1-溴丙烷职业接触限值的研制

发布时间：2018-03-11 14:09

本文选题：1-溴丙烷　切入点：气相色谱法　出处：《复旦大学》2013年硕士论文　论文类型：学位论文

【摘要】：1-溴丙烷(1-Bromopropane,1-BP)主要用于生产喷雾粘合剂、精密仪器的清洗剂和脱脂剂,也用作制药产业、杀虫剂和季胺类化合物合成的中间体。随着国际社会对氟氯昂类化合物的禁止生产和使用,1-BP被广泛用作其替代物,生产和使用量在世界范围内逐年增长。我国作为1-BP生产大国,暴露于1-BP的人群随着产量和使用量的增加而逐年增长。1-BP对人体具有多种毒作用。动物实验显示,1-BP具有神经毒性、生殖和发育毒性和致癌性等多种毒作用。人群调查和多起病例报告也提示,长期接触1-BP可能会导致中枢和外周神经系统出现病变,血液和生化系统以及肝脏病变。我国目前尚未制定1-BP职业接触限值,本次研究基于实验室研究结果和职业现场调查,综合相关研究成果,为制定我国1-BP职业接触限值和规范实验室检测方法提供依据。为测定工作场所空气中1-BP,我们建立了气相色谱-氢火焰离子化检测法(GC-FID),采用SPB-1色谱柱(30m×0.25mm×0.25μm),使用程序升温法,以N2为载气,进行分流进样。用主动式采样器连结活性炭管采集工作场所空气中1-BP,经二硫化碳溶剂解吸,以保留时间定性,以峰面积定量。我们对该方法的各项指标进行了检验。检验结果显示,该方法能够有效分离1-BP和常见污染物2-BP,线性范围广,相关系数R2=0.9996,可检测空气中1-BP最低浓度为0.08mg/m3(以采集3L空气样本计)。批间和批内相对标准偏差RSD10%,加标回收率介于95%-105%之间,解吸效率90%,常温下保存,第五天下降率10%,穿透容量大于1.75mg。.该方法满足GBZ/T210.4-2008《工作场所空气中化学物质测定方法》的要求,适用于工作场所空气中1-BP的测定。为了解1-BP职业接触与工人健康之间的关系,我们对某1-BP生产企业进行了职业卫生调查。收集企业生产信息,掌握1-BP生产流程,收集1-BP工厂工人的职业史及个人基本信息,采用定点采样和个体采样方法监测环境和个体暴露水平。收集先前的各种健康监护资料,分析1-BP暴露和工人健康效应之间关系。调查结果显示该职业场所广泛存在1-BP,最高检测浓度达153.08mg/m3,精馏房处检测浓度几何均数最高,为43.62mg/m3,非1-BP生产区域也可检测到最低1.95mg/m3的环境浓度。个体暴露水平在主动采样和被动采样之间无统计学差异p0.10)。健康监护资料显示,目前1-BP暴露工人健康状况良好。此次职业卫生调查,未发现该职业场所1-BP暴露对工人健康产生危害。相关的研究结果显示,采用胫神经远端潜伏期作为效应终点,计算的基准剂量BMD和其下限值BMDL分别为36.77mg/m3和21.73mg/m3;采用肌酸激酶作为效应终点,计算出基准计量BMD和下限值BMDL分别为88.28mg/m3和44.52mg/m3;采用促甲状腺激素作为效应终点,BMD和BMDL分别为47.23mg/m3和31.54mg/m3。参照其他国家提出的1-BP接触限值,结合本次研究结果,我们建议以外周神经系统损伤作为基准效应指标,以其BMDL21.73mg/m3作为职业接触限值建议的基础,将我国1-BP职业接触限值(TWA-8h)定为21.00mg/m3,并加注经皮吸收标识。
[Abstract]:1- bromopropane (1-Bromopropane, 1-BP) is mainly used for the production of spray adhesives, cleaning and degreasing agent for precision instruments, is also used in pharmaceutical industry, pesticides and quaternary ammonium compounds as synthetic intermediates. With the international society for the CFC compounds banned the production and use, 1-BP is widely used as the substitute, production and usage increase year by year in the world. China is the largest producer of 1-BP production in 1-BP exposed groups increased with the quantity of production and consumption and increased year by year.1-BP has a variety of toxic effects on the human body. Animal experiments show that 1-BP has the nerve toxicity, reproductive and developmental toxicity and carcinogenicity and other toxic effects. Epidemiological investigation and cases the report also suggested that long-term exposure to 1-BP may cause the central and peripheral nervous system lesions, blood and biochemical system and liver disease. China has yet to formulate 1-BP occupational exposure limit This research is based on the results of laboratory studies and field surveys, and provides the basis for formulating 1-BP occupational exposure limits and standardizing laboratory testing methods.
For the determination of 1-BP in the air of workplace, we established a gas chromatography flame ionization detection (GC-FID), a SPB-1 column (30M * 0.25mm * 0.25 m), the use of temperature programming method with N2 as carrier gas, shunt injection. In workplace air was collected by active 1-BP sampler link activated charcoal tube by solvent desorption of carbon disulfide, qualified by retention time and peak area as the quantitative indicators of the method. We tested. Test results show that this method can effectively separate 1-BP and 2-BP common pollutants, wide linear range, correlation coefficient R2=0.9996, can detect the lowest concentration of 1-BP in air 0.08mg/m3 (3L meter to collect air samples). The inter and intra relative standard deviation RSD10%, the rate of recovery is 95%-105%, desorption efficiency of 90%, stored at room temperature, the fifth day of decline rate is 10%, the penetration capacity of more than 1.75mg.. This method meets GBZ/T The requirement for the determination of chemical substances in the air of 210.4-2008< workplace is applicable to the determination of 1-BP in the air of the workplace.
In order to understand the 1-BP occupation contact and the relationship between health workers, we conducted a survey of occupation health 1-BP production enterprises. Collect production information, grasp the 1-BP production process, the history of occupation collection 1-BP factory workers and the basic personal information, using fixed-point sampling and individual sampling monitoring of the environment and individual exposure levels to collect all kinds of health. Monitoring data of the previous analysis of the relationship between 1-BP exposure and health effects of workers. The survey results show that the occupation place widely existed in 1-BP, the highest concentration of 153.08mg/m3 detection, detection of real distillation geometric mean highest concentration, 43.62mg/m3, non 1-BP production areas can also be detected. 1.95mg/m3 environment was the lowest level in the active and passive sampling there was no significant difference between the sampling p0.10 exposure). Individual health care information, the current status of workers exposed to 1-BP in good health. The occupation health It was not found that exposure to 1-BP in the workplace was harmful to the health of the workers.
The results show that the effect of tibial nerve distal latency as the end point, the benchmark dose of BMD computing and its limit value of BMDL were 36.77mg/m3 and 21.73mg/m3; the effect of creatine kinase as the end point, calculate the benchmark BMD and the lower limit value of BMDL were 88.28mg/ m3 and 44.52mg/m3; the effect of thyroid stimulating hormone as the end point, and BMD BMDL 47.23mg/m3 and 31.54mg/m3. respectively for the reference of other countries proposed 1-BP exposure limits, combined with the research results, we suggest that the peripheral nervous system damage as the benchmark effect index, with its BMDL21.73mg/m3 as the basis of occupation contact limiting values suggest, 1-BP will contact the limits of our occupation (TWA-8h) for 21.00mg/m3, and add the the skin absorption logo.

【学位授予单位】：复旦大学
【学位级别】：硕士
【学位授予年份】：2013
【分类号】：R134

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