Relationship between dietary exposure and serum perfluorochemical (PFC) levels--a case study.

Daily dietary intake of perfluorinated chemicals (PFCs) in relation to serum levels was assessed by determination of nine PFCs including perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in matched daily diet duplicates and serum samples. Diet and serum were collected in year 2004 from 20 women in Osaka and Miyagi, Japan. Only PFOS and PFOA were detected in the diet samples and no significant difference between cities was seen. After adjusted by water content, diet concentration of PFOA was significantly higher in Osaka. The median daily intake calculated using the measured diet concentrations was 1.47 ng PFOS/kg b.w. and 1.28 ng PFOA/kg b.w. for Osaka, and 1.08 ng PFOS/kg b.w. and 0.72 ng PFOA/kg b.w. for Miyagi. A significant difference between cities was seen for the serum concentrations with median of 31 ng/mL PFOS and PFOA in Osaka, compared to 14 ng/mL PFOS and 4.6 ng/mL PFOA in Miyagi. Carboxylates such as perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUnDA) were also detected in serum at median levels 6.9 ng/mL and 3.2 ng/mL (Osaka), and 2.8 ng/mL and 5.1 ng/mL (Miyagi). Based on one-compartment model under steady state, dietary intake of PFOS and PFOA accounted for only 22.4% and 23.7% of serum levels in Osaka females, and in contrast 92.5% and 110.6% in Miyagi females, respectively.

Development of new-type rapid analysis technology of polychlorinated biphenyls by using liquid chromatographic clean-up material (polyvinyl alcohol gel).

We developed a new-type rapid polychlorinated biphenyl (PCB) analysis technology on the basis of a liquid chromatographic clean-up system combined with a large-volume injection GC-LRMS. Among 18 kinds of materials such as polymer gels, normal-phase silica gels, reversed-phase silica gels, carbon material and ion-exchange material, polyvinyl alcohol (PVA) gel and poly (hydroxylmethacrylate) gel were found to give rather good separation performance for insulating oil. Especially, PVA gel was confirmed to be the most suitable for rapid PCB analysis because of its least required quantity of fraction liquid as well as the highest resolution. Then, we confirmed elution characteristics of all PCB isomers and removal efficiency of insulating oil on PVA gel under an optimized condition, and established high-performance clean-up system using a combination of octadecyl silica gel (ODS), porous graphite carbon (PGC) and PVA gel. In this system, we applied newly valve-switching method that could remove other impurities. In addition, it was demonstrated that the proposed clean-up system could become highly sensitive and rapid PCB analysis technology with 2-h analysis time, lower measurement limit of less than 0.05 mg/kg, and a variation coefficient of less than 5%, by coupling with a large-volume injection type GC-LRMS. Thus, we can conclude that this rapid PCB analysis technology has not only good correlativity (R2>0.999) with standard analysis method but also high durability and can be fully applied to actual PCB-treatment plants.

Perfluorinated compounds in river water, river sediment, market fish, and wildlife samples from Japan.

Perfluorinated organic compounds (PFCs) such as PFOS, PFOA, PFBS, PFHxS, PFOSA and PFDoA were determined in river water, river sediment, liver of market fish and liver of wildlife samples from Japan. Concentrations of PFOA and PFOS in water samples were 7.9-110 and <5.2-10 ng/L. Only PFOA were detected in sediment from Kyoto river at 1.3-3.9 ng/g dry wt. Among fish, only jack mackerel showed PFOA and PFOS at 10 and 1.6 ng/g wet wt. Wildlife liver contained PFOSA, PFOS, PFDoA, PFOA and PFHxS in the range of 0.31-362, 0.15-238, <0.03-28, >0.07-7.3 and <0.03-1.5, respectively, on ng/g wet wt. Cormorants showed maximum accumulation followed by eagle, raccoon dog and large-billed crow.

Impact of FEBRA (fermented brown rice with Aspergillus oryzae) intake and concentrations of PCDDs, PCDFs and PCBs in blood of humans from Japan.

Impact of FEBRA (fermented brown rice with Aspergillus oryzae, a rich dietary fiber) intake on the concentrations of polychlorinated-biphenyls (PCBs), -dioxin-like polychlorinated biphenyls (DLPCBs), -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) in blood of nine married Japanese were studied for 2 years. Concentrations of total PCBs (average+/-standard deviation) were greater 326,000+/-263,000 and 207,000+/-89,000 in FEBRA-intake and non-FEBRA-intake groups, respectively, on pg/g lipid (from now onwards data expressed on pg/g lipid). DLPCBs were second major contaminants 94,000+/-77,000 and 60,000+/-28,000, orderly in FEBRA-intake and non-FEBRA-intake groups. The concentrations of PCDD/DFs were several orders of magnitude lower than those of PCBs, whereas PCDDs were greater (433+/-233 and 512+/-511, in FEBRA-intake and non-FEBRA-intake groups, respectively) than PCDFs (56+/-50 and 43+/-35). Calculated toxic equivalency (TEQ) concentrations were 34+/-24 and 23+/-10 in FEBRA-intake and non-FEBRA-intake groups, respectively. In order to corroborate the impact of FEBRA, the changes of PCDD/DFs and PCB concentrations for 0.5-year, 1-year, 1.5-year, and 2-year samples were estimated from average concentration of 1-day before study commences and 1-week study samples. The results explicit FEBRA-intake group eliminated 7%, 33%, 45%, 36%, and 26% and non-FEBRA-intake group eliminated 8%, 28%, 36%, 31%, and 20% of DLPCBs, PCDDs, PCDFs, PCDD/DF TEQ and total TEQ, respectively. This study is the first of its kind showing the possible elimination of PCDDs, PCDFs and their TEQ in humans from Japan after the consumption of FEBRA.

Impact of fermented brown rice with Aspergillus oryzae (FEBRA) intake and concentrations of polybrominated diphenylethers (PBDEs) in blood of humans from Japan.

The isotope dilution technique was applied for the analysis of new polybrominated diphenylethers (PBDEs) calibration standard (both labeled and non-labeled) using high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS). The relative response factor (RRF) and relative standard deviation (RSD) for new calibration standard in Finnigan Thermo Electron (MAT-95XL) and Micromass (Autospec Ultima) were more or less identical with mean RRF (0.9882), RSD (0.0865) and CV% of (8.75). The results also revealed for DeBDE-209 quantification; labeled DeBDE-209 is essential. Furthermore, we recommend on column injection technique with a thin film instead of splitless injection in order to reduce the thermal degradation of DeBDE-209 and formation of octabromodibenzofurans (OBDF). Besides, analysis of human blood (n = 156) of FEBRA-intake and non-FEBRA-intake individuals elucidated frequent detection of eighteen PBDE congeners. The average PBDE concentrations in non-FEBRA intake and FEBRA-intake humans were 6000-11,000 (mean: 8400) and 5400-15,000 (mean: 9900) respectively on pg/g fat basis. Although FEBRA-intake individuals showed slightly greater PBDEs, computer-normalized concentrations of TeBDE-47 corroborate FEBRA-intake individual from four family showed reduced concentrations. The contamination profiles of PBDEs varied in between family, gender as well as geography. International comparison with predominant PBDE congener (TeBDE-47) prevailed lower levels in Japan when compared to Korea, Germany and USA nevertheless, congener specific profiles were different which is in accordance with different technical PBDE usage in between countries.

Formation of polychlorinated naphthalenes, dibenzo-p-dioxins, dibenzofurans, biphenyls, and organochlorine pesticides in thermal processes and their occurrence in ambient air.

Mono- through octachlorinated naphthalenes (PCNs) were measured in start-up, steady operation, and shutdown of machinery operation flue gas and fly ash generated during different stages of MSWI and other incineration thermal processes. Besides, electroprecipitator fly ash (EP-ash) was dechlorinated using the Hagenmeier process and analyzed for congener profiles. In addition to PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and major organochlorine pesticides were determined in ambient air samples from three different sites of western Japan in the summer and winter of 1992. The PCNs from flue gas contained 15,000, 4300, and 13,000 ng/m3 during start-up, steady operation, and shutdown conditions, respectively. Whereas fly ash contained 470, 370, and 1400 ng/g PCNs under start-up, steady operation, and shutdown condition, respectively. The dechlorination process reduced PCN concentrations considerably. Concentrations of PCNs and PCDD/PCDFs in air samples collected in winter were slightly higher than in summer. PCBs, organochlorine pesticides such as chlordanes, DDTs, and HCHs were higher in summer air samples. WHO toxic equivalency (WHO-TEQ) concentrations in air samples were 0.3-0.9 pg/m3 for PCDD/DFs and 0.029-0.31 pg/m3 for dioxin-like PCBs.