Computer assisted peak recognition for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in environmental samples

A software has been developed for the peak recognition of 136 polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) after high resolution gas chromatography coupled with mass spectrometry (HRGC/HRMS). Based on the retention times of C-13 labelled 2,3,7,8-substituted PCDD/F internal standards, the retention times of all PCDD and PCDF can be calibrated automatically and accurately. Therefore, it is very convenient to identify the peaks by comparing the retention of samples and the calibrated retention times of their chromatograms. Hence, this approach is very significant because it is impossible to obtain always a standard chromatogram and PCDD/F analysis are very expensive and time consuming. The calibration results can be transferred to Excel for calculation. The approach is a first step to store costly and environmentally relevant data for future application.

A new method of predicting of gas chromatographic retention indices for polychlorinated dibenzofurans (PCDFs)

A new method has been developed to describe the quantitative relationship between molecular structures of PCDFs and their gas chromatographic retention indices on a 30-m fused silica column coated with DB-5 stationary phase. The regression equation is derived with a multiple correlation coefficient greater than 0.9995. The highest residual is 20 index units. The standard deviation is less than 7 index units. Using this regression equation, the retention indices of PCDFs for which data is not available have also been predicted. (C) 2000 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.

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.

Distribution patterns of PCDD/Fs in chlorinated chemicals

The purpose of this research was to determine polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in five chlorinated chemicals (phthalocyanine copper, phthalocyanine green, chloranil-1 and 2, and triclosan), and to compare their 2,3,7,8-tetrachlordibenzo-IpI-dioxin equivalents (TEQ). The distribution patterns of total PCDD/Fs and 2,3,7,8-substituted PCDD/Fs were elucidated in detail. The TEQ values of toxic PCDD/Fs in all chemicals were in the range of 5.03-1379.55 ng I-TEQ/kg. The contribution of OCDD and OCDF in phthalocyanine green was 75% of the total TEQ. For chloranils, the maximum contribution of toxic PCDD/Fs was from 2,3,7,8-substituted HxCDF and 2,3,7,8-substituted HpCDF. The TEQ of HxCDF and HpCDF in chloranil-1 was 90% and in chloranil-2 was 71%. And the toxic contribution increased with the degree of chlorination for PCDFs. (C) 2005 Elsevier Ltd. All rights reserved.

Polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs) monitored by tree bark in an E-waste recycling area

To investigate the environmental levels and profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), tree bark samples (n = 22) were collected from Luqiao, an E-waste recycling area, in east China in July 11-13, 2006. The average concentrations of PCDD/Fs, PBDEs, and PCBs determined by isotope dilution-high resolution gas chromatography (HRGC) coupled with high resolution mass spectrometer (HRMS) were 0.1 +/- 0.0, 1.4 +/- 0.2, and 6.5 +/- 0.8 lg g (1) lipid weight, respectively. PCDD/F-toxic equivalent (TEQ, WHO-1998), PCB-TEQs, and total dioxin-like TEQs were 1.3 +/- 0.1, 0.5 +/- 0.0, and 1.8 +/- 0.2 ng g (1) lipid weight, respectively. The profiles of these pollutants in the tree bark were also discussed. Tetra-CDFs, deca-BDE and tri-CBs were the main homologues and accounted for 47% of total PCDD/Fs, 79.3% of total PBDEs, and 33.2% of total PCBs, respectively; As for TEQs, 2,3,4,7,8-PeCDF and PCB126 were the main contributors and accounted for 36% of the total PCDD/F-TEQs and 81.2% of the total PCB-TEQs, respectively. High accumulation of PCDD/Fs, PBDEs, and PCBs detected in the tree bark indicated heavy contaminations of these pollutants in Luqiao area. (C) 2008 Elsevier Ltd. All rights reserved.

Elevated levels of urinary 8-hydroxy-2'-deoxyguanosine in male electrical and electronic equipment dismantling workers exposed to high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans, polybrominated diphenyl ethers, and polychlorinated biphenyls

To investigate the occupational exposure levels to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), indoor dust (n = 3) in workshops and hair samples from male workers (n = 64) were collected at two electrical and electronic equipment waste (E-waste) dismantling factories located in the LQ area in east China in July 11-13, 2006. Pre- and postworkshift urines (64 of each) were also collected from the workers to study oxidative damage to DNA using 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker. The concentrations of PCDD/Fs, PCDD/F-WHO-TEQs, PBDEs, PCBs and PCB-WHO-TEQs were (50.0 +/- 8.1) x 10(3), 724.1 +/- 249.6, (27.5 +/- 5.8) x 10(6), (1.6 +/- 0.4) x 10(9), (26.2 +/- 3.0) x 10(3) pg/g dry weight (dw) in dust, and (2.6 +/- 0.6) x 10(3), 42.4 +/- 9.3, (870.8 +/- 205.4) x 10(3), (1.6 +/- 0.2) x 10(6), 41.5 +/- 5.5 pg/g dw in hair, respectively. The homologue and congener profiles in the samples demonstrated that high concentrations of PCDD/Fs, PBDEs, and PCBs were originated from open burning of E-waste. The 8-OHdG levels were detected at 6.40 +/- 1.64 mu mol/mol creatinine in preworkshift urines. However, the levels significantly increased to 24.55 +/- 5.96 mu mol/mol creatinine in postworkshift urines (p < 0.05). Then, it is concluded that there is a high cancer risk originated from oxidative stress indicated by the elevated 8-OHdG levels in the E-waste dismantling workers exposed to high concentrations of PCDD/Fs, PBDEs, and PCBs.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in surface sediment and bivalve from the Changjiang Estuary, China

Surface sediments and bivalves were collected from the Changjiang Estuary in December 2003 and November 2004, respectively. Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in these samples were measured with high-resolution chromatography (HRGC)/High Resolution Mass Spectrometer (HRMS). The concentrations of total PCDD/Fs and toxic equivalent (TEQ) were 169.83 +/- 119.63 and 0.81 +/- 0.36 pg/g dry weight (dw) in sediments, and 580.33 +/- 240.17 and 7.24 +/- 3.65 pg/g dw in bivalves. The homolog compositions of PCDD/Fs were similar among samples, the most abundant congener was octa-chlorinated dibenzo-p-dioxin (OCDD) and then octa-chlorinated dibenzofuran (OCDF) and 1,2,3,4,6,7,8-hepta-chlorinated dibenzo-p-dioxin (HOCDD). The herbicide pentachlorophenol (PCP) and sodium pentachlorophenol (Na-PCP) were proved the main source of PCDD/Fs in this area.

Preliminary hazard assessment of polychlorinated biphenyls, polybrominated diphenyl ethers, and polychlorinated dibenzo-p-dioxins and dibenzofurans to Yangtze finless porpoise in Dongting Lake, China

Yangtze finless porpoise (Neophocaena phocaenoides asiaeorientalis), a protected endangered species, is the sole freshwater subspecies of finless porpoise, living only in the middle and lower reaches of the Yangtze River, China, and its appended lakes. Its population has decreased sharply to 1,400 because of human activities, including environmental contamination. In the present study, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in the blubber, liver, kidney, stomach, small intestine, and brains of five individual Yangtze finless porpoises collected from 1998 to 2004. The results showed PCB concentrations ranged from 0.06 to 1.89 mu g/g lipid weight in the organs and consisted mainly of penta-, hexa-. and decachlorinated biphenyls. The PBDE concentrations were between 5.32 and 72.76 ng/g lipid weight. Tetra-, penta-, and hexabrominated diphenyl ethers were the major homologues. The PCDD/F concentrations ranged from 65 to 1,563 pg/g lipid weight, and their predominant homologues were penta- and hexachlorinated dibenzofurans and hepta- and octachlorinated dibenzo-p-dioxins. The hazard quotients (HQs) based on toxic equivalency were determined to be greater than one in all individuals for PCBs, for PCDD/Fs, and for PCBs and PCDD/Fs In addition, HQs would be higher if PBDEs were included. The results suggest that reduction of environmental contamination may contribute greatly to protecting this highly endangered species.

Body loadings and health risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans at an intensive electronic waste recycling site in China

This study is one of the very few investigating the dioxin body burden of a group of child-bearing-aged women at an electronic waste (e-waste) recycling site (Taizhou, Zhejiang Province) (24 +/- 2.83 years of age, 40% were primiparae) and a reference site (Lin'an city, Zhejiang Province, about 245 km away from Taizhou) (24 +/- 2.35 years of age, 100% were primiparae) in China. Five sets of samples (each set consisted of human milk, placenta, and hair) were collected from each site. Body burdens of people from the e-waste processing site (human milk, 21.02 +/- 13.81 pg WHO-TEQ(1998/g) fat (World Health Organization toxic equivalency 1998); placenta, 31.15 +/- 15.67 pg WHO-TEQ(1998/g) fat; hair, 33.82 +/- 17.74 pg WHO-TEQ(1998/g) dry wt) showed significantly higher levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurnas (PCDD/Fs) than those from the reference site (human milk, 9.35 +/- 7.39 pg WHO-TEQ(1998/g) fat, placenta, 11.91 +/- 7.05 pg WHO-TEQ(1998/g) fat; hair, 5.59 +/- 4.36 pg WHO-TEQ(1998/g) dry wt) and were comparatively higher than other studies. The difference between the two sites was due to e-waste recycling operations, for example, open burning, which led to high background levels. Moreover, mothers from the e-waste recycling site consumed more foods of animal origin. The estimated daily intake of PCDD/Fs within 6 months by breast-fed infants from the e-waste processing site was 2 times higher than that from the reference site. Both values exceeded the WHO tolerable daily intake for adults by at least 25 and 11 times, respectively. Our results implicated that e-waste recycling operations cause prominent PCDD/F levels in the environment and in humans. The elevated body burden may have health implications for the next generation.

Contamination and distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in agriculture fields in Ya-Er Lake area, China

The contamination and distribution of polychlorinated dibeinizo-p-dioxins and dibenzofurans (PCDD/Fs) from two agricultural fields of a heavily polluted lake area in China (Ya-Er Lake) are presented. The vertical distribution pattern of total PCDD/Fs in soil cores reveals that the maximum concentration was in the layer of 20-30 cm. The concentrations in the top layer of soil at the two sites were similar (17.48 ng/kg at Site 1 and 18.10 ng/kg at Site 2), but the maximum concentration of Site 1 (120.8 ng/kg) was two times higher than that of Site 2 (64.39 ng/kg). The maximum concentration of PCDD/Fs in mud cores in rice fields (0-50 cm) at Sites 1 and 2 was in the layer of 0-10 cm. The maximum PCDD/F concentration in the top layer in mud at Site 1 (203.1 ng/kg) was higher than that at Site 2: (143.3 ng/kg). Significant correlations were found between the mind PCDD/Fs and the organic carbon content (R = 0.9743, P< 0,05 at Site 1; R = 0.9821, P< 0.05 at Site 2), the two variables being highly correlated (R = 0.9049, P< 0.05, at Site 1; R = 0.9916, P< 0.05 at Site 2). All correlation coefficients were significant at the 95% level. Concentrations were highly correlated with organic carbon, indicating that sorption to organic carbon was the dominant mechanism. Using principal component analysis, the homologue profiles of soil, mud, and plants (rice and radish) were compared. The PCDD/F patterns in plants were found not to be correlated to those in soil and mud. This suggests that atmospheric deposition may be the main source of PCDD/Fs in rice grain. However, mixed exposure involving uptake mechanisms and atmospheric deposition is considered main the source of PCDD/F pollution in radishes. (C) 2002 Elsevier Science (USA).

Mobility and profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans in sediment of Ya-Er Lake, China

The sediment of Ya-Er Lake had been heavily polluted by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from the former chloralkali industry. The total amounts of PCDD/Fs and I-TEQ decreased along the water flow direction and also decreased from top to bottom layers of sediment cores. Sediment of Pond 1 was dominated by PCDF, especially TCDF. In contrast, in the other four ponds, PCDD dominated in all layers and octachlorinated dibenzo-p-dioxin (OCDD) predominated in all of the homologues. When homologue profiles from sediments and water samples were compared using principal component analysis (PCA), the first two principal components represented 95.2% of the variance in the data. The first component explained 75.9% of the variance and the second one 19.3%. Two clusters were most distinct, presenting a shift in PCDD/Fs composition from PCDF to heptachlorinated dibenzo-p-dioxin (HpCDD) and OCDD in sediments and water from Pond I to Ponds 2-5. The pattern variation between Pond 1 and Ponds 2-5 in Ya-Er Lake was most likely due to the change of process in the chemical plant after the dams between the ponds were built. The results of the present study also showed that log K-oc of PCDD/Fs calculated from data of sediment and water in the field were comparable with theoretical log K-oc. The results also implied that the concentrations of PCDD/Fs in water and sediments could be predicted from each other by log K-oc. (C) 2001 Elsevier Science Ltd. All rights reserved.

Persistence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) in Ya-Er Lake area, China

The concentrations of polychlorinayed dibenzo-p-dioxins and dibenzofurans (PCDD/F) in surface sediment, soil, human hair, acid fish muscle from Ya-Er Lake area, China, were analyzed. The results showed that there were very high concentrations of PCDD/F existing in these samples. The results also indicated that Ya-Er Lake, which received a large amount of waste water from a nearby chloroalkali plant, was heavily polluted by PCDD:F. The present study demonstrated that those congeners, which possess at least three chlorine atoms in the lateral position with a fourth chlorine atom in the neighborhood bond of the third single chlorine atom, such as 1,2,7,8-TCDF and 2,3.6,7-TCDF, were very resistant to biodegradation due to the "neighbor effect" of every two chlorine atoms. The present study suggested that human hair may be a suitable alternative bioindicator for detecting PCDD/F exposure. (C) 2001 Elsevier Science Ltd. All rights reserved.

Bioaccumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans in the foodweb of Ya-Er Lake area, China

Bioaccumulation of PCDD/F in the foodweb was investigated in the Ya-Er Lake area, which was heavily polluted by PCDD/F. The high concentrations of PCDD/F in sediment can be transferred and bioaccumulated by aquatic organisms and humans through various pathways. Benthonic invertebrate animals and aquatic plants with a lot of fibers in the root can accumulate PCDD/F from sediment and water. Snail (Bellamya aeruginosa), shrimp (Macrobranchium sp.) and freshwater mussel (Acuticosta chinensis (Lea)) took up PCDD/F from the water and maintained the emission patterns, whereas fish tended to selectively accumulate 2,3,7,8-substituted isomers. The tissues of fish-eating bird and duck (Anas platyrhynchos) were very highly contaminated by PCDD/F due to ingestion of fish and other aquatic organisms from sediment. The residual concentration in breast milk depended on the original concentration of PCDD/F in the food. A resident in Ya-Er Lake area showed a daily intake of PCDD/ F of about 9.14 pg TEQ/kg body weight/day. This is higher than the tolerable daily intake (TDI) for PCDD/F (1 pg TEQ/kg body weight/day), which was recommended by the World Health Organization (WHO). (C) 2001 Elsevier Science Ltd. All rights reserved.