benzofurans and 2-4-6-trichlorophenyl-4-nitrophenyl-ether

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 7.0 pg-TEQL(-1) and the average was 2.7 pg-TEQL(-1); eight of 12 samples exceeded the environmental quality standard in Japan (1.0 pg-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.

Topics: Benzofurans; Dibenzofurans, Polychlorinated; Dioxins; Fresh Water; Herbicides; Japan; Pentachlorophenol; Phenyl Ethers; Polychlorinated Biphenyls; Polychlorinated Dibenzodioxins; Rivers; Water Pollutants, Chemical; Water Pollution

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)were analyzed in preserved paddy soils periodically collected from 7 sites around Japan since 1960 to trace the changes in concentrations, to elucidate their sources, and to estimate their mass balance in Japanese paddy fields. Concentrations of sigma PCDD/Fs in paddy soils from all sites increased during the 1960s and the 1970s, then decreased. The results of principal component analysis and chemical mass balance based on functional relationship analysis indicate that the increase in sigma PCDD/F concentrations in paddy soils was due to the increased use of pentachlorophenol (PCP) and chlornitrofen (CNP); more than 95% of PCDD/Fs in all paddy soils were derived from impurities in these herbicides. The half-lives of PCDD/F for disappearance from the paddy soils were estimated to be 10 to 20 years (mean: 17.3 years). The estimated PCDD/F mass balance using the above half-life during the past 40 years in paddy fields indicates that about 80% of PCDD/Fs have disappeared. The soil puddling (mechanically mixing of paddy soil with pooled irrigation water) is implied as one reason for the PCDD/F disappearance from paddy fields. However, as the amounts of PCDD/Fs added through the use of PCP and CNP were extremely large, PCDD/F concentrations in Japanese paddy soils will decrease gradually, and PCDD/F runoff from paddy fields to surrounding catchments will continue.

Topics: Agriculture; Benzofurans; Dibenzofurans, Polychlorinated; Environmental Monitoring; Gas Chromatography-Mass Spectrometry; Japan; Oryza; Pentachlorophenol; Phenyl Ethers; Polychlorinated Dibenzodioxins; Principal Component Analysis; Soil; Soil Pollutants