Treatment technologies used for the removal of As, Cr, Cu, PCP and/or PCDD/F from contaminated soil: A review.

The contamination of soils by metals such as arsenic, chromium, copper and organic compounds such as pentachlorophenol (PCP) and dioxins and furans (PCDD/F) is a major problem in industrialized countries. Excavation followed by disposal in an appropriate landfilling is usually used site to manage these contaminated soils. Many researches have been conducted to develop physical, biological, thermal and chemical methods to allow the rehabilitation of contaminated sites. Thermal treatments including thermal desorption seemed to be the most appropriate methods, allowing the removal of more than 99.99% of organic contaminants but, they are ineffective for inorganic compounds. Biological treatments have been developed to remove inorganic and hydrophobic organic contaminants but their applications are limited to soils contaminated by easily biodegradable organic compounds. Among the physical technologies available, attrition is the most commonly used technique for the rehabilitation of soils contaminated by both organic and inorganic contaminants. Chemical processes using acids, bases, redox agents and surfactants seemed to be an interesting option to simultaneously extract organic and inorganic contaminants from soils. This paper will provide an overview of the recent developments in the field of decontamination technologies applicable for the removal of As, Cr, Cu, PCP and/or PCDD/F from contaminated soils.

Removing pentachlorophenol from water using a nanoscale zero-valent iron/H2O2 system.

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.

Effect of pyrolysis temperature on polycyclic aromatic hydrocarbons toxicity and sorption behaviour of biochars prepared by pyrolysis of paper mill effluent treatment plant sludge.

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).

Silver nanoparticles decorated anatase TiO22nanotubes for removal of pentachlorophenol from water.

One-dimensional nanotubes are promising materials for environmental applications. In this study, anatase TiO2 nanotubes (TNTs) were fabricated using an alkaline hydrothermal method at 130°C and then calcinated at 400°C for 2h. Ag nanoparticles were photo-deposited onto the TNTs for enhanced photodegradation of pentachlorophenol (PCP) under simulated solar light. The samples were characterized using transmission electron microscopy, physical adsorption of nitrogen, X-ray diffraction, X-ray photoelectron spectroscopy and UV-Visible diffuse reflectance spectroscopic techniques. The as-synthesized TNTs showed tubular structures with the outer and inner diameter of 9-10 and 5-6 nm, respectively. The results showed that metallic Ag nanoparticles were uniformly dispersed on the TNTs surface, and Ag/TNTs exhibited significant visible-light absorption. After 180 min irradiation, about 99% PCP was removed by Ag/TNTs (5.4 at.%), compared to 54.3% by P25 and 59.4% by pure TNTs. This is attributed to the synergistic effects between Ag nanoparticles acting as traps to effectively capture the photo-generated electrons, and the localized surface plasmon resonance (LSPR) of Ag nanoparticles promoting the absorption of visible light. The intermediates during the PCP photodegradation were systematically analyzed, ruling out the existence of high toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Ag/TNTs showed excellent stability even after five cycles.

The reactivity of well-dispersed zerovalent iron nanoparticles toward pentachlorophenol in water.

In order to prevent the aggregation of nanoparticles (NPs), surface modification or the addition of a stabilizer are used for stabilization. However, the real reactivity of NPs is still unclear because of the surface coating. For different physical dispersion methods, the particle stabilization for nanoscale zerovalent iron (NZVI) particles and their reactivity are studied. The particle properties of different preparations and their reactivity toward one polychlorinated aromatic compound, pentachlorophenol (PCP), with different electrolytes are also evaluated. Ultrasonication (US) with magnetic stirring disperses NZVI and Pd/Fe NPs well in water and does not affect the surface redox property a lot under the operating conditions in this study. The well-suspended NZVI cannot dechlorinate PCP but adsorption removal is observed. Compared to shaking, which gives limited removal of PCP (about 43%), Pd/Fe NPs remove 81% and 93% of PCP from water in the US and the US/stirring systems, respectively, which demonstrates that a greater surface area is exposed because of effective dispersion of Pd/Fe NPs. As the Pd doping increases, the dechlorination kinetics of PCP is improved, which shows that a catalyst is needed. With US/stirring, chloride ions do not significantly affect the removal kinetics of PCP, but the removal efficiency increases in the presence of nitrate ions because PCP anions were adsorbed and coagulated by the greater amount of iron (hydro)oxides that are generated from the reduction of nitrate on Pd/Fe. However, bicarbonate ions significantly block the adsorption and reaction sites on the Pd/Fe NP surface with US/stirring. The US/stirring method can be used to evaluate the actual activity of NPs near the nanoscale. The use of Pd/Fe NPs with US/stirring removes PCP from water effectively, even in the presence of common anions expect a high concentration of bicarbonate.

Pentachlorophenol aerobic removal in a sequential reactor: start-up procedure and kinetic study.

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.

Biosorption of pentachlorophenol by Anthracophyllum discolor in the form of live fungal pellets.

Pentachlorophenol (PCP) is an extremely dangerous pollutant for every ecosystem. In this study we have detected how PCP concentration and pH levels can influence PCP adsorption by Anthracophyllum discolor in the form of live fungal pellets. PCP adsorption was evaluated after 24 hours in KCl 0.1 M electrolyte solution with initial PCP concentrations of 5 and 10 mg L (-1) and with pH values between 4 and 9 (at intervals of 0.5). Fourier Transform Infrared Spectroscopy (FTIR) was used to identify functional groups of fungal biomass that can interact with PCP. The amount of PCP that was adsorbed by A. discolor was >80% at pH values between 5 and 5.5, whatever the concentration tested. PCP adsorption significantly decreased in liquid medium of pH > 6.0. FTIR results showed that amides, alkanes, carboxylates, carboxyl and hydroxyl groups may be important to the PCP adsorption for pellets of A. discolor. Live fungal pellets of A. discolor may be used as a natural biosorbent for liquid solutions contaminated by PCP.

Synthesis of the magnetic biochar composites for use as an adsorbent for the removal of pentachlorophenol from the effluent.

The zero-valent iron magnetic biochar composites (ZVI-MBC) were synthesized from the paper mill sludge biochar and used for the treatment of the synthetic and real effluent containing pentachlorophenol (PCP). During the synthesis of ZVI-MBC, NaBH4 was used as the reducing agent to reduce Fe(II) to Fe(0) and cetyltrimethylammonium bromide was added as surfactant. The effect of the molar ratio of FeSO4 to NaBH4, dose of the surfactant and the ZVI to biochar ratio on the PCP removal efficiency was investigated. It was found that the ZVI-MBC combines the advantages of biochar and ZVI particles for the simultaneous adsorption and dechlorination of PCP in the effluent and the complete removal of PCP was obtained. The ageing tests showed that biochar prevents the formation of oxide film on the ZVI particles and leaching tests confirmed the stability of ZVI on biochar matrix as very low iron leaching was noticed.

Enhanced photocatalytic removal of sodium pentachlorophenate with self-doped Bi2WO6 under visible light by generating more superoxide ions.

In this study, we demonstrate that the photocatalytic sodium pentachlorophenate removal efficiency of Bi2WO6 under visible light can be greatly enhanced by bismuth self-doping through a simple soft-chemical method. Density functional theory calculations and systematical characterization results revealed that bismuth self-doping did not change the redox power of photogenerated carriers but promoted the separation and transfer of photogenerated electron-hole pairs of Bi2WO6 to produce more superoxide ions, which were confirmed by photocurrent generation and electron spin resonance spectra as well as superoxide ion measurement results. We employed gas chromatography-mass spectrometry and total organic carbon analysis to probe the degradation and the mineralization processes. It was found that more superoxide ions promoted the dechlorination process to favor the subsequent benzene ring cleavage and the final mineralization of sodium pentachlorophenate during bismuth self-doped Bi2WO6 photocatalysis by producing easily decomposable quinone intermediates. This study provides new insight into the effects of photogenerated reactive species on the degradation of sodium pentachlorophenate and also sheds light on the design of highly efficient visible-light-driven photocatalysts for chlorophenol pollutant removal.

Decontamination of metals, pentachlorophenol, and polychlorined dibenzo-p-dioxins and dibenzofurans polluted soil in alkaline conditions using an amphoteric biosurfactant.

In this paper, flotation in acidic conditions and alkaline leaching soil washing processes were compared to decontaminate four soils with variable contamination with metals, pentachlorophenol (PCP), and polychlorodibenzo dioxins and furans (PCDD/F). The measured concentrations of the four soils prior treatment were between 50 and 250 mg/kg for As, 35 and 220mg/kg for Cr, 80 and 350mg/kg for Cu, and 2.5 and 30mg/kg for PCP. PCDD/F concentrations reached 1394, 1375, 3730, and 6289ng/kg for F1, S1, S2, and S3 soils, respectively. The tests were carried out with masses of 100g of soil (fraction 0-2 mm) in a 2 L beaker or in a 1 L flotation cell. Soil flotation in sulphuric acid for 1 h at 60 degreeC with three flotation cycles using the surfactant cocamidopropyl betaine (BW) at 1% allows the solubilization of metals and PCP with average removal yields of 85%, 51%, 90%, and 62% for As, Cr, Cu, and PCP, respectively. The alkaline leaching for 2 h at 80 degreeC solubilizes As, Cr, Cu, and PCP with average removal yields of 60%, 32%, 77%, and 87%, respectively. Tests on PCDD/F solubilization with different surfactants were carried out in combination with the alkaline leaching process. PCDD/F removal yields of 25%, 72%, 70%, and 74% for F1, S1, S2, and S3 soils, respectively, were obtained using the optimized conditions.

Microwave/H2O2 efficiency in pentachlorophenol removal from aqueous solutions.

BACKGROUND: Pentachlorophenol (PCP) is one of the most fungicides and pesticides. Acute and chronic poisoning from PCP may be occurred by dermal absorption, and respiration or ingestion. With respect to health and environmental effects of PCP, many methods were considered regarding its removal. Microwave assisted other methods are environmental friendly, safety, and economical method, consequently, in this study; microwave assisted with hydrogen peroxide (MW/H2O2) was used for PCP removal from aquatic solutions. METHODS: The possible of PCP removal was considered by application of a modified domestic microwave. PCP removal rate was considered under different factors such as H2O2 dose (0.01, 0.02, 0.1, 0.2, 0.3 mol/L), PCP concentration (100,200, 300, 400, 500, 750, 1000 mg/L), pH (3, 7, 11), energy intensity (180,450, 600 W), COD (344 mg/L), and scavenger testes (0.02 mol/L from each of Tert- butyl alcohol (TBA), NaCl, NaHCO3, and Na2CO3). The concentration changes of PCP were determined using spectrophotometer and HPLC spectra, respectively. RESULTS: The best PCP removal was obtained in condition of pH 11, 0.2 mol/L H2O2, and 600 W energy intensity. Moreover, COD removal in this condition was 83%. Results obtained from radical scavengers indicated that OH° had only an initiator role, and had not a dominant role, and order reaction was in first order. CONCLUSIONS: The results of microwave/H2O2 application showed that this process is suitable for removal of PCP and other chlorinated organic compounds in alkaline pH.

Determination of pentachlorophenol residue in meat and fish by gas chromatography-electron capture detection and gas chromatography-mass spectrometry with accelerated solvent extraction.

A novel analytical method, using gas chromatography-electron capture detection (GC-ECD) and GC-mass spectrometry detection (MS), was developed for the qualitative and quantitative measurement of pentachlorophenol in meat and fish. The analyte was extracted by methanol-2% trichloroacetic acid (3/1, v/v) with accelerated solvent extraction (ASE). The eluted fraction was evaporated and derivatized with acetic anhydride-pyridine (1/1, v/v) for GC-ECD analysis and GC-MS confirmation. The parameters for extraction pressure, temperature and cycle of ASE, cleanup, derivatization and analysis procedure were optimized. The averaged decision limits and detection capability of the method were in the ranges of 0.25-0.41 and 0.49-1.01 µg/kg in the muscle and liver of swine and bovine and in the muscle of carp and finless eel, respectively. Spiked recoveries from levels of 0.5-2.0 µg/kg were found to be more than 71.1%, with relative standard deviation less than 14.7% in GC-ECD and GC-MS. This rapid and reliable method can be used for the characterization and quantification of residues of pentachlorophenol in animal and fish tissues.

Nanoscale Fe(0) particles for pentachlorophenol removal from aqueous solution: temperature effect and particles transformation.

Pentachlorophenol (PCP), as an important contaminant which was toxic and intractable, has received extensive attention. In this paper, the temperature effect during the transformation of PCP using nanoscale Fe(0) particles was studied, and the transformation processes of PCP and iron particles was explained. The results revealed that the removal processes of PCP followed pseudo first-order kinetics. The scale of dechlorination to the transformation of PCP increased with the increase of temperature, though the transformation rate decreased after reacting for 2 h under the experimental condition. However, the initial apparent transformation rate constants were calculated to be 0.312-0.536 h(-1) at the temperature of 20-50 degrees C, which showed an increase of transformation rate along with the increase of temperature. And the surface-area-normalized rate constants were calculated to be 9.50 x 10-3-1.63 x 10-2 L . h-1 . m-2. The experimental activation energy was calculated to be 15.0 kJ x mol(-1) from these rate constants using Arrhenius equation. A phenomenon observed at 50 degrees C indicated that more than one chlorine atom was removed from PCP and suggested ß-elimination might be the major pathway for transformation. Sorption experiments showed that the sorption process on the surface of particles could be ignored in the kinetics and thermodynamics models. The changes of morphologies of nanoparticles before and after reaction indicated the transformation process of iron particles, and could be used to explain the changes of activity of nanoparticles. Magnetite (Fe3O4) and/or maghemite (Fe2O3) and lepidocrocite (γ-FeOOH) were corrosion products of iron. And along with the increase of temperature, the increased intensity of XRD peaks revealed the related a better crystallizing.

Removal of PCP-Na from aqueous systems using monodispersed pompon-like magnetic nanoparticles as adsorbents.

Novel monodispersed pompon-like magnetite/chitosan (Fe3O4/CS) composite nanoparticles were synthesized by a solvothermal method and used as adsorbents for the removal of toxic sodium pentachlorophenate (PCP-Na) from aqueous media. The adsorption behavior of PCP-Na on Fe3O4/CS obeyed the Langmuir isotherm and fitted the pseudo-second-order kinetics model. Thermodynamic parameters showed that the adsorption process was exothermic and spontaneous. Moreover, the adsorption was strongly pH-dependent. The results of XPS, thermodynamics, pH-dependent and desorption studies suggested that electrostatic attraction, hydrogen bonding and π-π interactions were all believed to play a role in PCP-Na adsorption on Fe3O4/CS. Having a saturation magnetization of 22.2 emu · g(-1), the Fe3O4/CS can be easily separated from water with magnets within 2 min. The adsorption equilibrium was achieved quite rapidly (within 30 min) and the maximum removal of PCP-Na (91.5%) was obtained at 25 °C and pH 6.5. The Fe3O4/CS investigated can be used to remove PCP-Na and other contaminants from wastewater.

Direct electron transfer from electrode to electrochemically active bacteria in a bioelectrochemical dechlorination system.

Pentachlorophenol (PCP) was dechlorinated by electrochemically active bacteria using an electrode as the direct electron donor. Dechlorination efficiency and coulombic efficiency (CE) were investigated. When hydrogen evolution reaction was eliminated by controlling the potential, both dechlorination efficiency and CE increase as the potential decreases, which implied the dechlorination was stimulated by electric current rather than hydrogen gas. Further investigation of the cyclic voltammetry characterization of the medium revealed nearly no redox mediator secreted by the bacteria. Moreover, the comparison of dechlorination experiments carried out with filtered and unfiltered medium provided convincible evidence that the dominating electron transfer mechanism for the dechlorination is direct electron transfer. Additionally, 454 pyrosequencing technique was employed to gain a comprehensive understanding of the biocathodic microbial community. The results showed Proteobacteria, Bacteroidetes and Firmicutes were the three predominant groups. This paper demonstrated the direct electron transfer mechanism could be involved in PCP dechlorination with a biocathode.

Enhanced removal of a pesticides mixture by single cultures and consortia of free and immobilized Streptomyces strains.

Pesticides are normally used to control specific pests and to increase the productivity in crops; as a result, soils are contaminated with mixtures of pesticides. In this work, the ability of Streptomyces strains (either as pure or mixed cultures) to remove pentachlorophenol and chlorpyrifos was studied. The antagonism among the strains and their tolerance to the toxic mixture was evaluated. Results revealed that the strains did not have any antagonistic effects and showed tolerance against the pesticides mixture. In fact, the growth of mixed cultures was significantly higher than in pure cultures. Moreover, a pure culture (Streptomyces sp. A5) and a quadruple culture had the highest pentachlorophenol removal percentages (10.6% and 10.1%, resp.), while Streptomyces sp. M7 presented the best chlorpyrifos removal (99.2%). Mixed culture of all Streptomyces spp. when assayed either as free or immobilized cells showed chlorpyrifos removal percentages of 40.17% and 71.05%, respectively, and for pentachlorophenol 5.24% and 14.72%, respectively, suggesting better removal of both pesticides by using immobilized cells. These results reveal that environments contaminated with mixtures of xenobiotics could be successfully cleaned up by using either free or immobilized cultures of Streptomyces, through in situ or ex situ remediation techniques.

Low-temperature anaerobic treatment of low-strength pentachlorophenol-bearing wastewater.

The anaerobic treatment of low-strength wastewater bearing pentachlorophenol (PCP) at psychro-mesophilic temperatures has been investigated in an expanded granular sludge bed reactor. Using an upward flow rate of 4 m h(-1), a complete removal of PCP, as well as COD removal and methanization efficiencies higher than 75% and 50%, respectively, were achieved. Methanogenesis and COD consumption were slightly affected by changes in loading rate, temperature (17-28°C) and inlet concentrations of urea and oils. Pentachlorophenol caused an irreversible inhibitory effect over both acetoclastic and hydrogenotrophic methanogens, being the later more resistant to the toxic effect of pentachlorophenol. An auto-inhibition phenomenon was observed at PCP concentrations higher than 10 mg L(-1), which was accurately predicted by a Haldane-like model. The inhibitory effect of PCP over the COD consumption and methane production was modelled by modified pseudo-Monod and Roediger models, respectively.

Developing an alcoholic-assisted dispersive liquid-liquid microextraction for extraction of pentachlorophenol in water.

Optimization of alcoholic-assisted dispersive liquid-liquid microextraction of pentachlorophenol (PCP) and determination of it with high-performance liquid chromatography (UV-Vis detection) was investigated. A Plackett-Burman design and a central composite design were applied to evaluate the alcoholic-assisted dispersive liquid-liquid microextraction procedure. The effect of seven parameters on extraction efficiency was investigated. The factor studied were type and volume of extraction and dispersive solvents, amount of salt, and agitation time. According to Plackett-Burman design results, the effective parameters were type and volume of extraction solvent and agitation time. Next, a central composite design was applied to obtain optimal condition. The optimized conditions were obtained at 170-µL 1-octanol and 5-min agitation time. The enrichment factor of PCP was 242 with limits of detection of 0.04 µg L(-1). The linearity was 0.1-100 µg L(-1) and the extraction recovery was 92.7%. RSD for intra and inter day of extraction of PCP were 4.2% and 7.8%, respectively for five measurements. The developed method was successfully applied for the determination of PCP in environmental water samples.

The sorption of pentachlorophenol by aged sediment supplemented with black carbon produced from rice straw and fly ash.

Black carbon (BC) is a potential material for controlling hydrophobic organic contaminants in sediment because it has a high sorption capacity. In the present study, the sorption of pentachlorophenol (PCP) onto sediments supplemented with rice straw biochar (RC) and fly ash (FC) aged for different times and at temperatures were investigated. The sorption of PCP increased with increasing amounts of BC and decreased with aging time and storage temperature of the BC-supplemented sediments. The sorption of PCP onto RC-supplemented sediments was higher than those supplemented with FC regardless of whether or not BCs were aged in sediments. For aged sediments containing 2% BCs, the sorption capacity was 9.15- and 2.87-fold higher than that of FC when supplemented with RC aged at 25 and 45°C, respectively. Therefore, biochar is better than fly ash for controlling organic pollutants even when the RC was present in sediment for a long time.

Multi-class pesticide analysis in human hair by gas chromatography tandem (triple quadrupole) mass spectrometry with solid phase microextraction and liquid injection.

A method for the simultaneous detection and quantification of 22 pesticides from different chemical classes was developed using solid-phase microextraction (SPME) and gas chromatography tandem (triple quadrupole) mass spectrometry. Pesticides were extracted from 50mg of pulverized hair with acetonitrile. The extract was submitted to two successive steps of direct immersion-SPME at 30°C and 90°C or to a liquid injection without SPME in order to obtain optimized conditions for each of the 22 analytes investigated. Validation parameters were significantly influenced by both the injection mode (SPME vs liquid injection) and the temperature of SPME. Limits of quantification ranged from 0.05 pg mg(-1) for trifluralin to 10 pg mg(-1) for pentachlorophenol. The application of the validated method to the analysis of samples collected from non-occupationally exposed volunteers demonstrated the presence of pesticides in all the samples tested. Altogether, 13 different analytes were detected at concentration above the limit of quantification.