Pentachlorophenol Residues Research Articles

Synthesis of magnetic molecularly imprinted microsphere and development of an enhanced semi-homogeneous method for detection of pentachlorophenol in fish

In this study, pentachlorobenzene was used as dummy template to synthesize a type of magnetic molecularly imprinted microsphere for pentachlorophenol. At the same time, pentachloroaniline was coupled to streptavidinated horseradish peroxidase to synthesize an enzyme labeled tracer. The two reagents were used to develop a semi-homogeneous method on conventional microplate for detection of pentachlorophenol in fish samples. Due to the use of biotinylated horseradish peroxidase as signal amplification agent, the method sensitivity was improved for 375 folds in comparison with the use of conventional horseradish peroxidase labeled tracer with a limit of detection of 0.8 fg/g. After comparison, it was found that this method showed better performances than the previous immunoassays and molecularly imprinted polymer based methods for detection of pentachlorophenol. This study for the first time reported a magnetic molecularly imprinted microsphere based semi-homogeneous method for detection of small molecule, and this method could be used for routine determination of pentachlorophenol residue in fish samples.

Non-Destructive Detection of Pentachlorophenol Residues in Historical Wooden Objects.

Wood is a natural polymeric material that is an important constituent of many heritage collections. Because of its susceptibility to biodegradation, it is often chemically treated with substances that can be harmful to human health. One of the most widely used wood preservatives was pentachlorophenol (PCP), which is still present in museum objects today, although its use has been restricted for about forty years. The development of non-destructive methods for its determination, suitable for the analysis of valuable objects, is therefore of great importance. In this work, two non-destructive solid-phase microextraction (SPME) methods were developed and optimized, using either headspace or contact mode. They were compared with a destructive solvent extraction method and found to be suitable for quantification in the range of 7.5 to 75 mg PCP/kg wood at room temperature. The developed semi-quantitative methods were applied in the wooden furniture depot of National Museum of Slovenia. PCP was detected inside two furniture objects using headspace mode. The pesticide lindane was also detected in one object. The indoor air of the depot with furniture was also sampled with HS SPME, and traces of PCP were found. According to the results, SPME methods are suitable for the detection of PCP residues in museum objects and in the environment.

A four-year phytoremediation trial to decontaminate soil polluted by wood preservatives: phytoextraction of arsenic, chromium, copper, dioxins and furans

Widely used as wood preservatives for the last century, Pentachlorophenol (PCP) and chromated copper arsenate (CCA) have been shown to leach from treated surfaces and contaminate soil of wood storage sites. We performed a four-year field phytoremediation trial in southern Quebec (Canada) on a site contaminated with PCP and CCA with the following objectives: (1) assess the potential of willow, fescue, alfalfa and Indian mustard to tolerate and translocate CCA and PCP residues in their aerial tissues, (2) investigate the possibility of phytoextraction of dioxins and furans, and (3) test the effect of nitrogen fertilizer on phytoremediation performance. We showed that while nitrogen fertilization increased the chlorophyll content of plants, it did not result in a significantly greater plant biomass. We also showed that plants grown in the presence of PCP/CCA residues were able to translocate and concentrate trace elements in their aerial tissues, but also dioxins and furans (PCDD/F). This suggests that plants grown on sites polluted by PCP might contain dioxins and furans and should be treated as contaminated by these toxic chemicals. Finally, the reduction of soil contaminants at the end of the trial suggests that phytoremediation is a promising approach for decontaminating such sites.

The association of cancer risks with pentachlorophenol exposure: Focusing on community population in the areas along certain section of Yangtze River in China

Pentachlorophenol (PCP) was used in large quantities, and mainly for killing the intermediate host snails of schistosome in China, thereby resulting in ubiquitous PCP residue in the environment. However, studies considering the carcinogenicity of PCP for humans mainly focused on occupational workers, and the actual carcinogenicity of PCP for general population is uncertain. To investigate the association between cancer risks and PCP exposure in a community population, an ecological study was conducted in three contaminated areas along the Yangtze River. Standardized rate ratio (SRR) was calculated to represent the risk of cancer incidence, by using incidence in the low PCP exposure category as the reference group. A total of 15,962 cancer records were collected, and 76 water samples and 213 urine samples in three areas were examined. Our findings suggested that compared with the low PCP group, the high PCP group had significantly excessive incidences of various cancers related to different organs including lymph (SRR = 19.44, 95% CI = 15.00–25.19), blood (SRR = 17.24, 95% CI = 12.92–23.01), nasopharynx (SRR = 3.97, 95% CI = 3.75–4.21), gallbladder (SRR = 3.46, 95% CI = 3.09–3.87), pancreas (SRR = 3.41, 95% CI = 3.07–3.79), respiratory system (SRR = 3.41, 95% CI = 3.27–3.57) and liver (SRR = 3.31, 95% CI = 3.09–3.56). Taken together, our present study provides evidence that general community population exposed to high level of PCP exhibits a broader spectrum of increased cancer risks as compared to occupational groups.

Evaluation of Pentachlorophenol Residues in Some Hygienic Papers Prepared from Virgin and Secondary Pulp by Electron Capture Gas Chromatographic Method

In this study, residual amount of pentachlorophenol (PCP) as the most important paper preservative, which is extremely hazardous pollutant, was determined in some tissue papers and napkins. Twenty-five samples of two producing hygienic paper factories prepared from virgin and secondary pulp were analyzed for the presence of trace amount of PCP. The analytical procedure involved direct extraction of PCP from hygienic paper and its determination by gas chromatography with electron capture detection. The statistical results for the analysis of all samples revealed that there were significant differences between mean of PCP in hygienic papers prepared from virgin and secondary pulp ( P <0.05). This method gave recoveries of 86-98% for hygienic paper made from virgin pulp and 79-92% for hygienic paper made from secondary pulp. The limit of detection (LOD) and limit of quantification (LOQ) for PCP were 6.3 and 21.0 mg/kg, respectively. The analytical method has the requisite sensitivity, accuracy, precision and specificity to assay PCP in hygienic papers. This study demonstrates a concern with exposition to PCP considering that hygienic paper is largely consumed in the society.

Effects of Dielectric Barrier Discharge Plasma Treatment on Pentachlorophenol Removal of Granular Activated Carbon

The pentachlorophenol (PCP) adsorbed granular activated carbon (GAC) was treated by dielectric barrier discharge (DBD) plasma. The effects of DBD plasma on the structure of GAC and PCP decomposition were analyzed by N2 adsorption, thermogravimetric, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and gas chromatography mass spectrometry (GC-MS). The experimental data of adsorption kinetics and thermodynamics of PCP on GAC were fitted with different kinetics and isotherm models, respectively. The results indicate that the types of N2 adsorption isotherm of GAC are not changed by DBD plasma, while the specific surface area and pore volume increase after DBD plasma treatment. It is found that the weight loss of the saturated GAC is the highest, on the contrary, the weight loss of DBD treated GAC is the least because of reduced PCP residue on the GAC. The XPS spectra and SEM image suggest that some PCP on the GAC is removed by DBD plasma, and the surface of GAC treated by DBD plasma presents irregular and heterogeneous morphology. The GC-MS identification of by-products shows that two main dechlorination intermediate products, tetrachlorophenol and trichlorophenol, are distinguished. The fitting results of experimental data of adsorption kinetics and thermodynamics indicate that the pseudo-first-order and pseudo-second order models can be used for the prediction of the kinetics of virgin GAC and DBD treated GAC for PCP adsorption, and the Langmuir isotherm model fits better with the data of adsorption isotherm than the Freundlich isotherm in the adsorption of PCP on virgin GAC and DBD treated GAC.

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.

Determination of residues of pentachlorophenol and its sodium saltin aquatic product by gas chromatography using internalstandard method

The aim of this study was to reduce the loss of preliminary treatment of sample such as deriva-tives and emulsification,to enhance the maneuverability and accuracy of method,to promote the in stabil-ity of detection.Residues of pentachlorophenol and its sodium salt in edible tissues of crucian,freshwater shrimp,cod and chinese mitten crab were determined by gas chromatography using internal standard method.Such factors as derivation method,Whether n-hexane was blowed or not for pentachlorophenol and its sodium salt were compared in this paper.Moreover,the chromatographic conditions were surveyed and optimized for detection of the residues of pentachlorophenol and its sodium salt in edible tissues.The target compounds were first extracted two times with n-hexane in an acidic medium,and then back ex-tracted with potassium carbonate solution.The extract was derived with acetic anhydride,and the deriva-tive was extracted with n-hexane.The HP-5MS(30 m×0.32 mm×0.25 μm) column and the micro-cell elec-tron capture detector was used for the determination.This method chooses 2,4,6-TBP as internal standard substance.The working curves were linear(R2=0.9996) in the range of 0.2-20.0 μg/L.When spiked with 2.0,5.0,10.0,50.0 μg/kg of pentachlorophenol and 50 μg/kg of 2,4,6-tribromophenol,the average recov-eries were 85.8%-109.0% and the RSD were 0.8%-9.3%.The detection limit was 0.6 μg/kg.

TiO2 AND TiO&lt;sub&gt;2&lt;/sub&gt;/ ACTIVE CARBON PHOTOCATALYSTS IMMOBILIZED ON TITANIUM PLATES

Study of TiO2 and TiO2 active carbon photocatalyst was done. Immobilization was carried out by sol-gel process using titanium diisopropokside bis-acetylacetonato as titanium precursor. The catalyst was characterized using XRD and SEM. The activity of catalyst was tested using 10 ppm of pentachlorophenol (PCP) as a model of organic waste. The test was done by irradiating PCP solution using UV lamp and varying the catalysts of TiO2, and TiO2/C of 8/2 and 5/5. About 5 mL of sample was taken out at interval time of 1, 2, 4, 6, 8 and 10 h iradiation followed by the measurement of PCP residue and chloride ions. From the characterization results it is known that calcined TiO2 andTiO2/C of 8/2 and 5/5 have anatase structure and active as a catalyst. The activity results using PCP as an organic waste showed that combination of TiO2 and active carbon would increase the activity of the catalyst, but at high percentage of active carbon the performance of the photocatalyst decreased. Keywords: catayist TiO2, catayist TiO2/active carbon, photocatalysis

Development of an enzyme-linked immunosorbent assay for the detection of pentachlorophenol residues in water samples

An indirect competitive enzyme-linked immunosorbent assay (ELISA) for pentachlorophenol (PCP) was developed with a polyclonal antiserum produced against a hapten, 4-(2,3,5,6-tetrachloro-4-hydroxyphenoxy)-butyric acid, conjugated to bovine serum albumin (BSA). The ELISA of PCP showed an IC50 of 18 ng/ml and a limit of detection (LOD) of 0.9 ng/ml at the optimal concentration of NaCl (0.2 M) in the assay buffer. This assay was slightly affected by up to 10% (v/v) methanol or acetone. The IC50 and A max values showed little change in a pH range of 5 and 7. Very low cross reactivities (≤2.5%) were observed for some structurally-related compounds, except for 2,3,4,6-tetrachlorophenol (5.6%) and 2,3,5,6-tetrachlorophenol (9.2%). The average recoveries of PCP from fortified water were in the range of 71–118%. The results by GC and ELISA for the same fortified water samples showed non-significant difference (p>0.05). Finally, this ELISA was applied to monitor PCP in 100 river water samples and no PCP was detected. This ELISA is a good alternative tool for monitoring PCP residues in water samples.

Pentachlorophenol Residues in Suspended Particulate Matter and Sediments from the Yangtze River Catchment of Wuhan, China

Pentachlorophenol Residues in Suspended Particulate Matter and Sediments from the Yangtze River Catchment of Wuhan, China

Generalized models for prediction of pentachlorophenol dissipation dynamics in soils

Dissipation of pentachlorophenol (PCP) in soil was investigated and the chemical relationships with soil properties were addressed. The results indicate that the dissipation of extractable PCP residues can be described using first-order kinetics equations, with a half-dissipation time ( T 1/2) ranging from 6.5 to 173.3 d. The sharply different patterns of PCP dissipation in different soils were closely related to soil properties. Correlations of stepwise regression equations obtained were significant at 0.01 probability level between soil parameters and extractable PCP residues ( R 2 = 0.974**) as well as T 1/2 values ( R 2 = 0.882**). Using pH together with organic carbon content (OC) and soil particle size distribution, the dissipation dynamics of PCP in soil could be accurately predicted.

Laboratory trials on the bioremediation of aged pentachlorophenol residues

Abstract The variable nature of field-contaminated soil requires reliable assessments or treatability studies to optimise the bioremediation process in the field. In a series of laboratory-based studies, experiments were developed and conducted to determine fungal isolate variations, optimum fungal inoculum concentration, optimum treatable contaminant concentration and predict pentachlorophenol (PCP) degradation over time. Generally, biodegradation of PCP in old (>30 years) field-contaminated soil (i.e. aged residues) was similar between New Zealand native isolates compared to the American isolates of Phanerochaete chrysosporium or P. sordida. A concentration of up to 2786 mg freshly added PCP kg−1-soil was readily biodegraded if augmented with live or dead white-rot isolates. However, no biodegradation or soil colonisation was observed at these high PCP concentrations when aged residues were used. Increasing the amount of fungal inoculum (>30%; v/v) for soil augmentation with white-rot fungi did not improve colonisation of field-contaminated PCP soil. Generally, soil colonisation by white-rot fungi did not correlate with PCP decline. However, soil colonisation and PCP biodegradation were isolate dependent. When aged residues were used, the variation between repeated residue analyses was high and similar to the variance among isolates and among isolates within sampling dates. Therefore stratified sampling protocols were developed for PCP residue analysis to be able to determine differences between fungal treatments. The results of the described experiments were then used to standardise treatability studies.

Spectrophotometric detection of pentachlorophenol (PCP) in water using immobilized and water-soluble porphyrins

The spectrophotometric properties of porphyrins are altered upon interaction with chlorophenols and other organochlorine pollutants. Meso-tetra(4-sulfonatophenyl)porphyrin (TPPS), zinc meso-tetra(4-sulfonato phenyl)porphyrin (Zn-TPPS), monosulfonate-tetraphenylporphyrin (TPPS 1), meso-tri(4-sulfonatophenyl)mono(4-carboxyphenyl)porphyrin (C 1TPP), meso-tetra(4-carboxyphenyl)porphyrin (C 4TPP), and copper meso-tetra(4-carboxyphenyl)porphyrin (Cu-C 4TPP) in solution exhibit a broad absorbance in the range 400–450 nm Soret region. The interaction of the above mentioned porphyrins in solution with pentachlorophenol (PCP) induces a red shift in the Soret spectrum with absorbance losses at 413, 418, 403, 405, 407, and 404 nm, respectively, and the appearance of new peaks at 421, 427, 431, 416, 417, and 416 nm, respectively. The intensity of the Soret spectral change is proportional to the pentachlorophenol concentration with a detection limit of 1, 0.5, 1.16, 1, 0.5, and 0.5 ppb, respectively. The interaction of (C 4TPP) and (Cu-C 4TPP) in solution with PCP shows to concentration dependent for concentrations less than 4 ppb the dependence was log-linear. However, for concentrations greater than 4 ppb the relation was linear. Monosulfonate-tetraphenylporphyrin immobilized as a monolayer on a Kimwipe ® tissue exhibits an absorbance peak in the Soret region at 422 nm. The interaction of the porphyrin with PCP induces a red shift in the Soret spectrum with absorbance loss at 419 nm and the appearance of new peaks at 446 nm. The intensity of the Soret spectral change is proportional to the log of PCP concentration. The detection limit with immobilized TPPS 1 for PCP is 0.5 ppb. These results suggest the potential for development of spectrophotometric chemosensor for PCP residues in water with detection limits less than US EPA maximum contaminate level (MCL) of 1 ppb. The immobilized TPPS 1 on the Kimwipe ® will make it possible to develop a wiping sensors to monitor the PCP or other pesticides residues on the vegetables or wood products.

Spectrophotometric detection of pentachlorophenol (PCP) in water using water soluble porphyrins

The spectrophotometric properties of porphyrins are altered upon interaction with chlorophenols and other organochlorine pollutants. Meso-tetra (4-sulfonatophenyl)porphyrin (TPPS), zinc meso-tetra (4-sulfonato phenyl) porphyrin (Zn-TPPS), monosulfonate tetraphenylporphyrin (TPPS 1), meso-tri (4-sulfonatophenyl)-mono(4-carboxyphenyl)porphyrin (C 1TPP), meso-tetra (4-carboxyphenyl) porphyrin (C 4TPP), and copper meso-tetra (4-carboxyphenyl)porphyrin (Cu-C 4TPP) in solution exhibit a broad absorbance in the range of 400–450 nm Soret region. The interaction of the above mentioned porphyrins in solution with pentachlorophenol induces a red shift in the Soret spectrum with absorbance losses at 413, 418, 403, 405, 407, and 404 nm, respectively, and the appearance of new peaks at 421, 427, 431, 416, 417, and 416 nm, respectively. The intensity of the Soret spectral change is proportional to the pentachlorophenol concentration with a detection limit of 1, 0.5, 1.16, 1, 0.5, and 0.5 ppb, respectively. The interaction of (C 4TPP) and (Cu-C 4TPP) in solution with PCP is dependent on concentration; for concentrations less than 4 ppb the dependence was log-linear. However, for concentrations greater than 4 ppb the relation was linear. These results suggest the potential for development of spectrophotometric chemosensor for PCP residues in water with detection limits less than US EPA maximum contaminate level (MCL) of 1 ppb.

Determination of tribromophenol and pentachlorophenol and its metabolite pentachloroanisole in Asparagus officinalis by gas chromatography/mass spectrometry

AbstractA GC‐MS method was developed and optimized for simultaneous determination of pentachlorophenol (PCP), 2,4,6‐tribromophenol (TBP), and pentachloroanisole (PCA) residues in the edible part of Asparagus officinalis. For this purpose, two procedures were evaluated: the direct separation of PCP, TBP, and PCA and the separation of acetyl‐PCP, acetyl‐TBP, and non‐acetylated PCA. Better sensitivity and quantitative results, especially for PCP, were obtained after acetylation. The residues of PCP and TBP were extracted as phenolates and acetylated in a carbonate solution. Acetylated compounds were extracted by liquid‐liquid extraction with hexane, while PCA was directly leached with this solvent. The proposed method allows the rapid quantification of traces of PCP, TBP, and PCA in a concentration ranging between 1.0 and 8.0 ng mL–1 in solution (corresponding to 0.3 and 8.0 μg kg–1 in asparagus). In this concentration range, typical recoveries for PCA, TBP, and PCP from asparagus samples were 59%, 86%, and 97% respectively (RSDs 3–7%).

Removal of biocide pentachlorophenol in water system by the spent mushroom compost of Pleurotus pulmonarius

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

Treated wood in livestock facilities: relationships among residues of pentachlorophenol, dioxins, and furans in wood and beef

Wood and other environmental samples were collected from sites that produced beef with higher than average residues of dibenzo- p-dioxin (PCDD) and dibenzofuran (PCDF). Analyses of these samples for PCDD/Fs and pentachlorophenol (PCP) indicated that the high beef residues were associated with PCP-treated wood in the animal facilities. Concentrations of PCDD/Fs in wood as toxic equivalents ranged from 10 to 320,000 pg/g. These concentrations were closely related to the concentrations of PCP, indicating that analysis for PCP provides an economical method to identify wood with high concentrations of PCDD/Fs. Further evidence for the PCP-treated wood as the source of the beef residues is provided by the similarity of the congener profiles in beef from the sites and those profiles predicted from the profiles in wood.

Treating an aged pentachlorophenol- (PCP-) contaminated soil through three sludge handling processes, anaerobic sludge digestion, post-sludge digestion and sludge land application

The extensive pentachlorophenol (PCP) contamination and its increasing treatment costs motivate the search for a more competitive treatment alternative. In a municipal wastewater treatment plant, anaerobic sludge-handling processes comprises three bio-processes, namely the anaerobic sludge digestion, post-sludge digestion and sludge land application, which reduce sludge organic content and make sludge a good fertilizer for land application. Availability and effectiveness make the anaerobic sludge handling processes potential technologies to treat PCP-contaminated soil. The technical feasibility of using anaerobic sludge bioprocesses was studied by treating PCP soil in two pilot digesters to simulate the primary sludge digestion, in serum bottles to mimic the post-sludge digestion, and in glass pans to represent the on-site sludge application. For primary digestion, the results showed that up to 0.98 and 0.6 mM of chemical and soil PCP, respectively, were treated at nearly 100% and 97.5% efficiencies. The PCP was transformed 95% to 3-MCP, 4.5% to 3,4-DCP, and 0.5% to 3,5-DCP. For post-digestion, 100% pure chemical PCP and greater than 95% soil PCP were removed in less than 6 months with no chlorophenol residues of any kind. Complete removal of PCP by-products makes this process a good soil cleanup method. For on-site treatment, PCP was efficiently treated by multiple sludge application; however, the PCP residue was observed due to the high initial PCP content in soil. Overall, more mass PCP per unit sludge per day was processed using the primary sludge digestion than the on-site soil treatment or post-sludge digestion. And, sludge acclimation resulted in better PCP treatment efficiencies with all three processes.

Atmospheric pentachlorophenol concentrations in relation to air temperature at five Canadian locations

Pentachlorophenol (PCP), used as a wood preservative and as a disinfectant, has been found in human urine samples from Saskatchewan and in air samples from three Canadian sites. To confirm the presence of atmospheric PCP residues and to explore seasonality, weekly samples were collected at five Canadian sites for three consecutive weeks, in the months of July and October, 1995 and January, April and May, 1996, using a high volume sampler equipped with polyurethane foam (PUF) plugs. PCP was present in all samples collected adjacent to a utility pole storage site with concentrations ranging from 0.7 to 1233.0 ng m −3. There was a very strong correlation between average weekly air temperature, measured over a range of −29.3 to +20.0°C, and the log 10 of the average weekly concentration of PCP at this site. PCP was measured in 7 of 11 air samples from each of two small cities (concentrations ranging from 0.2 to 6.8 ng m −3) and the correlation between temperature and PCP concentration, for these two city sites, was similar to that for the utility pole storage site. Concentrations of PCP at two rural sites were lower (0.1-1.5 ng m −3)) and detected less frequently. As a consequence, the correlation between air temperature and PCP concentration was more variable.