Nobuyasu Hanari

Isomer-specific analysis of chlorinated biphenyls, naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia.

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.

Polychlorinated naphthalene contamination of some recently manufactured industrial products and commercial goods in Japan

Abstract A follow-up case study was performed after two incidents of recent illegal import and use in Japan both of technical PCNs mixture and contaminated with those compounds an industrial raw material. In case 1, above 18 tons of PCNs mixture, resembling Halowax 1001, which is a technical PCNs formulation, were imported from the United Kingdom. An illegally imported PCNs mixture was used for manufacture of a wide spectrum of industrial materials and commercial goods including sealants, putty, shock absorbing materials, adhesive materials, insulating materials and rubber belts. About 1.3 tons of PCNs contained in the Neoprene FB manufactured reached domestic market and 9.3 tons could reach other markets. In case 2, which became known in 2001, the Japanese company imported from Canada 54 tons of PCNs contaminated raw rubber material for industrial use. In weathering test (40°C for up to 168 h) of the feral rubber coated sheets for rubber bands 98% of di- and 66% of tri-CNs vaporized. A loss rate of tetra-, penta-, and hexa-CN during initial 12 h of the weathering test ranged from ˜10 to ˜20%, while from 12 to 168 h remained negligible.

Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999.

Pine needle samples collected at ten spatially distant sites around Tokyo Bay in 1999 indicated a widespread lower troposphere pollution with ultra-trace dioxin-like compounds such as chlorodibenzo-p-dioxins (PCDDs), -furans (PCDFs), non-ortho- and mono-ortho-chlorobiphenyls (pPCBs), and -naphthalenes (PCNs). Elevated concentration of planar PCBs and the total PCNs were found at the sites which are located innermost to the Bay, suggesting the regional importance of the evaporative nature of the source of pollution by those compounds over this vast area. The concentrations and profiles for PCDDs and PCDFs remained largely uniform. An exception was the site near the town of Tateyama in the Chiba Prefecture, which is the southernmost but also relatively separate from the inner Bay. The site near Tateyama showed somehow background contamination with all compound groups and highly different profiles of PCNs. The principal component analysis (PCA) of the data matrix has revealed that around the Tokyo Bay, apart from the evaporative emission sources for PCNs and PCBs, combustion related processes also play an important role as sources of the ambient air contamination not only with PCDDs/Fs but also with chloronaphthalenes and planar chlorobiphenyls.

Clophen A60 Composition and Content of CBs, CNs, CDFs, and CDDs after 2D-HPLC, HRGC/LRMS, and HRGC/HRMS Separation and Quantification

Abstract Chlorobiphenyl (CB) and by-side chlorodibenzofuran (CDF), chlorodibenzo-p-dioxin (CDD), and chloronaphthalene (CN) homologue group and congener composition, and concentrations have been examined in technical CBs mixture Clophen A60. 101 peaks representing 116 CB congeners were quantified in Clophen A60, and most contributing were CBs nos. 138, 153, 134/144/149, and 180 with 15.4, 12.3, 8.2, and 6.5%, respectively. Di-, tri-, tetra-, penta-, hexa-, hepta-, and octa-CBs constituted, respectively, 0.03, 0.03, 0.32, 9.9, 52.7, and 4.9% of chlorobiphenyls content of the Clophen A60, while mono-, nona-, and decaCB were not quantified. Tetra- to octaCDDs were absent in Clophen A60 at concentration above the method limit of quantification of <0.01 μg/g, while the total CDFs and CNs were found at 12 and 42 μg/g, respectively. Tetra-, penta-, hexa-, and hepta-CDF with 27, 46, 19, and 7% contribution, respectively, dominated in homologue group profile of CDFs, while octa-CDF was absent in Clophen A60. In compositional profile of CDF congeners the most abundant were 1,2,4,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 1,2,3,4,7,8-HxCDF and each had >5% contribution. Amongst the CN homologue groups the profile in descending order followed by hepta-, hexa-, octa-, and penta-CNs with 56, 26, 16, and 2%, respectively. In compositional profile of CNs the most abundant were the congeners such as 1,2,3,4,5,6,7-HpCN (no. 73), 1,2,3,4,6,7-/1,2,3,5,6,7-HxCN (nos. 66/67), and 1,2,3,4,5,6,7,8-OcCN (no. 75) with 55, 21, and 16%, respectively. In terms of dioxin-like toxicity of Clophen A60 the contribution from planar non-ortho and mono-ortho CBs, CDFs, and CNs was 5280, 594.5, and 33.1 ng TCDD TEQ/g, respectively, and the total TEQ of planar analogues was 5908 ng/g.

Airborne chloronaphthalenes in Scots pine needles of Poland

The amounts, profiles and origin of CNs (from triCNs to octaCN) sequestered in Scots pine needles collected from 25 spatially distant sites in Poland have been studied based on congener-specific data obtained after a several clean-up and fractionation steps and final HRGC/HRMS separation and determination. The absolute concentrations of CNs varied largely from site to site, i.e., by 15-fold. The sum of tri- to octaCN concentration at fifteen of the least contaminated sites ranged from 70 to 280 pg g(-1) ww, and at further eight sites were from 340 to 540 pg g(-1) ww, while at two the most contaminated were 1000 and 1100 pg g(-1)ww. There were some substantial similarities but also variations in triCN to octaCN homologue group profiles depending on the site. Among triCNs the isomers such as 1,2,4-/1,3,7-/1,4,6-triCNs (nos. 14/21/24) dominate in Scots pine needles. For majority of the sites examined 1,2,4-/1,3,7-/1,4,6-triCNs are also the major contributors to the bulk of CNs determined. Among tetraCNs isomer 1,2,5,8-tetraCN (no. 38) was dominant contributor at eighteen sites, while 1,2,4,6-/1,2,4,7-/1,2,5,7-tetraCN (nos. 33/34/37) at seven other sites. In the case of pentaCNs isomer 1,2,4,5,8-pentaCN (no. 59), was dominant contributor alone. Octachloronaphthalene frequently contributed substantially to the bulk of CNs. The Cluster Analysis and Principal Component Analysis did indicate that the compositional profiles of CNs found in Scots pine needles resemble somehow these found in the bottom ashes after coke and coal burning as well as of Halowax 1000 and 1099 formulations.

Concentrations and Fluxes of Chloronaphthalenes in Sediment from Lake Kitaura in Japan in Past 15 Centuries

Abstract The concentrations of 63 congeners of chloronaphthalene (CN; polychlorinated naphthalenes, PCNs) in dated on ˜500 B.C. to 2000 sediment core from the Lake Kitaura in Japan have been quantified by HRGC/HRMS after double column HPLC fractionation. Sediment from the Lake Kitaura showed a time-dependent pattern in distribution of CNs since the ˜500 B.C. Starting from the 1910s the total CNs content increased accelerating from the 1960s, and, in parallel, the pattern of CN congeners has changed with a substantial increase in contribution from the penta, hexa, hepta, and octaCN. The total CNs content normalized to dry weight of sediment peaked out in the layer dated on 1984–1985, and next nearly two-fold decreased with further gradually decreasing concentration in 1987–2000. An occurrence of tri and tetraCNs in deep sediment layers corresponded to preindustrial synthesis and use of CNs seems to be connected to relatively greater water solubility and mobility in the pore water of those CN homologue groups. Based on CN congener pattern and results of multivariate analysis three main layers were separated in the sediment core. Starting from 1981 the emission sources related to combustion marker congeners become substantial contributors to flux of annually deposited CNs, while relative significance of the evaporative source marker congeners decreased after 1985. The annual flux of CNs into sediments of the Lake Kitaura was 0.073–0.31 pg/cm2 before 1926, increased to 5.5–14 pg/cm2 in 1963–1970 and next sharply increased to 50–107 pg/cm2 in 1971–1985, and after that decreased to 17 pg/cm2 in 1997–2000.

Development of certified reference material for quantification of two pesticides in brown rice.

Brown rice powder certified reference material, NMIJ CRM 7504-a, for the analysis of pesticide residues was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial Science and Technology. Brown rice sample was harvested to contain the pesticides such as etofenprox and fenitrothion, and that was collected from a field in Ibaraki Prefecture in Japan. The certification was carried out using multiple analytical methods such as pressurized liquid extraction, homogenization, and solid-liquid extraction (shaking); the values of target pesticides were obtained by isotope dilution mass spectrometry. Certified values were 0.19 +/- 0.05 mg/kg and 0.109 +/- 0.017 mg/kg for etofenprox and fenitrothion, respectively.

Dioxin-like compound compositional profiles of furnace bottom ashes from household combustion in Poland and their possible associations with contamination status of agricultural soil and pine needles.

A compositional profile of PCDDs, PCDFs, non- and mono-ortho PCBs, and PCNs of several type furnace bottom ashes obtained after the heating muffle stove for domestic use combustion of hard coal, coke, wood, and solid domestic waste mixture have been examined as possible contributors to environmental diffusion with these compounds in Poland. The uppermost concentration of dioxin-like compounds with 2.0 ng TEQ kg(-1) dry weight found for wood ash was dominated by PCDDs and PCDFs, while for other types of ashes were in the range from 0.052 ng TEQ kg(-1) to 0.67 ng TEQ kg(-1) dry weight. The multivariate statistical analysis displayed some compositional similarity of PCDDs, PCDFs and PCNs between the ashes and environmental pine needle or agricultural soil matrices collected in Poland.

Polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs) in pine needles of Poland.

There is scarcity of data on sources, environmental diffusion and concentrations of PCDD/Fs and dioxin-like compounds in the Eastern and Central Europe. A study has been conducted using pine needles as passive matrix on diffusion of airborne 17 highly toxic PCDD/Fs in Poland. The target compounds were quantified using isotope dilution and HRGC/HRMS. One-year-old pine needles collected from 25 spatially distant sites in October 2002 revealed a relatively very low aerial emission and degree of pollution with PCDD/Fs. The most toxic 2,3,7,8-TCDD was absent (< 0.44 pg/g) in fresh pine needles sampled and absent at all sites were also 1,2,3,7,8-PeCDD, 1,2,3,4,7,8-HxCDD, 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD and 1,2,3,7,8,9-HxCDF (< 0.27 pg/g). OCDD at concentration range from 1.4 to 34 pg/g and OCDF at range from 1.5 to 41 pg/g were the only among 17 compounds found at each site, and next in prevalence was 1,2,3,4,7,8,9-HpCDF (total range from < 0.41 to 8.1 pg/g), which was found at 24 off 25 sites. The I-TEQ transformed concentrations of PCDD/Fs of pine needles of Poland ranged from < 0.01 to 1.28 pg/g ww or from 0.01 to 3.18 pg/g dw. The CDD/F homologue groups and congeners profiles of pine needles with highly dominant HpCDD/F and OCDD/F found in this survey suggest on lack of significant other than coal/lignite/wood combustiont sources of PCDD/Fs diffusion to ambient air in Poland.

Highly toxic chlorobiphenyl and by-side impurities content and composition of technical chlorofen formulation.

Abstract Non- and mono-ortho CBs as well as also highly toxic by-side impurities such as chlorodibenzofurans, chlorodibenzo-p-dioxins, and chloronaphthalenes after a subsequent 2D-HPLC and HRGC-HRMS separation, detection, and identification were quantified in technical chlorobiphenyl Chlorofen formulation. Chlorofen is highly chlorinated CB mixture and its compositional profile of mono-ortho CBs is occupied by 2,3,3′,4,4′,5′-HxCB (no. 157) with 96.6% and followed by 2,3,3′,4,4′,5-HxCB (no. 156) with 3.3% and 2,3′,4,4′,5,5′-HxCB (no. 167) with <0.1%, while nos. 105, 114, 118, 123, and 189 remained undetected (<10 µg/g). Amongst non-ortho CBs only a trace of 3,3′,4,4′-TeCB (no. 77) was found at 15 µg/g, while CBs nos. 81, 126, and 169 were absent. TCDD TEQ for mono- and non-ortho CBs in Chlorofen was 2320 and 1.5 ng/g, respectively, while for CDFs and CNs were 45 and 731 ng/g, respectively, and for both types of contaminants most contributing were OcCDF and OcCN. No tetra- to OcCDD was found in Chlorofen.