Determination of PAH, PCB, and OCP in water from the Three Gorges Reservoir accumulated by semipermeable membrane devices (SPMD)

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were measured in the water column from Three Gorges Reservoir (TGR) collected in May 2008 using semipermeable membrane devices (SPMDs). The sampling sites spanned the whole reservoir from the upstream Chongqing to the great dam covering more than 600 km long distance with water flow velocities ranging from <0.05 to 1.5 m s(-1). This is the first experience of SPMD application in the biggest reservoir in the world. The results of water sampling rates based on performance reference compounds (PRC) were tested to be significantly correlated with water flow velocities in the big river. Results of back-calculated aqueous concentrations based on PRC showed obvious regional variations of PAH, PCB and OCP levels in the reservoir. Total PAH ranged from 13.8 to 97.2 ng L-1, with the higher concentrations occurring in the region of upstream and near the dam. Phenanthrene, fluoranthene, pyrene and chrysene were the predominant PAH compounds in TGR water. Total PCB ranged from 0.08 to 0.51 ng L-1, with the highest one occurring in the region near the dam. PCB 28, 52, 101, 138, 153, 180, 118 were the most abundant PCB congeners in the water. The total OCP ranged from 2.33 to 3.60 ng L-1 and the levels showed homogenous distribution in the whole reservoir. HCH, DDT and HCB, PeCB were the major compounds of OCP fingerprints. Based on water quality criteria, the TGR water could be designated as being polluted by HCB and PAH. Data on PAH, PCB and OCP concentrations found in this survey can be used as reference levels for future POP monitoring programmes in TGR. (C) 2009 Elsevier Ltd. All rights reserved.

Apoptosis induction on human hepatoma cells Hep G2 of decabrominated diphenyl ether (PBDE-209)

Polybrominated diphenyl ethers (PBDEs) are an important class of halogenated organic brominated flame retardants. Because of their presence in abiotic and biotic environments widely and their structural similarity to polychlorinated biphenyls (PCBs), concern has been raised on their possible adverse health effects to humans. This study was designed to determine the anti-proliferative, apoptotic properties of decabrominated diphenyl ether (PBDE-209), using a human hepatoma Hep G2 line as a model system. Hep G2 cells were cultured in the presence of PBDE-209 at various concentrations (1.0-100.0 mu mol/L) for 72 h and the percentage of cell viability was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. The results showed that PBDE-209 inhibited the cells viability in time and concentration-dependent characteristics at concentrations (10.0-100.0 mu mol/L). We found that anti-proliferative effect of PBDE-209 was associated with apoptosis on Hep G2 cells by determinations of morphological changes, cell cycle and apoptosis. Mechanism study showed that PBDE-209 could increase the generation of intracellular reactive oxygen species (ROS) concentration-dependently. Antioxidant N-acetylcyteine partially inhibited the increase of ROS. The mechanism for its hepatoma-inhibitory effects was the induction of cellular apoptosis through ROS generation. In addition, activity of lactate dehydrogenase (LDH) release increased when the cells incubated with PBDE-209 at various concentrations and times. These results suggested that PBDE-209 had the toxicity activity of anti-proliferation and induction of apoptosis in tumor cells in vitro. (c) 2007 Elsevier Ireland Ltd. All rights reserved.

PCBs and OCPs in human milk and selected foods from Luqiao and Pingqiao in Zhejiang, China

This study was conducted to measure the levels of 23 PCB congeners and 6 organochlorine pesticides (OCPs) in human milk and three food types collected from Luqiao and Pingqiao in Zhejiang Province, China. An effort was also made to explore the potential health risk for the mothers and breast-fed infants living in these two localities. Luqiao was selected as the sampling site because it is the largest place for the disassembly of obsolete transformers and electrical waste in China. Pingqiao, located 100 kin NW of Luqiao, is not known to be a place for any electronic or electrical waste and hence was chosen as the control site. Both localities are important agricultural places in the province. The organochlorines were measured in the samples using the GC-PECD technique. Micro-EROD bioassay method was also used as a complement of the chemical analysis to estimate the TEQ levels of dioxin-like PCBs in human milk. The data showed that the human milk, rice, hen egg, and fish samples from Luqiao were more heavily contaminated with PCBs than those from Pingqiao, suggesting that the mothers and their breast-fed infants in Luqiao tended to receive greater exposure to PCBs than those living in Pingqiao. The OCP levels in the two localities were found comparable, suggesting that the major source of contamination with these pesticides was from their agricultural uses. Significant correlation (R-2 = 0.87, P < 0.001) of PCB TEQs was found between the bioassay and chemical analysis method, suggesting that micro-EROD is an effective method for comprehensive determination of TEQ levels in human milk. Comparison with literature data showed that the PCB levels in milk samples from Luqiao were significantly higher than those from localities in other Chinese provinces and comparable to those in developed or industrialized countries. (c) 2007 Published by Elsevier B.V.

Prenatal exposures to persistent organic pollutants as measured in cord blood and meconium from three localities of Zhejiang, China

Prenatal exposures to persistent organic pollutants were assessed using the levels of PCBs and organochlorine pesticides (OCPs) measured in cord blood and meconium samples from Luqiao and two other localities of the Zhejiang province in China. Luqiao is a town with the largest site for disassembly of PCB-containing obsolete transformers and electrical waste in China. The other two localities Pingqiao (100 km NW of Luqiao) and Lin'an (500 km NW of Luqiao) are towns without known electronic or electrical waste sites. A total of 23 PCB congeners (including 12 dioxin-like) and 6 OCPs were measured using the traditional GC-mu ECD technique. Micro-EROD bioassay was additionally used to measure TCDD-based TEQ levels of the 12 dioxin-like PCBs. Significant correlations were found between the TEQs measured by the two methods, supporting the application of micro-EROD as a practical toot for complementing the chemical analysis. The data showed that beta-HCH, p,p'-DDE, and 6 PCB congeners (101, 138 153, 180, 183, and 187) were the predominant pollutants, with PCB 138 being the best indicator (predictor) for total PCB levels. Cord blood and meconium from Luqiao have higher levels of PCBs than those from the other two localities, suggesting that a disassembly site for electronic and electric waste would provide an environment for greater exposure to these chemicals. The cord blood or meconium levels of beta-HCH, though likewise considerably high, were comparable in the three localities. Similar findings were observed for p,p'-DDE. Pollution by these OCPs might have come from past use of agricultural pesticides in the three localities. (c) 2007 Published by Elsevier B.V.

Primary cultured cells as sensitive in vitro model for assessment of toxicants-comparison to hepatocytes and gill epithelia

In an effort to develop cultured cell models for toxicity screening and environmental biomonitoring, we compared primary cultured gill epithelia and hepatocytes from freshwater tilapia (Oreochromis niloticus) to assess their sensitivity to AhR agonist toxicants. Epithelia were cultured on permeable supports (terephthalate membranes, "filters") and bathed on the apical with waterborne toxicants (pseudo in vivo asymmetrical culture conditions). Hepatocytes were cultured in multi-well plates and exposed to toxicants in culture medium. Cytochrome P4501A (measured as 7-Ethoxyresorufin-O-deethylase, EROD) was selected as a biomarker. For cultured gill epithelia, the integrity of the epithelia remained unchanged on exposure to model toxicants, such as 1,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), benzo(a)pyrene B[a]P, polychlorinated biphenyl (PCB) mixture (Aroclor 1254), and polybrominated diphenyl ether (PBDE) mixture (DE71). A good concentration-dependent response of EROD activity was clearly observed in both cultured gill epithelia and hepatocytes. The time-course response of EROD was measured as early as 3 h, and was maximal after 6 h of exposure to TCDD, B [alp and Aroclor 1254. The estimated 6 h EC50 for TCDD, B [a]P, and Aroclor 1254 was 1.2x10(-9), 5.7x10(-8) and 6.6x10(-6) M. For the cultured hepatocytes, time-course study showed that a significant induction of EROD took place at 18 h, and the maximal induction of EROD was observed at 24 h after exposure. The estimated 24 It EC50 for TCDD, B[a]P, and Aroclor 1254 was 1.4x10(-9), 8.1x10(-8) and 7.3x10(-6) M. There was no induction or inhibition of EROD in DE71 exposure to both gill epithelia and hepatocytes. The results show that cultured gill epithelia more rapidly induce EROD and are slightly more sensitive than cultured hepatocytes, and could be used as a rapid and sensitive tool for screening chemicals and monitoring environmental AhR agonist toxicants. (c) 2006 Elsevier B.V. All rights reserved.

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r(2) > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.

Quantitative structure-property relationships (QSPRs) on direct photolysis of PCDDs

By the use of partial least squares (PLS) method and 27 quantum chemical descriptors computed by PM3 Hamiltonian, a statistically significant QSPR were obtained for direct photolysis quantum yields (Y) of selected Polychlorinated dibenzo-p-dioxins (PCDDs). The QSPR can be used for prediction. The direct photolysis quantum yields of the PCDDs are dependent on the number of chlorine atoms bonded with the parent structures, the character of the carbon-oxygen bonds, and molecular polarity. Increasing bulkness and polarity of PCDDs lead to decrease of log Y values. Increasing the frontier molecular orbital energies (E-lumo and E-homo) and heat of formation (HOF) values leads to increase of log Y values. (C) 2001 Elsevier Science Ltd. All rights reserved.

Quantitative structure-property relationship studies on n-octanol/water partitioning coefficients of PCDD/Fs

Based on some fundamental quantum chemical descriptors computed by PM3 Hamiltonian, by the use of partial least-squares (PLS) analysis, a significant quantitative structure-property relationship (QSPR) model for logK(ow) of polychlorinated dibenzo-p-dioxins and dibenzo-p-furans (PCDD/Fs) was obtained. The QSPR can be used for prediction. The intermolecular dispersive interactions and thus the bulkness of the PCDD/Fs are the main factors affecting the logK(ow). The more chlorines in the PCDD/F molecule, the greater the logK(ow) values. (C) 2001 Elsevier Science Ltd. All rights reserved.

Peak identification for PCDD/Fs in environmental samples at different temperature programs

A method has been developed for peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at different temperature programs. Their retention behaviours are predicted on the basis of an identification database of retention values (A, B) of gas chromatography. By the retention times of C-13 labelled 2,3,7,8-substituted PCDD/F internal standards, the retentions of all PCDDs and PCDFs can be calculated. After comparison with the retentions of practical environmental samples, the predicted values have been proved to be very accurate. (C) 2000 Elsevier Science Ltd. All rights reserved.

PCDD/F-s, PCBs, HCHs and HCB in sediments and soils of Ya-Er lake area in China: Results on residual levels and correlation to the organic carbon and particle size

Sediments and soils collected from the Ya-Er Lake area in China were analysed for the polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs), hexachlorocyclohexane (HCHs) and hexachlorobenzene (HCB). The results indicated the main pollution problems in the Ya-Er Lake area, which was heavily polluted by HCHs and chlorobenzenes, now is dominantly polluted by PCDD/Fs, PCBs and HCB. The occurrence of PCDD/Fs and PCBs with relatively high levels of HpCDDs, OCDD and low chlorinated-substituted PCBs, is attributed to the discharge of waste water and biodegradation. The vertical distributions of HCH-residues are related with the content of organic carbon and particle size. Copyright (C) 1996 Elsevier Science Ltd

INFLUENCE OF LINEAR ALKYLBENZENE SULFONATE (LAS) AS ORGANIC COSOLVENT ON LEACHING BEHAVIOR OF PCDD/FS FROM FLY-ASH AND SOIL

The leaching of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was measured in soil and standard fly ash column eluted with pure water and linear alkylbenzene sulfonate (LAS)- water. The data obtained were used to evaluate the leachability of PCDD/Fs from waste dump like incineration residual slag and fly ash deposition. The leaching rate was shown to be increased significantly by using LAS water. The leachate contents of PCDD/Fs were above their known water solubility. Concentration of PCDD/Fs in the leachates as well as the relative leaching (calculated on the fly ash content) increased with increasing chlorinating degree and decreasing water solubility. LAS above the critical micelle concentration (CMC) probably enhances PCDD/Fs solubility.

Remediation of Persistent Organic Pollutants (POPs) in Two Different Soils

Persistent organic pollutants (POPs) are a set of chemicals that are toxic, persist in the environment for long periods of time, and biomagnify as they move up through the food chain. The most widely used method of POP destruction is incineration, which is expensive and could result in undesirable by-products. An alternative bioremediation technology, which is cheaper and environ-mentally friendly, was tested during this experiment. Two different soil types containing high and low organic matter (OM) were spiked with 100 mg/kg each of pyrene and Aroclor 1248 and planted with three different species of grasses. The objective of the study was to determine residue recovery levels (availability) and potential effectiveness of these plant species for the remediation of POPs. The results showed that recovery levels were highly dependent on the soil organic matter content—very low in all treatments with the high OM content soil compared to recoveries in the low OM soil. This indicates that availability, and, hence, biodegradability of the contaminants is dependent on the organic matter content of the soil. Moreover, the degree of availability was also significantly different for the two classes of chemicals. The polyaromatic hydrocarbon (PAH) recovery (availability) was extremely low in the high organic matter content soil compared to that of the polychlorinated biphenyls (PCBs). In both soil types, all of the plant species treatments showed significantly greater PCB biodegradation compared to the unplanted controls. Planting did not have any significant effect on the transformation of the PAHs in both soil types; however, planting with switchgrass was the best remedial option for both soil types contaminated with PCB.

零价金属降解多氯联苯(PCBs)

多氯联苯(polychlorinated biphenyls,简称PCBs)是一类对环境有不利影响的有毒有机物,它在环境中广泛而大量分布。许多科学家都在致力于有效处理PCBs污染介质(包括水、油、沉积物和土壤)的修复技术的研究。本文综述了国内外在零价金属还原脱氯降解PCBs领域的研究状况。在高温等特殊条件下或有钯、铂、镍和铜等催化剂存在的条件下,零价金属能有效促进PCBs还原脱氯。讨论了零价铁还原脱氯的3个可能的途径:金属直接反应,将零价铁表面的电子转移到有机氯化物使之脱氯;铁腐蚀的直接产物Fe2+具有还原能力,它可使得一部分氯代烃脱氯;铁反应产生的氢气可使有机氯化物还原。评述了零价金属还原脱氯PCBs具有有效、廉价和易得的特点。展望了零价金属还原脱氯降解PCBs研究领域的发展前景。

Organochlorine micropollutants in the Jiulong River Estuary and Western Xiamen Sea, China

Organochlorine contaminants including 12 polychlorinated biphenyl (PCB) congeners and 18 insecticides were determined in water, pore water and sediments of the Jiulong River Estuary and Western Xiamen Sea, China. The results showed that the levels of the total PCBs ranged from non-detectable to 1500 ngl(-1) in water, from 209 to 3870 ngl(-1) in pore water, and from 2.78 to 14.8 ng g(-1) dry weight in sediments. Total organochlorine insecticide concentrations were from below the limit of detection to 2480 ngl(-1) in water, from 267 to 33400 ngl(-1) in pore water, and from 4.22 to 46.3 ng g(-1) dry weight in sediments. Concentrations of PCBs and insecticides in pore water were significantly higher than those in surface water, due to the high affinity of these hydrophobic compounds for sediment phase. The PCB congeners with the highest concentrations were CB153, CB180 and CB194, which together accounted for 68-87% of total PCBs in water, pore water and sediment. Among the hexachlorocyclohexane (HCH) compounds, beta-HCH was found to be a major isomer. Analysis of 1,1,1-trichloro-2,2-bis-chlorophenyl-ethane (DDT) and its metabolites showed that 1, 1-dichloro-2[o-chlorophenyl]-2[p-chlorophenyl]-ethylene (DDE) was dominant in the group. In comparison to a 1998 study in the Western Xiamen Sea, levels of organochlorines were enhanced due probably to recent inputs and changes in sediments. (c) 2004 Elsevier Ltd. All rights reserved.