Chemical Studies on Tobacco Smoke. IX: Quantitative Analysis of Chlorinated Hydrocarbon Insecticides

Q3 Agricultural and Biological Sciences
Dietrich Hoffmann, G. Rathkamp, Ernest L. Wynder
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引用次数: 7

Abstract

Abstract An analytical method was developed for the qualitative and quantitative determination of chlorinated hydrocarbon insecticides in tobacco products. It is based on three consecutive liquid-liquid distributions, followed by column chromatography on deactivated alumina. This procedure leads to a degree of enrichment which permits the direct assessment of the insecticides by gas chromatography. For the isolation and identification of the individual components the column chromatography endfractions are separated by gas chromatography and collected from the effluent of the column. These materials are used for mass spectrometric analysis. For the quantitative analysis C14-labelled DDT is employed as internal standard and the amount of insecticides is determined with the aid of a gas chromatograph with an electron capture detector with a sensitivity for chlorinated insecticides of 1 nanogram (10-9 g). In 1.0 g cigarette tobacco were found 11.7 µg 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane [DDD]; 4.8 µg 1,1-dichloro-2-(o-chlorophenyl)-2-(p´-chlorophenyl)ethane [o,p´-DDD]; 7.8 µg 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane [DDT] and 3.6 µg of an admixture of 1,1,1-trichloro-2-(o-chlorophenyl)-2-(p´-chlorophenyl)ethane [o,p´-DDT] and 1,1-dichloro-2-(m-chlorophenyl)-2-(p´-chlorophenyl)ethane [m,p´-DDD]. The mainstream smoke of an 85 mm U.S. blended cigarette without filter tip contained 1.75 µg DDD, 0.45 µg o,p´-DDD, 0.81 µg DDM, 0.77 µg DDT, 0.70 µg o,p´-DDT plus m,p´-DDD, 0.21 µg 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene and 0.21 µg 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene [DDE] and 1.52 µg trans-4,4´-dichlorostilbene [trans-DCS]. Endrin was neither detected in cigarette smoke nor in commercial U.S. tobacco samples purchased during the winter 1967-68. The transfer rates for unchanged chlorinated insecticides from cigarette tobacco into mainstream smoke were 18 % for DDD, 11.6 % for o,p´-DDD and 12.4 % for DDT. The extraction of tobacco with n-hexane does not yield a complete extraction of chlorinated insecticides. A study in which a single leaf of a tobacco plant was sprayed with C14-labelled DDT indicated that the insecticide to some degree permeates the tobacco plant by diffusion into the lower layers of the leaf. In tobacco smoke condensate, which is exposed to sunlight or white laboratory light, one pyrolysis product of DDD and DDT, trans-4,4´dichlorostilbene, is photoisomerized to its cis-isomer. In an in vitro test cis-4,4´-dichlorostilbene was found to be dehydrogenated in air up to 0.5 % to 3,6-dichlorophenanthrene. Pyrolysis experiments at 880°C with DDD and DDT have been discussed briefly. In addition to components already found in cigarette smoke, chlorobenzene, the highly reactive 9-methylenefluorene and tentatively 1-chloro-2,2-(p-chlorophenyl)ethane as well as 3,6-dichloro-9-chloromethylfluorene were identified in the pyrolyzate. The findings of this study are compared with earlier investigations and discussed in respect to the formation of some of the chlorinated aromatic hydrocarbons. Animal studies are needed to evaluate the possible tumorigenicity of the major pyrolysis products of DDT and DDD.
烟草烟雾的化学研究。九、氯代烃类杀虫剂的定量分析
建立了烟草制品中氯代烃类杀虫剂的定性定量测定方法。它是基于三个连续的液-液分布,其次是失活氧化铝的柱层析。这个程序导致一定程度的富集,允许气相色谱法直接评估杀虫剂。为了分离和鉴定单个组分,用气相色谱法分离柱层析的末组分,并从柱的流出物中收集。这些材料用于质谱分析。定量分析采用c14标记的滴滴涕作为内标,采用气相色谱仪和电子捕获检测器测定杀虫剂的含量,该检测器对氯化杀虫剂的灵敏度为1纳克(10-9克)。在1.0 g卷烟中发现11.7µg 1,1-二氯-2,2-双(对氯苯)乙烷[DDD];4.8µg 1,1-二氯-2-(o-氯苯基)-2-(p′-氯苯基)乙烷[o,p′- ddd];7.8µg 1,1,1-三氯-2,2-二(对氯苯)乙烷[DDT]和3.6µg 1,1,1-三氯-2-(邻氯苯)-2-(对氯苯)乙烷[o,p ' -DDT]和1,1-二氯-2-(间氯苯)-2-(对氯苯)乙烷[m,p ' - ddd]的混合物。85 mm美国无过滤嘴混合卷烟主流烟中DDD含量为1.75µg、0.45µg o、p′-DDD、0.81µg DDM、0.77µg DDT、0.70µg o、p′-DDT + m、p′-DDD、0.21µg 1,1-二氯-2,2-二(对氯苯)乙烯、0.21µg 1,1-二氯-2,2-二(对氯苯)乙烯和1.52µg反式4,4′-二氯二苯乙烯。Endrin既没有在香烟烟雾中检测到,也没有在1967-68年冬季购买的美国商业烟草样品中检测到。未改变的氯代杀虫剂从卷烟烟草向主流烟雾的转移率分别为:DDD 18%, o,p´-DDD 11.6%,滴滴涕12.4%。用正己烷提取烟草不能完全提取氯化杀虫剂。在一项研究中,在烟草植物的单叶上喷洒了c14标记的滴滴涕,结果表明,这种杀虫剂在一定程度上通过扩散到叶片的下层而渗透到烟草植物中。在暴露于阳光或实验室白光下的烟草烟雾冷凝物中,DDD和DDT的一种热解产物反式4,4′二氯二苯乙烯被光异构为其顺式异构体。在体外试验中发现,顺式-4,4′-二氯二苯乙烯在空气中脱氢至0.5%为3,6-二氯菲。简要讨论了DDD和DDT在880℃下的热解实验。除了已经在香烟烟雾中发现的成分,氯苯,高活性的9-亚甲基芴和暂时的1-氯-2,2-(对氯苯)乙烷以及3,6-二氯-9-氯甲基芴在热解产物中被鉴定出来。本研究的结果与早期的研究结果进行了比较,并讨论了一些氯化芳香烃的形成。需要动物实验来评估DDT和DDD的主要热解产物可能的致瘤性。
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来源期刊
Beitrage zur Tabakforschung International/ Contributions to Tobacco Research
Beitrage zur Tabakforschung International/ Contributions to Tobacco Research Agricultural and Biological Sciences-Agronomy and Crop Science
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