Katsunori Anezaki

Determination of dioxin concentrations in fish and seafood samples using a highly sensitive reporter cell line, DR-EcoScreen cells.

There is a strong need for the development of relatively rapid and low-cost bioassays for the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in environmental and food samples. In this study, we applied a reporter gene assay using DR-EcoScreen cells (DR-cell assay), which is highly sensitive to dioxins, to the determination of PCDD/Fs and dl-PCBs in fish and seafood samples. The PCDD/Fs and dl-PCBs were extracted from homogenated samples (10 g) of 30 fish and shellfish, purified by clean-up procedure using a multilayered silica gel column and an alumina column, and applied to DR-cell assay. Interestingly, the bioanalytical equivalent (BEQ) values obtained from the DR-cell assay [<0.1∼5.4 pg BEQ g(-1) wet weight (ww)] were closely correlated with the toxicity equivalent (TEQ) values from conventional high-resolution gas chromatography/high-resolution mass spectrometry (HRGC-HRMS) analysis (r(2)=0.912), and the slope of regression line was 0.913. Therefore, we multiplied the BEQ values from the DR-cell assay by a conversion coefficient (1.095, the reciprocal of 0.913) to approximate the TEQ values from the HRGC-HRMS analysis. Furthermore, we used this DR-cell assay to perform a prescreening test of PCDD/Fs and dl-PCBs in 16 fish and seafood samples purchased from a supermarket, revealing that a sample from the fatty flesh of a bluefin tuna exceeded 8 pg TEQ g(-1)ww (the European Union-tolerance limit). Taken together, these results suggest that the DR-cell assay might be applicable as a rapid and low-cost prescreening method to determine dioxin levels in fish and seafood samples.

Unintentional PCB in chlorophenylsilanes as a source of contamination in environmental samples

This paper discusses the concentrations and congener patterns of PCBs unintentionally present in chlorophenylsilanes. Chlorophenylsilanes are used in the production of silicone-based adhesives and phenyl silicones. The concentration of PCBs in adhesives was found to range from not-detectable concentrations to 40mg/kg. The concentrations of PCBs in trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, and diphenylsilanediol were 0.00072-2.7, 6.5-1,500, 0.019-1.1, and 0.12-120mg/kg, respectively. Dichlorodiphenylsilane and diphenylsilanediol, in particular, had high PCB concentrations. The PCB concentration of some specimens exceeded the 50mg/kg limit set by the transportation regulations of the Stockholm Convention. In the adhesives and chlorophenylsilanes, mono- and di-chlorinated biphenyls were detected in high proportions. The congeners detected in dichlorinated biphenyls had a structure in which one chlorine atom was substituted at each of the two aryls of the biphenyl backbone. This indicated that the chlorobenzene used for synthesizing chlorophenylsilanes undergoes dimerization. The congener and homologue patterns of the adhesives containing PCBs were similar to dichlorodiphenylsilane and diphenylsilanediol. It was concluded that the production of the adhesives is based on these substances. In addition, these results indicate that silicone-based products may become a source of PCBs in the environment, leading to irregular PCB values in environmental analysis.

Characterization of polychlorinated biphenyls, pentachlorobenzene, hexachlorobenzene, polychlorinated dibenzo-p-dioxins, and dibenzofurans in surface sediments of Muroran Port, Japan.

We determined the distribution of polychlorinated biphenyls (PCBs), pentachlorobenzene (PeCBz), hexachlorobenzene (HxCBz), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in surface sediments at 21 sites inside and outside Muroran Port, Japan. The concentration ranges and geometric means of PCBs (Σ209PCB), PeCBz, HxCBz, and PCDD/Fs and toxicity equivalence quantity (total TEQ) of dioxins inside Muroran Port were 1,100–65,000 (mean, 17,000) pg/g dw, 37–220 (100) pg/g dw, 31–810 (84) pg/g dw, 69–410 (170) pg/g dw, and 0.51–6.2 (2.3) pg TEQ/g dw, respectively. Their corresponding inventories inside Muroran Port were estimated to be 76, 0.31, 0.32, 0.55, and 7.8 g TEQ, respectively. The amounts of these pollutants were higher inside the port than outside the port and especially large in the inner part of the port. Most PCBs were homologues and congeners of penta- to hepta-chlorinated compounds, and the PCBs around Muroran Port were derived from technical PCBs, especially KC500 and KC600. As for PCDD/Fs, the influence of pentachlorophenol was significant, although pollution due to chloronitrofen and combustion was detected. The congeners of PCDD/Fs predominantly contributed to total TEQ. The concentration distributions of PeCBz, HxCBz, and PCDD/Fs and total TEQ were highly correlated with one another. This indicates that they are derived from the same combustion process.

Estimation of Polychlorinated Biphenyl Sources in Industrial Port Sediments Using a Bayesian Semifactor Model Considering Unidentified Sources.

Using the chemical balance method, and considering the presence of unidentified sources, we estimated the origins of PCB contamination in surface sediments of Muroran Port, Japan. It was assumed that these PCBs originated from four types of Kanechlor products (KC300, KC400, KC500, and KC600), combustion and two kinds of pigments (azo and phthalocyanine). The characteristics of these congener patterns were summarized on the basis of principal component analysis and explanatory variables determined. A Bayesian semifactor model (CMBK2) was applied to the explanatory variables to analyze the sources of PCBs in the sediments. The resulting estimates of the contribution ratio of each kind of sediment indicate that the existence of unidentified sources can be ignored and that the assumed seven sources are adequate to account for the contamination. Within the port, the contribution ratio of KC500 and KC600 (used as paints for ship hulls) was extremely high, but outside the port, the influence of azo pigments was observable to a limited degree. This indicates that environmental PCBs not derived from technical PCBs are present at levels that cannot be ignored.