Mercury and cadmium in common cormorants (Phalacrocorax carbo)

Mercury (Hg) and cadmium (Cd) in common cormorants (Phalacrocorax carbo) collected in Lake Biwa, Japan and Tokyo, Japan, were investigated to elucidate the biological behaviors of these elements, and to assess exposure to these pollutants of wild, fish-eating birds. Hg and Cd concentrations were highest in the liver and kidneys, respectively. The lowest levels of both elements were observed in chicks. Hg concentrations in all tissues except brain increased significantly with growth from chicks to juveniles (p<0.05, U-test). Cd concentrations in the kidneys and liver also increased significantly during growth from juvenile to adult (p<0.005, U-test). When comparing hepatic Hg and Cd in adult birds between 10 samples from Lake Biwa and nine samples from Tokyo, the Cd concentrations in the Lake Biwa samples (1.4+/-0.37 microg/g dry wt) (mean+/-SD) were significantly higher than those from Tokyo (0.32+/-0.16 microg/g dry wt) (p<0.005, U-test), while no statistically significant difference was found in the Hg concentrations. Possible causes of these differences were discussed in relation to their prey.     

Specific accumulation of 20 trace elements in great cormorants (Phalacrocorax carbo) from Japan

This study is to elucidate the specific accumulation of 20 trace elements in tissues/organs of great cormorants from two different colonies (Lake Biwa and Mie) in Japan. In the body distribution of trace elements, some elements revealed tissue-specific accumulation such as most of the burden of Mo, Ag and Cd in liver, Tl and Cd in kidney, Cu, Rb and Cs in muscle, and V, Sr and Ba in bone. Gender-related variation was not observed in both populations for most of the trace elements, except for higher hepatic Sr in males from Lake Biwa. Hepatic V, muscular Hg and Tl, and Cd in liver, kidney and muscle increased with growth. Comparison of trace element levels in tissues between the two colonies showed that Cr, Rb, Sr, Cd, Cs, Ba and Tl levels were higher in Lake Biwa than in Mie, whereas Zn, Co and Hg in Mie samples were greater than Lake Biwa. Variations of elemental levels in stomach contents also showed similar patterns, thus, showing that dietary sources tended to be the main factor for these regional variations. Toxic Hg and Cd concentrations in the liver of cormorants from the two colonies were lower than those from other areas, implying relatively low exposure to these metals in the present study sites. Concentrations of V, Co, Ag, Cd, Cs, Hg, Tl, Pb and Bi in liver remained more or less at the same level between 1993 and 2003, while hepatic Cr, Mn, Cu, Zn, Se, Rb, Sr and Ba showed apparent decrease, which might be related to the biological factors.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji,Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Specific accumulation of polychlorinated biphenyls and organochlorine pesticides in Japanese common squid as a bioindicator

Organochlorines (OCs) representing Persistent Organic Pollutants (POPs) such as PCBs (polychlorinated biphenyls), DDTs (DDT and its metabolites), CHLs (chlordane compounds), HCHs (hexachlorocyclohexane isomers) and HCB (hexachlorobenzene) were determined in the liver of Japanese common squid (Todarodes pacificus) collected from the waters around Japan (Japan Sea and western North Pacific Ocean). Among OCs concentrations, PCBs (upto 5600 ng/g lipid wt.) were the highest, and those of other OCs were in the order of DDT> CHLs > HCHs > HCB. Studies on growth trend and seasonal variation of OCs in this species suggest a rapid reflection of the pollution levels in seawater where and when they were collected, regardless of body-length and time of collection. These results indicate that Japanese common squid is a suitable bioindicator for monitoring OCs pollution in waters around Japan. With regard to the geographical distribution of OCs in this species collected from waters around Japan, OCs concentrations in specimens from Japan Sea were higher than those from the Pacific Ocean. This result might reflect some existing of local pollution sources of OCs around Japan Sea, and slower water exchange between Japan Sea and open ocean.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in the Kanto Region, Japan

The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in blood collected from 195 pregnant women in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho coplanar polychlorinated biphenyls (non-ortho PCBs), and mono-ortho coplanar polychlorinated biphenyls (mono-ortho PCBs) in blood collected between 2002 and 2004 from 195 pregnant women living in Sapporo City of Hokkaido Prefecture, Japan. The present study is one of the few studies in which PCDDs, PCDFs, and dioxin-like PCBs have been measured in the blood of pregnant women. Of the 195 pregnant women, 101 were primipara (mean: 28.8 years) and 94 were multipara (mean: 32.4 years). The arithmetic mean total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs of primiparous and multiparous mothers in Sapporo City were 17.4 (median: 15.7) and 14.0 (median: 13.9)pgTEQ/glipid, respectively, and the concentrations were in the range of 6.6-43.4 and 3.4-28.2pgTEQ/glipid, respectively. In regard to the relationship between the total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in maternal blood and the number of deliveries or age of primiparous and multiparius mothers, the levels of these dioxin-like compounds tended to decrease with increases in the number of deliveries and significantly increased with increasing maternal age in both groups. Furthermore, significant correlations were observed between the total TEQ concentrations of these dioxin-like compounds and the age of primiparae and multiparae. The total TEQ concentration of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs measured in 195 pregnant women has decreased compared to past levels in Japan for the last several decades. The results of the present study have indicated that dioxin contamination in the blood of young women in Japan is continuing to decrease.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0-23 (mean: 13, median: 14) and 2.7-20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16-326 (mean: 107, median: 100) and 12-252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.     

Concentrations of polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans,and polychlorinated biphenyls in blood and breast milk collected from pregnant women in Sapporo City,Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0–23 (mean: 13, median: 14) and 2.7–20 (mean: 8.6, median: 8.5) pg TEQ g⁻¹ lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16–326 (mean: 107, median: 100) and 12–252 (mean: 73, median: 67) ng g⁻¹ lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.     

Health risk assessment for polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans, and polychlorinated naphthalenes in seafood from Guangzhou and Zhoushan, China

This study determined the concentrations of organochlorine contaminants in common seafood in two Chinese coastal cities (Guangzhou and Zhoushan), and assessed the health risk due to the daily consumption of contaminated seafood. Twenty-six pooled samples, belonging to five food categories (fish, bivalves, shrimp, crab, and cephalopods), were purchased from local markets in Guangzhou and Zhoushan in 2003 and 2004. These samples were analyzed for total polychlorinated biphenyls (PCBs), non- and mono-ortho-PCBs (coplanar PCBs), polychlorinated naphthalenes (PCNs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs). The concentrations of total PCBs and coplanar PCBs in fish samples were higher in Guangzhou than in Zhoushan, while the levels of PCNs and PCDDs/DFs were comparable between the two cities. The total daily intake values of dioxin-like compounds were 1.05 and 0.86pg WHO-TEQ/kg body weight in Guangzhou and Zhoushan, respectively. Hazard ratios of non-cancer risk in the two cities were all less than unity.     

Concentrations of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in blood and breast milk collected from 60 mothers in Sapporo City, Japan

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs), and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) in paired samples of blood and breast milk collected from 60 mothers in Sapporo City, Hokkaido Prefecture, Japan. The present study is one of the few studies in which PCDDs, PCDFs, and dioxin-like PCBs have been measured in blood and breast milk collected from 60 same mothers. Of these 60 mothers, 30 were primipara (mean: 30.1 years, median: 28.0 years) and 30 were multipara (mean: 32.2 years, median: 32.5 years). The arithmetic mean TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the primiparous mothers were 9.0, 3.3, 5.7, and 0.4 pg TEQ g(-1) lipid, respectively, and 5.2, 2.2, 4.5, and 0.4 pg TEQ g(-1) lipid, respectively, with the total TEQ concentrations of these dioxin-like compounds being 9.3-42.9 (mean: 18.4, median: 17.3) and 7.0-41.1 (mean: 12.3, median: 11.4) pg TEQ g(-1) lipid, respectively. In the case of multiparous mothers, the arithmetic mean TEQ concentrations of these dioxin-like compounds in blood and breast milk were 7.1, 2.7, 5.3, and 0.4 pg TEQ g(-1) lipid, respectively, and 3.9, 1.7, 3.8, and 0.4 pg TEQ g(-1) lipid, respectively, with the total TEQ concentrations being 3.4-28.1 (mean: 15.5, median: 13.9) and 2.7-20.0 (mean: 9.8, median: 9.2)pg TEQ g(-1) lipid, respectively. The total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of primiparous mothers in Sapporo City appeared to be generally lower than those recently surveyed throughout the greater area of Japan. Significant correlations were observed between age and the total TEQ concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in the blood of primiparae and multiparae, and significant correlations were also observed between age and the total TEQ concentrations of these dioxin-like compounds in the breast milk of primiparae and multiparae. The total TEQ concentrations of PCDDs, PCDFs, and dioxin-like PCBs in the blood of primiparous mothers showed a close correlation to those in their breast milk and also showed good correlations between the total TEQ concentrations of these dioxin-like compounds in the blood of multiparous mothers and those in their breast milk. The result of a comparison of the arithmetic mean concentrations of each congener of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk indicated that the transfer of octachlorodibenzo-p-dioxin (OCDD) from the blood to the breast milk was lower than those of other congeners. In contrast, among mono-ortho PCBs congeners, the arithmetic mean concentrations of 2,3',4,4',5-pentachlorobiphenyl (PentaCB) (#118) and 2,3,3',4,4'-PentaCB (#105) in the breast milk were slightly higher than those in the blood, which suggested that breast-fed infants may be at higher risk from mono-ortho PCBs.     

Specific biomagnification of polychlorinated dibenzo-p-dioxins and dibenzofurans in tufted ducks (Aythya fuligula), common cormorants (Phalacrocorax carbo) and their prey from Lake Shinji, Japan

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs) were detected in waterfowl such as common cormorants, tufted ducks, and their prey, namely fish and bivalves from Lake Shinji, Japan. The concentration of total PCDDs/DFs-TEQ was found to be higher in the muscle tissues of common cormorants than in those of tufted ducks. The results of hierarchical cluster analysis implied that the residue distribution pattern of PCDD/DF homologues was considerably different between these two species. Furthermore, biomagnification factors (BMFs) were estimated from bivalves as prey to tufted duck muscles as target organs. Despite the highest concentrations of 1,3,6,8- and 1,3,7,9-TeCDD in tufted ducks and their prey, however, the BMFs of these isomers were calculated to be lower than those of the toxic 2,3,7,8-substituted PCDDs/DFs. On the other hand, log BMF of toxic 2,3,7,8-substituted PCDDs/DFs were significantly higher for lower chlorinated isomers than those of the higher chlorinated isomers. The biota-sediment accumulation factors (BSAFs) of PCDDs/DFs were also estimated using shijimi clam and fish samples against sediment from Lake Shinji. The average BSAFs were estimated and ranged from 4.0×10⁻³ to 2.2×10⁻¹ and 2.0×10⁻⁴ to 2.0×10⁻¹ for bivalve and fish samples, respectively. Based on calculated BMFs and BSAFs, the total PCDD/DF-TEQ levels in the tufted duck were estimated to have been lowest (2.0 pg TEQ/g dry weight basis) in 1947 and highest (9.8 pg TEQ/g) in 1971.     

Persistent chlorinated pesticides and polychlorinated biphenyls in selected fish species from Lake Tanganyika, Burundi, Africa

Concentrations of selected organochlorine pesticides and PCBs in seven fish species (cichlids) from the north end of the Lake Tanganyika, Burundi, Africa were determined. Results were compared to previous work on the Lake Tanganyika and other water bodies and to the European Community maximum residue levels (MRLs) in edible fat. The analytical method included a hot Soxhlet extraction with a mixture of acetone: hexane (1:3, v/v), gravimetrically lipid determination, and a single step clean-up. For PCBs and stable pesticides, the clean-up was done on activated silica gel impregnated with concentrated sulfuric acid, while for non acid-stable pesticides superposed layers of alumina, silica and florisil impregnated with 15% methanolic solution of KOH were successively used. Recoveries of organochlorine pesticides from certified reference material (CRM 430) were ranging from 86% for p,p'-DDT to 107% for endrin, while recoveries from blank fat spiked fortified at three different levels were between 65% for alachlor at the lowest fortification level and 107% for mirex at the highest fortification level. The limits of detection for each analyte were ranging from 0.1 ng/g to 0.5 ng/g fat. All chlorinated pesticides were found in the analyzed species but at low concentrations. Boulengerochromis microlepis contained the highest concentrations of HCHs (288.2 +/- 15.5 ng/g fat) and DDTs (909.1 +/- 42.5 ng/g fat), while the highest PCB levels (166.7 +/- 37.4 ng/g fat for the sum of 12 congeners) were found in Oreochromis niloticus. However, there is no evidence that Lake Tanganyika is more contaminated with pesticides than other African water bodies.     

Concentrations of polychlorinated biphenyls in water from US Lake Ontario tributaries between 2004 and 2008

Research on the environmental fate and transport of PCBs in Lake Ontario basin depends, among other aspects, on the availability of representative data sets for upstream sources, but data are lacking for most US Lake Ontario tributaries. In this study, water samples were collected between September 2004 and October 2008 from five tributaries and were analyzed for 209 polychlorinated biphenyls (PCB) with high-resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) following EPA Method 1668A. Total PCB concentrations ranged between 0.31 and 42.75 ng L⁻¹. Congeners between Di and Hexa PCBs accounted between 70 and 99% of the total PCB. The tributary with highest PCB concentrations presented similar pattern and percentage levels to Aroclor 1242. Total average loads for the sampling events ranged between 1.85 g d⁻¹ and 59.08 g d⁻¹. PCB concentrations were evaluated against other variables and other studies (including different matrices) to better understand their transport. The methodology used is reliable to assess PCB contamination in surface water.     

Polychlorinated dibenzo-p-dioxins/furans and polychlorinated biphenyls in sediments and aquatic organisms from the Taihu Lake, China

Sediments at 16 sites and muscles of four aquatic species collected in Taihu Lake were analyzed for polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) by HRGC/HRMS. The concentrations of total PCDD/Fs, PCBs and WHO-TEQ were 120.1-1315.1pg/gdw, 889.7-29747.8pg/gdw, and 0.83-17.72pgTEQ/gdw, respectively in sediments; and those in muscles were 5.49-35.84pg/gww, 1517.10-27647.98pg/gww, and 0.52-3.83pgTEQ/gww respectively. The concentrations of PCDD/Fs and PCBs in the sediments were decreasing gradually along the water flow. The pollution levels were compared with other studies and the possible sources were discussed.     

琵琶湖水污染形成与治理及毒性污染问题

介绍了日本琵琶湖水污染的成因及治理的措施，同时阐述了污染治理应控制毒性物质的重要性。     

Congener-specific analysis of non-dioxin-like polychlorinated biphenyls in blood collected from 195 pregnant women in Sapporo City, Japan

We conducted a congener-specific analysis of non-dioxin-like polychlorinated biphenyls (non-dioxin-like PCBs) in blood collected between July 2002 and July 2004 from 195 pregnant women living in Sapporo City of Hokkaido Prefecture, Japan. The present study is one of the few studies in which full congener concentrations of non-dioxin-like PCBs have been measured in the blood of pregnant women. Of the 195 pregnant women, 101 were primipara (mean: 28.8 years, median: 28.0 years) and 94 were multipara (mean: 32.3 years, median: 33.0 years). Among the 197 non-dioxin-like PCB congeners, 58 congeners were identified in the blood of pregnant women. The arithmetic mean total concentrations of 58 non-dioxin-like PCB congeners in the blood of primiparous and multiparous mothers in Sapporo City were 42.2-329.3 (mean: 114.5, median: 98.6) and 31.5-258.0 (mean: 100.3, median: 91.4)ngg(-1)lipid, respectively. The results show that the contamination of non-dioxin-like PCBs in the blood of women has decreased compared to past levels in other domestic areas, in which the subject age was similar to that in this study. The results of the present study indicate that current levels of non-dioxin-like PCBs in the blood of Japanese women and can be used as baseline data for future temporal trends. The sums of the ratios of the concentrations of hexaCBs and heptaCBs to the total concentrations of 58 non-dioxin-like PCB congeners in the blood of primiparous and multiparous mothers were 78.5% and 77.7%, respectively. The hexaCBs ratios in the blood of primiparous and multiparous mothers were 45.4% and 44.7%, respectively. HexaCB-153 among hexaCBs congeners, the most abundant congener in the blood of primiparous and multiparous mothers, contributed approximately 22.0% and 21.8% to the total concentrations of 58 non-dioxin-like PCBs congeners that were measured in the blood, respectively. Among the non-dioxin-like PCB congeners measured in the present study, hexaCB-138, heptaCB-170, heptaCB-180, and heptaCB-182/heptaCB-187 also showed high ratios to total concentrations of 58 non-dioxin-like PCB congeners detected in the blood of primiparous and multiparous mothers. With regard to the relationship between the total concentrations of 58 non-dioxin-like PCB congeners in maternal blood and the number of deliveries or the age of primiparous and multifarious mothers, the total levels of these PCB congeners tended to decreases with increases in the number of deliveries and significantly increased with increasing maternal age in both groups. Furthermore, significant correlations were observed between the total concentrations of these PCB congeners in blood and the age of primiparae and multiparae. The concentrations of hexaCB-153 in the blood of primiparous and multiparous mothers showed a close correlation to the total concentrations of these PCBs, suggesting that hexaCB-153 could be an indicator of total concentrations of non-dioxin-like PCB congeners in the blood of pregnant women.     

Concentration-dependent enantioselective accumulation of chiral polychlorinated biphenyls in Nelumbo nucifera Gaertn. root from contaminative sediment

Environmental Science and Pollution Research - Nelumbo nucifera Gaertn. (lotus) roots were collected from contaminated sediments which were artificially adding different concentrations of chiral...     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

Crystal structure and density functional theory studies of toxic quinone metabolites of polychlorinated biphenyls

Lower chlorinated polychlorinated biphenyls (PCBs) are readily metabolized via hydroxylated metabolites to reactive PCB quinones. Although these PCB metabolites elicit biochemical changes by mechanisms involving cellular target molecules, such as the aryl hydrocarbon receptor, and toxicity by interacting with enzymes like topoisomerases, only few PCB quinones have been synthesized and their conformational properties investigated. Similar to the parent compounds, knowledge of the three-dimensional structure of PCB quinones may therefore be important to assess their fate and risk. To address this gap in our knowledge, the gas phase molecular structure of a series of PCB quinones was predicted using HF/3-21G, B3LYP/6-31G?? and UB3LYP/6-311G?? calculations and compared to the respective solid state structure. All three methods overestimated the Cl-C bond length, but otherwise provided a reasonable approximation of the solid state bond angles and bond lengths. Overall, the UB3LYP/6-311G?? level of theory yielded the best approximation of the molecular structure of PCB quinones in the solid state. Chlorine addition at the ortho position of both rings was found to increase the dihedral angle of the resulting quinone compound, which may have important implications for their interaction with cellular targets and, thus, their toxicity.     

Congener-specific analysis of non-dioxin-like polychlorinated biphenyls in blood collected from 127 elderly residents in Nakagawa Town, Fukuoka Prefecture, Japan

We conducted congener-specific analysis of non-dioxin-like polychlorinated biphenyls (non-dioxin-like PCBs) in blood collected in February 2004 from 127 elderly residents living in Nakagawa Town, Fukuoka Prefecture, Japan. The present study is one of the few studies in which 56 non-dioxin-like PCBs congeners were measured in human blood. Of the 127 elderly residents, 51 were men (mean: 68.1 years) and 76 were women (mean: 68.1 years). Among 197 non-dioxin-like PCB congeners, 56 were identified in the blood of elderly residents. The arithmetic mean total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women in Nakagawa Town were 419 (median: 378) and 363 (median: 323)ngg(-1)lipid, respectively, and the concentrations were in the range of 172-1102 and 119-1226ngg(-1)lipid, respectively, indicating that the total concentrations in elderly men are significantly higher than those in elderly women. The contamination of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture was found to have decreased compared to past levels. The ratios of hexachlorinated biphenyls (hexaCBs) to the total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women were 44.6% and 45.6%, respectively, which was particularly high compared with those of other congeners. 2,2',4,4',5,5'-HexaCB (#153) among hexaCBs congeners, the most abundant congener in the blood of elderly men and women, contributed approximately 23.0% and 23.5% to the total concentrations of 56 non-dioxin-like PCBs congeners, respectively. Furthermore, 2,2',3,4,4',5'-hexaCB (#138), 2,3,3',4',5,6-hexaCB (#163)/2,3,3',4',5',6-hexaCB (#164), 2,2',3,4,4',5,5'-heptaCB (#180), and 2,2',3,4,4',5,6'-heptaCB (#182)/2,2',3,4',5,5',6-heptaCB (#187) also showed high ratios to the total concentrations of 56 non-dioxin-like PCBs congeners detected in the blood of elderly men and women. A statistical examination of the relationship between the total concentrations of 56 non-dioxin-like PCBs congeners in blood and the age of elderly residents who were over 60 years indicated statistically significant correlations between the total concentrations of these PCBs congeners and the age of elderly women. However, similar correlations were not observed in elderly men. The results of the present study have indicated the current levels of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture, Japan and can be used as baseline data for those over age 60.