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We performed PCB congener specific analysis using HRGC/HRMS and determined their concentrations and blood chromatogram classifications in 275 individual blood samples collected during annual Yusho examinations between 2007 and 2010. When both blood total PCB concentrations and blood chromatogram classifications were compared among eleven Yusho patients undergoing examinations between 2007 and 2010, the longitudinal concentrations and classifications in the respective individuals hardly changed over these years. In a subset of persons suspected of Yusho, it was found that the mean total blood concentrations of three index congeners, that is, 2, 3', 4, 4', 5-pentaCB (PCB118), 2, 2', 4, 4', 5, 5'-hexaCB (PCB153), 2, 3, 3', 4, 4', 5-hexaCB (PCB156) and mean blood total PCB concentrations gradually decreased between 2007 and 2010. Mean concentration of PCB118 in blood from persons suspected of Yusho was calculated as 0.035 ng/g in the 2010 examination, which was 36% lower than the mean value of 0.054 ng/g in the 2007 examination: the concentration of PCB118 showed the highest degree of decrease among the three index congeners. Among persons suspected of Yusho, occupational rates of persons with blood PCB concentrations below one ppb in the entire population increased from approx. 50% in 2007 to approx. 70% in 2010. The lowest concentration of PCB156 in blood of persons suspected of Yusho in 2010 was 0.43 pg/g, which was almost equivalent to the limit of the determination value on HRGC/HRMS, S/N = 10.

We analyzed sixty-eight PCB isomers and determined their concentrations and characteristics in fifty-eight individual blood samples collected during the annual Yusho inspection in 2006. The method used in this study consists of a rapid GPC clean-up and sensitive PCB isomer-specific identification with HRGC/HRMS. As a result, the highest total PCB concentration in inspected subjects was 6.6 ppb on a blood weight basis, which was 8.1 times higher than that of a control blood sample. When blood PCB patterns were compared among twenty-seven persons in undergoing examinations both 2004 and 2006, the longitudinal classifications in the respective individuals hardly changed between these years. Mean concentrations of each PCB isomer in the blood of pattern A subjects (n=4) were compared with those in the blood collected from Fukuoka prefecture residents (n=127). Consequently, the respective blood concentrations of PCB #157, #156, #189, #137, #195, #170, #99 were obviously higher than those of Fukuoka residents, while those of PCB #118, # 05 was evidently lower than those of Fukuoka residents.

This paper reports that we can replace a conventional PCB analytical method with an isomer specific analytical method in Yusho diagnosis. The authors analysed 109 blood samples from people who had the 2002 annual inspection for Kanemi rice oil poisoning using both methods. The data from these methods were compared and proved to be almost the same in the so-called "PCB pattern" which has been adopted as a Yusho diagnosis index since early 1970s.

The polychlorinated quaterphenyl (PCQ) concentrations in blood are important discriminative parameters in yusho patient. In this study, a rapid analytical method for PCQ using different diameter capillary column (rapid-Rtx65TG) with high-resolution gas chromatograph high-resolution mass spectrometer (HRGC/HRMS) instead of the gas chromatograph electron capture detector (ECD/GC) was developed. Using different diameter capillary columns, the analysis time of the HRGC/HRMS was drastically shortened, and the detection sensitivity was improved. In the rapid-Rtx65TG column, a small-bore capillary column (length 1m, I.D. 0.1mm) was connected with the inlet side of the GC, and behind that column, a large-bore capillary column (length 15mm, I.D. 0.53mm) for octadecachloroquaterphenyl (ODCQ) analysis was connected. In the HRGC/HRMS measurement of ODCQ by the rapid-Rtx65TG column, the minimum limit of detection for the apparatus was 0.4 pg, and the minimum limit of determination for the blood was 0.008 ppb. On ECD/GC in the conventional method and HRGC/HRMS in this study, the PCQ concentration in blood including yusho patients and yusho suspected persons was almost equivalent.

The concentrations of brominated dioxins which are polybrominated dibenzo-p-dioxins/polybrominated dibenzofurans (PBDD/DFs) and mono-bromo polychlorinated dibenzo-p-dioxins/dibenzofurans, polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA) were investigated in a total of 45 fish samples collected from three regions in Japan. In the brominated dioxins, 1,2,3,4,6,7,8-heptabromodibenzofuran (HpBDF) was the most abundant congener, and it was found in seven fish samples at 0.10-25.6 pg/g wet weight (ww). The highest concentration of 1,2,3,4,6,7,8-HpBDF was found in the pike eel. Regarding other congeners, 2,3,7,8-tetrabromodibenzo-p-dioxin was detected in the sea bream at 0.02 pg/g ww, and 2,3,7,8-tetrabromodibenzofuran was detected in the conger eel at 0.03 pg/g ww. 3-Bromo-2,7,8-trichlorodibenzofuran was detected in the Sardinella zunasi and the conger eel at 0.01 pg/g ww and 0.02 pg/g ww, respectively. Using toxic equivalency factors of chlorinated dioxins, we calculated the PBDD/DFs concentrations of these fish samples at 0.001-0.256 pg TEQ/g ww. PBDEs were detected in all of the fish samples. The concentrations of total PBDEs were 0.01-2.88 ng/g ww. The seerfish and the yellowtail containd PBDEs in high concentrations. The most dominant congener in most of the fish was 2,2',4,4'-tetrabromo diphenyl ether. TBBPA was detected in 29 fish samples at 0.01-0.11 ng/g ww. The mean level of TBBPA was about one-tenth or less of the total level of PBDEs. A good correlation was obtained between total PBDEs and fat content. On the other hand, no correlation was obtained between TBBPA and fat content. The daily intakes from fish were estimated to be 0.58 ng/kg body weight (bw)/day for total PBDEs, 0.03 ng/kg bw/day for TBBPA, and 0.01 pg TEQ/kg bw/day for brominated dioxins in the case assuming that the average bw of a Japanese adult person is 50 kg and that the average fish consumption is 82 g/day. For PBDEs, the provisionally calculated value was much less than the lowest observed adverse effect level value (1 mg/kg bw/day). For brominated dioxins, the daily intake was at a very low level compared with the Japanese daily intake of polychlorinated dioxins from fish. Even if the value of PBDD/DFs is added to the amount of chlorinated dioxin exposure, it was estimated that it is less than the tolerable daily intake (4 pg TEQ/kg bw/day) in Japan.

The polychlorinated quaterphenyl (PCQ) concentrations in the blood are important discriminative parameters in Yusho patients. The blood samples of 81 persons were analyzed for PCQ in the 2005 annual inspection for Kanemi rice oil poisoning. PCQ was detected in 28 blood samples (ranging from 0.02 to 4.05 ppb). The means of PCQ concentration in the blood were 1.80 ppb (0.33-4.05 ppb) in pattern A, 0.71 ppb (0.02-2.26 ppb) in pattern B, 0.03 ppb (0. 02-0.14 ppb) in pattern BC and 0.02 ppb (0.02-0.45 ppb) in pattern C, respectively. PCQ was still present at high concentration in the blood of patterns A and B. Since PCQ concentration is a useful diagnostic criteria, it is important to follow up on this survey of blood PCQ levels.

The polychlorinated quaterphenyl (PCQ) concentrations in the blood are important discriminative parameters in Yusho patients. In this study, the analytical method of PCQ was improved, and a high speed and precision analysis could be achieved. A recovery test showed satisfactory recoveries of 99.5% (RSD4.8%, n = 5). Using this method, the authors analyzed 62 blood samples which were collected from the 2004 annual inspection for Kanemi rice oil poisoning. PCQ was detected in 20 blood samples (ranging from 0.03 to 4.15 ng/g). The average concentration was 2.07 ng/g in the pattern A (typical Yusho patients), 0.76 ng/g in the pattern B, 0.18 ng/g in the pattern BC and 0.01 ng/g in the pattern C, respectively.

We studied the progressive analytical method for polychlorinated biphenyls (PCBs) in blood samples collected from Yusho patients. This study established a systematic procedure for determining both "total concentration of PCBs and their profiles" and "concentrations of mono-ortho PCBs as dioxin-like compounds", providing a significant index for diagnosis. The method we developed consists of a rapid clean-up using gel permeation chromatography (GPC) and sensitive identification with high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). This method provides identification of all of PCB congeners typically detected in human blood samples, especially it is worth noting that nine significant congeners on Yusho diagnosis (IUPAC #105, #114, #118, #123, #153, #156, #157, #167, #189) were detected from a five-gram blood sample. Using the present method, we analyzed sixty-six individual blood samples collected during the annual Yusho inspection in the 2004, and could identified sixty-eight PCB isomers in all samples. As a result, ten patients were classified into pattern A, the typical Yusho pattern. The mean total PCB concentration of pattern A subjects was 2.95 ppb, while that of control subjects was 0.77 ppb, at whole blood basis respectively.