Institute of Food Chemistry, University of Hohenheim , Garbenstraße 28, D-70599 Stuttgart, Germany.
University of Iceland, Keldur, Institute for Experimental Pathology , IS-112 Reykjavík, Iceland.
Environ Sci Technol. 2017 Aug 1;51(15):8335-8342. doi: 10.1021/acs.est.7b02662. Epub 2017 Jul 21.
Abiotic and biotic transformation of toxaphene (camphechlor) results in the selective enrichment of recalcitrant congeners while other, less persistent compounds of technical toxaphene (CTTs) are degraded. Until now, there has been little knowledge on oxidation transformation of toxaphene. For instance, the existence of hydroxylated CTTs (OH-CTTs) in authentic environmental and food samples has not been proven. For this reason, we synthesized a mixture consisting of tetra- to heptachlorinated OH-CTTs and simplified it by countercurrent chromatography (CCC). Thus, 227 OH-CTTs were detected in the CCC fractions (12 tetra-, 117 penta-, 81 hexa-, and 17 heptachlorinated OH-CTTs), which was >50% more than detected before the fractionation. One CCC fraction consisting of only 18 OH-CTTs was used to develop a sample cleanup method which aimed to remove CTTs, isobaric PCBs, and sample matrix. The final cleanup procedure consisted of (i) gel permeation chromatography (GPC) and adsorption chromatography using (ii) deactivated and (iii) activated silica gel. Hence, up to 320 and 4350 μg/kg lipid weight of octa- and nonachlorinated CTTs were detected in four liver samples and adipose tissue of polar bears, respectively. Furthermore, the presence of one hexachlorinated OH-CTT isomer could be verified in the samples, which was about 1% of the octachlorinated CTTs determined in the liver samples.
拟除虫菊酯（camphechlor）的非生物和生物转化导致其顽固同系物的选择性富集，而技术拟除虫菊酯（CTTs）中的其他持久性较低的化合物则被降解。到目前为止，人们对拟除虫菊酯的氧化转化知之甚少。例如，在真实的环境和食品样本中是否存在羟基化的 CTTs（OH-CTTs）尚未得到证实。出于这个原因，我们合成了一种由四氯至七氯羟基化 CTTs 组成的混合物，并通过逆流色谱（CCC）对其进行了简化。因此，在 CCC 馏分中检测到 227 种 OH-CTTs（12 种四氯、117 种五氯、81 种六氯和 17 种七氯羟基化 CTTs），比分离前检测到的数量增加了>50%。一个仅由 18 种 OH-CTTs 组成的 CCC 馏分被用于开发一种样品净化方法，旨在去除 CTTs、同系物 PCB 和样品基质。最终的净化程序包括（i）凝胶渗透色谱（GPC）和使用（ii）失活和（iii）活化硅胶进行吸附色谱。因此，在 4 个北极熊肝脏样本和脂肪组织中，分别检测到高达 320 和 4350μg/kg 脂质重量的八氯和非八氯 CTTs。此外，在样品中可以验证存在一种六氯羟基化 OH-CTT 异构体，其含量约为肝脏样本中确定的八氯 CTTs 的 1%。
