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Abstract: In Japan, Ayase River is one of the most polluted rivers by PCDDs, PCDFs and dioxin-like PCBs, which are referred to as dioxins in this paper. The water samples of the river were collected once per month for a year, and dioxins were analyzed to examine the dioxin sources and their contributions to toxic equivalent (TEQ). The WHO-2006 TEQs ranged from 0.26 to 7.0pg-TEQL−1 and the average was 2.7pg-TEQL−1; eight of 12 samples exceeded the environmental quality standard in Japan (1.0pg-TEQL−1). The TEQ value was high during the irrigation period from May to August. The most part of the dioxins in the river water existed in suspended solids (SS) and it seemed that the river received water with highly-dioxin-contaminated SS in the irrigation period. The homologue profiles of the water samples suggested that the dioxins were influenced by pentachlorophenol (PCP) and chlornitrofen (CNP) formulations which were widely used as herbicides for the paddy fields in Japan. According to TEQ apportionment estimated by using indicative congeners, the TEQ was mainly contributed by PCP. Moreover, it was also shown that the TEQ contributions of PCP and CNP formulations increased along with the increase of the total TEQ and the TEQ contribution was dominated by these herbicides during the irrigation period. Therefore, it was concluded that the herbicides-originated dioxins run off from the paddy fields into the river during the irrigation period and increased the dioxins level in the river water. The result from the principal component analysis was consistent with these conclusions. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

We investigated dioxin concentrations in freshwater fish in Japan by standardizing species to detect subtle decreasing trends of dioxin concentrations in the future with the reinforcement of regulations. The fish studied were crucian carp (Carassius auratus (gibelio) langsdorfii), an omnivorous species. Fish and sediments were collected from 14 rivers and lakes located in remote areas, agricultural areas, and small and large cities throughout Japan. The total toxic equivalent (TEQ) dioxin concentrations at the three remote sites were about 20% of the concentrations at the other 11 sites, which all had similar concentrations. The average concentrations in fish collected from these 11 sites were 0.69pgTEQg−1 wet wt. (95% CI 0.52–0.85) or 57.3pgTEQg−1 fat (95% CI 47.9–66.7). There were notable differences in congener profiles of polychlorinated p-dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) between sampling areas. A chemical mass balance method was used to estimate the proportions of dioxin contributions from different sources. The sampling areas were classified into four groups on the basis of the predominant source of dioxin contamination: a combustion group, a chlornitrofen herbicide group, a chlornitrofen and pentachlorphenol herbicide group, and a remote group. The congener profiles of dioxin like polychlorinated biphenyls (DL-PCBs) were almost the same in all areas and close to those in Kanechlor, which indicates that pollution from PCB products has spread throughout Japan. From samples collected during the spawning season, it was determined that about 20% of the dioxins in adult females were transferred to the eggs, resulting in higher dioxin concentrations in adult males than in females. Biota–sediment accumulation factors (BSAFs) of 2,3,7,8-substituted PCDDs/DFs for crucian carp were larger than those of non-2,3,7,8-substituted congeners, and BASFs decreased with increasing number of chlorines. The BSAFs of DL-PCBs were 10 times greater than those of PCDDs/DFs, and BSAFs of mono-ortho type DL-PCBs were higher than those of non-ortho types. [Copyright &y& Elsevier]