). In the in vivo assay, sexually matured rare minnow (Gobiocypris rarus) was exposed to environmental relevant concentrations of PCP (0, 0.5, 5, 50 μg L -1 ). In male fish, 14-d exposure caused up-regulation of mRNA levels of hepatic erα, erβ, ar, gr, vtg and gonadal erα, vtg, ar, dmrt1, providing evidence for agonistic activities for steroid receptors by PCP. The up-regulated mRNA of gnrh, crf, pomc in the brain also indicated feed-forward responses of the hypothalamic-pituitary-gonadal/interrenal (HPG/I) axis. However, at 28th d the feed-forward response of the HPG axis seemed eased back and the HPI axis showed negative feedback responses. Corresponding changes including increases of plasma steroid hormones, inhibition of spermatogenesis, and decreased RSI were observed in male fish upon 28-d exposure to PCP. In the females, a transition from feed-forward responses to negative feedbacks of the HPG/I axis was also indicated by the transcriptional profiles at 14th and 28th day. Corresponding changes including increased E2, T and decreased C levels, degenerated ovaries, and decreased GSI and RSI were also observed. Overall, we concluded that PCP could interfere with steroid receptors, evoke responses of HPG/I axis, and finally result in adverse effects on reproductive and interrenal system in rare minnow at environmental relevant concentrations., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Hexachlorobenzene is highly persistent, bioaccumulative, toxic and globally distributed, a model persistent organic pollutant. The major atmospheric removal process for hexachlorobenzene is its oxidation by hydroxyl radicals. Unfortunately, there is no information on the reaction mechanism of this important atmospheric process and the respective degradation rates were measured in a narrow temperature range not of environmental relevance. Thus, the geometries and energies of all stationary points significant for the atmospheric oxidation of hexachlorobenzene are optimized using MP2/6-311G(d,p) method. Furthermore, the single point energies were calculated with G3 method on the optimized minima and transition-states. It was demonstrated for the first time that the addition of hydroxyl radicals to hexachlorobenzene proceeds indirectly, via a prereaction complex. In the prereaction complex the hydroxyl radical is almost perpendicular to the aromatic ring while oxygen is pointing to its center. In contrast, in the transition state it is nearly parallel with the aromatic ring. The reliable rate constants are calculated for the first time for the atmospheric oxidation of hexachlorobenzene for all environmentally relevant temperatures. It was also demonstrated for the first time that pentachlorophenol is the major stable product in the addition of hydroxyl radicals to hexachlorobenzene and that atmosphere seems to be a new global secondary source of pentachlorophenol., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Soil iron oxides (IOs) and organic matter (OM) play varying roles in pentachlorophenol (PCP) retention and mobility, but the extent and mechanism are still unknown. Therefore, in order to have a better understanding of the adsorption of PCP on soils, batch sorption studies were carried out on whole soils and soils selectively treated to remove IOs (IOR) and OM (OMR). The effects of pH, time, and temperature were investigated. Results showed that PCP sorption was temperature and pH dependent; sorption decreased as both temperature and pH increased. Sorption was partly surface adsorption and partly partitioning within voids of IOs components as revealed by the kinetics models. The surface adsorption was multi-layer in nature. Equilibria were faster in the IOR soils than the untreated and OMR soils. IOs played greater roles in PCP sorption than OM. Removal of soil components, especially the IOs, as experienced in soils plagued by soil erosion, may lead to increased risks of PCP pollution of environmental media especially the aquifer., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Soil microorganisms play crucial roles in the fates of pollutants, and understanding the behaviour of these microorganisms is critical for the bioremediation of PCP-contaminated soil. However, shifts remain unclear in the community structure and Fe(III)-reducing and dechlorinating microorganisms during PCP transformation processes, especially during the stages from the lag to the dechlorination phase and from the dechlorination to the stationary phase. Here, a set of lab-scale experiments was performed to investigate the microbial community dynamics accompanying PCP transformation in paddy soil. 19μM of PCP was biotransformed completely in 10days for all treatments. T-RFLP analysis of the microbial community confirmed that Veillonellaceae and Clostridium sensu stricto were the dominant groups during PCP transformation, and the structures of the microbial communities changed due to the degree of biotransformation and the addition of lactate and AQDS. However, similar temporal dynamics of the microbial communities were obtained among all treatments. Furthermore, as revealed by quantitative PCR, the dynamics of Fe(III)-reducing and dechlorinating microorganisms, including Geobacter sp., Shewanella sp., and Dehalobacter sp., were consistent with the transformation kinetics of PCP, suggesting the critical roles played by these microorganisms in PCP transformation. These findings are valuable for making predictions of and proposing methods for the microbial detoxification of residual organochlorine pesticides in paddy soil., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A quick, easy, cheap, effective, rugged and safe (QuEChERS)-based extraction method has been optimized for the determination of pentachlorophenol, 4-tertoctylphenol and 4-nonylphenol in river sediments. The extraction method was followed by gas chromatography-triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) analysis, which ensures the reliable identification of the target compounds. The proposed method has been validated allowing the successful determination of the selected compounds, with recoveries ranging from 72 to 96%, when three concentration levels were evaluated (10, 50 and 100μgkg(-1)) and inter-day and intra-day precision, expressed as relative standard deviation (RSD), were lower than 20%. The method showed limits of detection (LODs) and limits of quantification (LOQs) ranging from 0.1 to 2.0μgkg(-1) and from 0.5 to 5.0μgkg(-1), respectively. Finally, 25 real samples from Poland have been analyzed, and only 4-tertoctylphenol was detected at concentrations up to 8.9μgkg(-1) of soil dry weight., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A novel process involving 254 nm UV-C and fructose to degrade pentachlorophenol (PCP), a pollutant, in low and high salinity (0-10 g/L salt) solutions is presented. The first order rate constants in the presence of 0, 300, and 500 mM fructose were 0.23 ± 0.04, 0.54 ± 0.01, and 1.18 ± 0.03 min(-1), respectively. Experimental evidence has shown generation of hydrogen peroxide and singlet oxygen from the UV-C exposure of fructose, which may have accelerated PCP degradation. Although salts (sodium, potassium, and calcium chloride, 1101:6.4:1) are expected to enhance the degradation rate due to generation of reactive halide species (RHS) from exposure to UV-C light, 10 g/L salt decreased the degradation rates in both the absence and presence of fructose. An LC-ESI-MS spectrum of the reaction mixture revealed a high relative abundance at m/z of 215 that corresponds to a fructose-chlorine adduct, indicating that fructose may have scavenged these RHS and prevented their reaction with PCP.

A novel bio-analytical method has been devised based on the change in catalytic activity of acetylcholinesterase (AChE) enzyme induced by captan, carbosulfan, 2,3,7,8-tetrachlorodibenzodioxin (TCDD) and pentachlorophenol (PCP) for the investigation of inhibition efficiency and sensitivity using Pt/ZnO/AChE/Chitosan bioelectrode. The inhibition curves of captan, carbosulfan, TCDD and PCP were similar to Michaelis-Menten curve. TCDD held the minimum inhibitor Michaelis-Menten constant ([Formula: see text]) value (10.2 nM) in comparison with PCP (10.9 nM), carbosulfan (14.5 nM) and captan (7.9 × 10(3) nM). The maximum inhibition of AChE enzyme by captan was about 100 %, which was much higher than that of TCDD (72.7 %), PCP (68.1 %) and carbosulfan (47.7 %). The calculated theoretical sensitivity was in the order of TCDD > PCP > carbosulfan > captan. Comparing with TCDD (35.3 %), PCP (47.8 %) and carbosulfan (20.9 %), only the inhibition efficiency of captan (55.0 %) was the maximum. The developed bioelectrode exhibited high recovery and low relative standard deviation in local tap water samples.

Pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and mercury were simultaneously removed from heavily contaminated soil using a continuous pilot-scale thermal system (CPTS). Operating the system at 700 °C with 22 min of retention time ensured that the residual contaminants in remediated soil are lower in concentration than the soil standards of Taiwan EPA require. Both PCP and PCDD/Fs are effectively destroyed during the treatment at high temperatures in the CPTS, but significant dechlorination of PCDD/Fs is also found, resulting in lower net destruction efficiencies of TCDD/F and PeCDD/F-congeners, compared with those of highly chlorinated Hx-, Hp- and OCDD/F congeners. Moreover, 2,3,7,8-TetraCDD is significantly formed if the retention time is not long enough for total destruction. Inadequate reaction time (or retention time) even may lead to a rise in TEQ-value due to incomplete dechlorination. Mercury is significantly desorbed from contaminated soil and discharged through the exhaust. For PCP and PCDD/Fs, the exhaust discharge percentages including both the remediated soil and the exhaust are <0.03% and 1.14% of the input, respectively, achieved with 700 °C and 33 min retention time. In contrast, some 97.8% of input mercury rate is desorbed and discharged via the exhaust, so that the latter should be carefully cleaned via efficient air pollution control devices, whereas this contribution focuses on the conditions required for reaching adequate soil cleaning., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Preferential removal of pentachlorophenol (PCP) from chlorophenols-containing wastewater has been attracted more attentions in wastewater treatment, since it is one of the most toxic pollutants. The adsorbent of N-doped ordered mesoporous carbon (M-OMC) with high BET surface area of 1901 m(2)/g, large pore volume of 1.64 cm(3)/g and uniform pore size of 3.45 nm has been successfully synthesized via evaporation-induced self-assembly (EISA) method. The effects of solution pH, pore structure of adsorbent and their surface chemical properties on PCP adsorption by M-OMC were investigated in comparison with ordered mesoporous carbon (OMC), and much higher PCP adsorption capacities of M-OMC were obtained. The significantly preferential adsorption of PCP was achieved in the treatment of tri-component wastewater including PCP, p-chlorophenol (CP) and 2.4.6-trichlorophenol (TCP), and its adsorption process well fitted the pseudo-second-order kinetics model and the Langmuir isotherm. The initial sorption rate of PCP was 103.5 μmol/(g/min), which was 2.97 times of TCP. It may be attributed to the intensification of π-π interaction between PCP and M-OMC with the nitrogen functional groups. Therefore, M-OMC is promising for removal of PCP in the adsorption pretreatment of chlorophenols-containing wastewater.

Nanoscale zero-valent iron (nZVI) is an environmentally benign material that has been widely used as a reducing agent to treat environmental pollutants. In this study, nZVI was used as a heterogeneous Fenton catalyst in an nZVI/H2O2 system to remove pentachlorophenol (PCP) from water. The PCP degradation process in the nZVI/H2O2 system was completed within 1h. The relative Cl(-) concentration increased throughout the test period (6h), indicating that the performance of the oxidative system in terms of dechlorination was excellent. The initial H2O2 concentration significantly influenced the PCP removal rate, and nZVI performed better than commercial zero-valent iron as a catalyst. Moreover, magnetite (Fe3O4), which was the main product of the corrosion of nZVI, was found to perform well as an adsorbent and catalyst, so it allowed the nZVI to be effectively reused., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The reductive dechlorination of pentachlorophenol (PCP) by Geobacter sulfurreducens in the presence of different biochars was investigated to understand how biochars affect the bioreduction of environmental contaminants. The results indicated that biochars significantly accelerate electron transfer from cells to PCP, thus enhancing reductive dechlorination. The promotion effects of biochar (as high as 24-fold) in this process depend on its electron exchange capacity (EEC) and electrical conductivity (EC). A kinetic model revealed that the surface redox-active moieties (RAMs) and EC of biochar (900 °C) contributed to 56% and 41% of the biodegradation rate, respectively. This work demonstrates that biochars are efficient electron mediators for the dechlorination of PCP and that both the EC and RAMs of biochars play important roles in the electron transfer process.

Pentachlorophenol (PCP) is a common residual persistent pesticide in paddy soil and has resulted in harmful effect on soil ecosystem. The anaerobic microbial transformation of PCP, therefore, has been received much attentions, especially the functional microbial communities for the reductive transformation. However, the key functional microorganisms for PCP mineralization in the paddy soil still remain unknown. In this work, DNA-based stable isotope probing (SIP) was applied to explore the key microorganisms responsible for PCP mineralization in paddy soil. The SIP results indicated that the dominant bacteria responsible for PCP biodegradation belonged to the genus Dechloromonas of the class β-Proteobacteria. In addition, the increased production of (13)CH4 and (13)CO2 indicated that the addition of lactate enhanced the rate of biodegradation and mineralization of PCP. Two archaea classified as the genera of Methanosaeta and Methanocella of class Methanobacteria were enriched in the heavy fraction when with lactate, whereas no archaea was detected in the absence of lactate. These findings provide direct evidence for the species of bacteria and archaea responsible for anaerobic PCP or its breakdown products mineralization and reveal a new insight into the microorganisms linked with PCP degradation in paddy soil., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The photodegradation of pentachlorophenol (PCP) in a surfactant-containing (single and mixed) complex system using graphene-TiO2 (GT) as catalyst was investigated. The objective was to better understand the behavior of surfactants in a GT catalysis system for its possible use in remediation technology of soil contaminated by hydrophobic organic compounds (HOCs). In a single-surfactant system, surfactant molecules aggregated on GT via hydrogen bonding and electrostatic force; nonideal mixing between nonionic and anionic surfactants rendered GT surface with mixed admicelles in a mixed surfactant system. Both effects helped incorporating PCP molecules into surfactant aggregates on catalyst surface. Hence, the targeted pollutants were rendered easily available to photo-yielded oxidative radicals, and photodegradation efficiency was significantly enhanced. Finally, real soil washing-photocatalysis trials proved that anionic-nonionic mixed surfactant soil washing coupled with graphene-TiO2 photocatalysis can be one promising technology for HOC-polluted soil remediation.

Natural soil montmorillonite and kaolinite nanoparticles (NPs) were tested as efficient sorbents for organic contaminant (OC) removal through mimicking their natural environmental dispersive states. Sorption of both mineral NPs decreased with increasing pH with ionizable pentachlorophenol (PCP), but increased with pH with non-ionizable phenanthrene (PHE), within the pH range of 4-10. In contrast, sorption decreased consistently for both PCP and PHE, as a function of increasing ion concentration (0.001-0.1 mol L(-1)). Sorption differences were likely caused by the electrolytic conditions dependent upon surface chemistry of OCs and mineral NPs. The results confirmed that the highly dispersive soil mineral NPs would prevail over both engineered NPs and their regular μm-sized colloids for OC removal, due to their ecological advantages and higher sorption properties. This finding provided a realistic assessment of the environmental function of soil natural minerals in water once they are released from soil into OC polluted aqueous systems., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200-700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs)., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In this study we evaluated the feasibility of two regeneration strategies of contaminated polymers employed for ex-situ soil remediation in a two-step process. Soil decontamination is achieved by sorption of the pollutants on the polymer beads, which are regenerated in a subsequent step. Tested soil was contaminated with a mixture of 4-chlorophenol and pentachlorophenol, and a commercial polymer, Hytrel, has been employed for extraction. Removal efficiencies of the polymer-soil extraction are in the range of 51-97% for a contact time ≤ 24 h. Two polymer regeneration strategies, solvent extraction and biological regeneration (realized in a two-phase partitioning bioreactor), were tested and compared. Performance was assessed in terms of removal rates and efficiencies and an economic analysis based on the operating costs has been performed. Results demonstrated the feasibility of both regeneration strategies, but the bioregeneration was advantageous in that provided the biodegradation of the contaminants desorbed from the polymer. Practically complete removal for 4-chlorophenol and up to 85% biodegradation efficiency for pentachlorophenol were achieved. Instead, in the solvent extraction, a relevant production (184-831 L kg(pol)(-1)) of a highly polluted stream to be treated or disposed of is observed. The cost analysis of the two strategies showed that the bioregeneration is much more convenient with operating costs of ∼12 €/kg(pol) i.e. more than one order of magnitude lower in comparison to ∼233 €/kg(pol) of the solvent extraction., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

In this study, we demonstrate that pentachlorophenol contaminated soil can be efficiently remediated with tetrapolyphosphate washing and subsequent zerovalent iron (ZVI)/Air treatment. 2 mmol L(-1) of tetrapolyphosphate could wash away 52.8% of pentachlorophenol (PCP) at pH 7.0 and 84.2% of pentachlorophenol at pH 11.0 from contaminated soil owing to the promotion effect of tetrapolyphosphate on the soil matrix dispersion and the subsequent solubilization of pentachlorophenol. More importantly, tetrapolyphosphate ions remained in the washing effluent could greatly enhance the molecular oxygen activation by ZVI to oxidize the desorbed PCP without any pH adjustment, and also avoid the competitive consumption of reactive oxygen species, as caused by the common organic surfactants in the washing effluent. Therefore, 85.1% of pentachlorophenol could be aerobically removed from the washing effluent by merely using 5 g L(-1) of ZVI. We also interestingly found that the dissolved iron ions released from the soil could enhance the oxidation of pentachlorophenol in the washing effluent, but the dissolved organic matter had the opposite effect. This study suggests the coupling tetrapolyphosphate washing and subsequent ZVI/Air treatment is an optional approach to remediate pentachlorophenol contaminated soil in view of its low cost and environmental benign., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The ubiquitous distribution coupled with their carcinogenicity has raised public concerns on the potential risks to both human health and the ecosystem posed by the halogenated aromatic compounds (XAr). Recently, advanced oxidation processes (AOPs) have been increasingly favored as an "environmentally-green" technology for the remediation of such recalcitrant and highly toxic XAr. Here, we show that AOPs-mediated degradation of the priority pollutant pentachlorophenol and all other XAr produces an intrinsic chemiluminescence that directly depends on the generation of the extremely reactive hydroxyl radicals. We propose that the hydroxyl radical-dependent formation of quinoid intermediates and electronically excited carbonyl species is responsible for this unusual chemiluminescence production. A rapid, sensitive, simple, and effective chemiluminescence method was developed to quantify trace amounts of XAr and monitor their real-time degradation kinetics. These findings may have broad biological and environmental implications for future research on this important class of halogenated persistent organic pollutants.