SR-X-ray fluorescence analysis of arsenic poisoning biopsy samples

应用同步辐射诱导X射线荧光（SR-XRF）分析技术研究了人发和皮肤中砷的含量。样品取自急性和慢性砷中毒患者。前者是从和歌山市的砷咖喱谋杀案受害者身上采集的，后者来自中国，那里存在严重的砷环境问题，慢性中毒发生在几十万人的规模上。用一维SR-XRF分析法测定了砷在头发中的沿着分布，用5 μm大小的X射线微束二维分析法测定了砷在头发中的垂直分布。还检查了通过活检获得的皮肤样品。砷的化学状态与毒性密切相关，因此砷中毒患者头发的一维分析表明，砷中毒患者头发中砷的含量较高， ...更多信息 持续1cm长度（约两周）。慢性砷中毒样品的砷含量呈单调分布。头发切片的二维分析显示，砷在头发的外边缘高度积累，而锌和硫均匀分布。铜的分布与砷相似。首次发现砷在慢性砷中毒患者皮肤中有蓄积现象。在真皮和表皮之间的区域观察到高砷水平。用XANES分析急性中毒者头发中的砷，发现砷以无机三价态存在。提示砷在急性中毒过程中未被代谢。本研究清楚地揭示了砷在急性和慢性砷中毒中的蓄积机制。本研究还表明，SR-XRF是一种强有力的非破坏性技术，以揭示微量砷在活检样品中的分布和化学形态。少

Synchrotron radiation induced X-ray fluorescence (SR-XRF) analysis was applied to reveal arsenic level in human hair and skin. The samples are obtained from patients of acute and chronic arsenic poisonings. The former specimens were collected from victim of arsenic curry murder occurred at Wakayama city and the latter were from China, where serious arsenic environmental problem exists and chronic poisoning is generated in a few hundred thousands person scale. The distribution of arsenic along the length of a hair was measured by one-dimensional SR-XRF analysis and that in the vertical section was measured by two-dimensional analysis utilizing X-ray microbeam in 5 μm size. The skin samples obtained by biopsy was also examined. Chemical state of arsenic is strongly related with toxicity and therefore it is another important subject of the present study.One dimensional analysis of hairs from victims of arsenic poisoning show that presence of a clear peak of arsenic and high arsenic level … More continued for 1cm length (about two weeks). On the other hand, the results for the samples of chronic poisoning show monotonous distribution of arsenic. Two dimensional analysis of hair section has revealed high accumulation of arsenic at outer rim of the hair whereas zinc and sulfur was uniformly distributed. The distribution of copper was similar to that of arsenic. It is found for the first time that the accumulation of arsenic does happen in the skin from patients of chronic arsenic poisoning. The high arsenic level was observed at a region between corium and epidermis of the skin. XANES analysis of arsenic in the hair of acute poisoning has revealed that arsenic exists in the form of inorganic trivalent state. This result suggests that the arsenic was not metabolized in the acute poisoning. The present study clearly revealed the accumulation mechanism of arsenic in both acute and chronic arsenic poisonings. This study also demonstrated that SR-XRF is a powerful nondestructive technique to reveal distribution and chemical form of trace arsenic in biopsy samples. Less