To analyze the dioxin content of samples, includingdibenzo-
p-dioxins/dibenzofurans, and coplanar polychlorinated biphenyls (Co-PCBs), a large volume is usuallynecessary. This is difficult, however, when analyzingclinical samples, such as serum and tissue. We thereforesought to increase the sensitivity of high-resolution gaschromatography/high-resolution mass spectrometry(HRGC/HRMS) in analyzing dioxins by injecting most ofthe extract from a small clinical sample. The concentrationof each congener was estimated by injecting extracts of5-g samples into a gas chromatography capillary precolumn (AT column) and by assaying extracts of 25-gsamples by conventional splitless methods. We found thatthe limit of detection with the AT column was lower thanthat obtained by the splitless technique. In the AT columntechnique, 100
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L of the 110-
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L final solution, equivalentto 4.5 g of the original sample, was injected into HRGC/HRMS. In contrast, 2
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L of the 20-
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L final solution,equivalent to 2.5 g of original sample, was assayed usingthe splitless method. Moreover, when 25 fg of ultratracedioxin was added to 100
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L of HRGC/HRMS sample andinjected into the AT column, the peak area was almostthe same as that obtained with 2
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L of HRGC/HRMSsample injected using the splitless method. Althoughassaying 10-20
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L of sample by the splitless methodpresents difficulties due to sample volatility, this problemcan be reduced by using volumes larger than 100
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L. Wetested this application by quantifying the parts-per-trillionlevels, on a lipid weight basis, of each congener in a serumsample of 5 g using the AT column HRGC/HRMS method.We found this application to be successful and practicalfor mass screening of dioxin exposure in clinical samples.