Daily variations and factors of atmospheric PCDD/Fs in post-harvest paddy fields: PCDD/F source estimation using a Bayesian semi-factor model.

We investigated the daily variations in the concentration of atmospheric dioxins (PCDD/Fs and DL-PCBs) in paddy fields after the autumn harvest. The geometric mean of the concentrations of dioxins during the research period was 0.042 pg-TEQ/m3, and the concentrations ranged from 0.0058 to 0.53 pg-TEQ/m3. When the weather was calm with no rain or snow and the atmosphere was stable, relatively high concentrations of dioxins were observed. The characteristics of congeners and homologues produced through the combustion of PCDD/Fs were classified into four groups using principal component analysis and cluster analysis. In addition, agricultural chemicals (pentachlorophenol, PCP and chlornitrofen, CNP) were identified as the source of PCDD/Fs using a Bayesian semifactor model. When the dioxin concentrations were high, the combustion of TeCDFs and PeCDFs produced large emissions, representing the impact of open burning of rice straw. When the dioxin concentrations were low, the contribution of CNP was strong, indicating the effects of the release of previously used agricultural chemicals from the soil.

Effects of unintentional PCBs in pigments and chemical products on transcriptional activity via aryl hydrocarbon and nuclear hormone receptors.

In recent years, some pigments and chemical products have been reported to contain polychlorinated biphenyl (PCB) congeners as unintentional byproducts, and these have also been detected in residential environments from indoor air and house dust. In this study, using in vitro reporter gene assays, we characterized the agonistic and antagonistic activities of a total of 25 PCB congeners contained in pigments (PCB-1 to -16, -20, -35, -40, -52, -56, -77, -101, -126, and -153) against five nuclear hormone receptors, (estrogen receptor (ER) α/ß, glucocorticoid receptor (GR), androgen receptor (AR), thyroid hormone receptor (TR) α1) and aryl hydrocarbon receptor (AhR). In the ERα/ß assays, 19 and 13 of the 25 PCBs tested showed ERα/ß agonistic and/or antagonistic activities, respectively. Relatively potent agonistic activities against ERα/ß were found in PCB congeners possessing chlorides at positions 2 and 3. In the GR and AR assays, five and all of the 25 PCB congeners showed antagonistic activity, respectively. Among the anti-androgenic PCB congeners, the activities were more potent in PCB congeners possessing more than three chlorides including consecutive ortho- and meta- or meta- and para-chlorides. In the AhR assay using a sensitive DR-EcoScreen cell line, five of the 25 PCB congeners showed agonistic activity. We newly found that PCB-1, -35 and -56 can act as AhR agonists. Despite these activities among the PCBs, the effects of PCB-11, mainly detected in pigments and chemical products, against these receptors were found to be weaker than those of other tested PCBs. These results suggest that unintentional PCBs in pigments and chemical products might act as agonists and/or antagonists against ERα/ß, AR, GR, and AhR, and some of the PCBs might disrupt endocrine functions via multiple receptors and/or simultaneously induce dioxin-like activity via AhR.

Concentration and congener pattern of polychlorinated biphenyls in blubber and liver of Hubbs' beaked whale (Mesoplodon carlhubbsi), using a sulfoxide and an Ag-ION solid phase extraction cartridge as a simplified cleanup technique for biological samples.

We performed the first known study of polychlorinated biphenyls (PCBs) concentrations and patterns in the blubber and liver of a Hubbs' beaked whale. Samples were pretreated with Supelclean™ sulfoxide and Discovery® Ag-ION solid phase extraction cartridges to remove whale oil. PCB concentrations in the blubber and liver were 13,000 and 7300ng/g lipid, respectively. Highly poisonous congeners such as dioxin-like (DL) PCBs tended to accumulate in the liver. The toxic equivalents (TEQ) of DL-PCBs in the liver (740pg-TEQ/g lipid) were higher than those in the blubber (74pg-TEQ/g lipid). The blubber and liver samples showed that hexachlorinated biphenyls were dominant among homologues, and PCB-153 was dominant among congeners. Several congeners accumulated disproportionately in the blubber and the liver (PCB-28, 52, 74, 99, and 118), while others did not persist (PCB-31, 70, and 110). This indicates that PCBs are metabolized differently according to their specific composition.

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.

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.

Polychlorinated biphenyl contamination of paints containing polycyclic- and Naphthol AS-type pigments.

This study reports the concentrations and congener partners of polychlorinated biphenyls (PCBs) in commercially available paints. Polycyclic-type pigments containing dioxazine violet (pigment violet (PV) 23, PV37) and diketopyrrolopyrrole (PR254, PR255) were found to contain PCB-56, PCB-77, PCB-40, PCB-5, and PCB-12, and PCB-6, PCB-13, and PCB-15, respectively, as major congeners. Dioxazine violet is contaminated with by-products during synthesis from o-dichlorobenzene, which is used as a solvent during synthesis, and diketopyrrolopyrrole is contaminated with by-products during synthesis from p-chlorobenzonitrile. The concentration of PCBs in paint containing PV23 or PV37 was 0.050-29 mg/kg, and toxic equivalency (TEQ) values ranged 1.1-160 pg-TEQ/g. The concentration of PCBs in paint containing PR254 or PR255 was 0.0019-2.4 mg/kg. Naphthol AS is an azo-type pigment, and PCB-52 was detected in paint containing pigment red (PR) 9 with 2,5-dichloroaniline as its source. PCB-146, PCB-149, and PCB-153 were identified from paint containing PR112 produced from 2,4,5-trichloroaniline, as major congeners. These congeners have chlorine positions similar to aniline, indicating that these congeners are by-products obtained during the synthesis of pigments. The concentrations of PCBs in paints containing PR9 and PR112 were 0.0042-0.43 and 0.0044-3.8 mg/kg, respectively. The corresponding TEQ for PR112 was 0.0039-8.6 pg-TEQ/g.

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.

Concentration levels and congener profiles of polychlorinated biphenyls, pentachlorobenzene, and hexachlorobenzene in commercial pigments.

The concentration levels and congener profiles of polychlorinated biphenyls (PCBs), pentachlorobenzene (PeCBz), and hexachlorobenzene (HxCBz) were assessed in commercially available organic pigments. Among the azo-type pigments tested, PCB-11, which is synthesized from 3,3'-dichlorobendizine, and PCB-52, which is synthesized from 2,2',5,5'-tetrachlorobendizine, were the major congeners detected. It is speculated that these were byproducts of chlorobendizine, which has a very similar structure. The total PCB concentrations in this type of pigment ranged from 0.0070 to 740 mg/kg. Among the phthalocyanine-type pigments, highly chlorinated PCBs, mainly composed of PCB-209, PeCBz, and HxCBz were detected. Their concentration levels ranged from 0.011 to 2.5 mg/kg, 0.0035 to 8.4 mg/kg, and 0.027 to 75 mg/kg, respectively. It is suggested that PeCBz and HxCBz were formed as byproducts and converted into PCBs at the time of synthesizing the phthalocyanine green. For the polycyclic-type pigments that were assessed, a distinctive PCB congener profile was detected that suggested an impact of their raw materials and the organic solvent used in the pigment synthesis. PCB pollution from PCB-11, PCB-52, and PCB-209 pigments is of particular concern; therefore, the monthly variations in atmospheric concentrations of these pollutants were measured in an urban area (Sapporo city) and an industrial area (Muroran city). The study detected a certain level of PCB-11, which is not included in PCB technical mixtures, and revealed continuing PCB pollution originating from pigments in the ambient air.

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.

Application of a bioassay using DR-EcoScreen cells to the determination of dioxins in ambient air: a comparative study with HRGC-HRMS analysis.

There is a strong need for the development of relatively rapid and low-cost bioassays for the determination of dioxins (polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls) in environmental and food samples. In this study, we applied a bioassay system using highly sensitive DR-EcoScreen cells (DR-cell assay) to the determination of low levels of dioxins in ambient air samples. The dioxins from 80 ambient air samples were extracted, purified by cleanup procedure, and applied to both DR-cell assay and high-resolution gas chromatography/high-resolution mass spectrometry (HRGC-HRMS) analysis. Interestingly, the toxic equivalents (TEQ) values obtained from the DR-cell assay were closely correlated with those from the HRGC-HRMS analysis (r2 = 0.957). Although the cell-based TEQ values were relatively (3.66-fold) higher than the TEQ values from the HRGC-HRMS analysis, this discrepancy was thought to be due to the difference between the toxic equivalency factor (TEF) and the relative potency (DR-REP) determined for individual dioxins. Therefore, we multiplied the TEQ values from the DR-cell assay by a conversion coefficient (0.273, the reciprocal of 3.66) and could approximate the values from the HRGC-HRMS analysis. These results clearly suggest at the DR-cell assay might be a promising method for the rapid and low-cost screening of dioxins in ambient air samples.