典型杀虫剂类POPs污染场地及其周边污染特征与环境风险评估研究

发布时间：2018-06-02 06:47

本文选题：HCHs + 硫丹　；参考：《重庆交通大学》2015年硕士论文

【摘要】：持久性有机污染物(POPs)由于高毒性、持久性、生物蓄积性和半挥发性,并且能够在全球范围内传输和分布,近几十年以来受到了人们的高度关注,POPs污染已成为影响人类生存与健康的重大环境问题。随着《关于持久性有机污染物的斯德哥尔摩》的生效,许多包括有机氯农药在内的化学品POPs已在全球范围内禁止生产和使用,而杀虫剂类POPs生产企业也成为了潜在的POPs污染高风险区。公约首批受控的杀虫剂类POPs共有9种,2009年和2011年分别又有六六六(HCHs)、硫丹等POPs成为公约受控的物质。然而,目前对这些新增杀虫剂类POPs污染场地及其周边环境介质中农药残留的调查研究十分有限,无法全面系统地评估其环境风险。开展杀虫剂类POPs污染场地及其周边环境介质以及生物体中杀虫剂类POPs的累积特征和残留机制,对于准确评估杀虫剂类污染场地的健康风险、开展场地修复与管理以及保障城市环境具有重要意义。本研究以HCHs和硫丹2个典型新增杀虫剂类POPs污染场地为研究对象,对场地及其周边的土壤、大气、地下水等环境介质和植物中的HCHs和硫丹残留水平、空间分布特征进行了系统地研究,并进一步对污染场地及其周边开展了健康风险评估研究。研究结果表明:(1)六六六(HCHs)污染场地厂区表层土壤中ΣHCHs(α-,β-,γ-,δ-HCH之和)的浓度范围为2.0~148.5 mg/kg,剖面土壤中ΣHCHs含量为0.05~21.27mg/kg,4种异构体α-HCH、β-HCH、γ-HCH、δ-HCH的检出率均为100%。剖面垂直方向上,土壤中ΣHCHs在地下1m深度范围内浓度较高,并呈现不均匀分布;当土壤深度超过1m时,土壤中ΣHCHs含量迅速降低,稳定在较低水平。厂区大气中HCHs浓度为10.2~132.8 ng/m3,尤其在废物存储区域附近的大气中HCHs浓度高达132.8 ng/m3。厂区地下水中ΣHCHs浓度为1.4~2.6μg/L。厂区内的植物中也检测出了HCHs残留,植物中ΣHCHs浓度范围为24.6~520.7 ng/g d.w.,浓度较高。通过对HCHs组成的分析,发现污染场地环境介质中HCHs来源于历史生产。(2)六六六(HCHs)污染场地周边表层土壤中ΣHCHs的浓度为46~665 ng/g,4种异构体α-HCH、β-HCH、γ-HCH、δ-HCH的检出率均为100%。周边土壤中HCHs的含量在1.0km范围内随距离增加呈现降低趋势,在距离厂区2.0km范围,土壤中HCHs的浓度出现了峰值,之后随着距离的增加浓度迅速降低。大气中ΣHCHs含量范围为1.52~13.79 ng/m3,且HCHs含量随着距离厂区的远近呈现波动趋势,在距离厂区2.0km范围内较高,之后缓慢下降,同周边土壤中HCHs变化趋势一致,经过对HCHs组成分析,土壤与大气中HCHs残留主要来自于历史生产。周边蔬菜样品中四种异构体的检测率是100%,且其ΣHCHs浓度范围为3.71~85.1 ng/g f.w.,豇豆中ΣHCHs含量超出了我国标准(GB2763-2014)的最大限量。周边环境介质中HCHs组成分析表明HCHs残留主要来源于历史生产。(3)硫丹污染场地表层土壤中,在硫丹乳油车间附近硫丹的浓度较高,为47.6mg/kg,其他点位硫丹浓度范围为0.09~2.85 mg/kg,剖面土壤中硫丹浓度为0.01~114 mg/kg。厂区内大气中硫丹的浓度范围为4.8~289.1 ng/m3,且通过计算Fα-endo值(Fα-endo=α-硫丹/(α-硫丹+β-硫丹)),发现大气中硫丹在环境中的降解程度很小。地下水中的硫丹的含量很低,9.92~12.6 ng/L。厂区植物中硫丹检出率为100%,浓度范围为4.15~25.3 ng/g d.w.,且硫丹硫酸盐占主要比例。(4)硫丹污染场地周边表层土壤中硫丹含量范围为1.37~53.57 ng/g,同一距离,从厂区上风向到下风向,硫丹浓度表现为上风向浓度低,向下风向浓度逐渐升高,随着距离的增加,浓度降低,在距离厂区2.0km是出现波动峰值。周边大气中硫丹的含量范围为0.89~10.36 ng/m3,随着厂区距离的增加,大气中硫丹含量呈现先升高后降低的趋势,并在距离厂区2.0km的大气中硫丹浓度最高达到10.36ng/m3。周边代表性的农作物(小麦、桑叶和油菜)硫丹的检出率为100%,随着距离厂区的距离越远,其中硫丹含量降低。(5)风险评估研究表明,六六六(HCHs)污染场地内HCHs致癌风险普遍较高,超出了我国污染场地可接受致癌水平(10-6),危害指数均小于1;周边致癌风险在可接受水平之内,但依然有2个点位致癌风险超标,危害指数均小于1。硫丹污染场地厂区内乳剂车间的危害指数超过了1,其他地方符合要求,周边硫丹危害指数符合要求。通过对周边成人和儿童风险的计算,发现儿童作为较敏感的人群,致癌风险与危害指数均高于成人。
[Abstract]:Persistent organic pollutants (POPs), which are highly toxic, persistent, bioaccumulative and semi volatile, can be transmitted and distributed globally, and have attracted great attention in recent decades. POPs pollution has become a major environmental problem affecting human survival and health. In effect, many POPs chemicals, including organochlorine pesticides, have been banned from production and use worldwide, and pesticide POPs production enterprises have also become a potential high-risk area for POPs pollution. The first batch of controlled POPs insecticides of the Convention have 9 kinds, 666 (HCHs) in 2009 and 2011, and POPs as endosulfan as public. However, the current investigation of pesticide residues in these new insecticide POPs contaminated sites and their surrounding environmental media is very limited, and the environmental risks are not systematically assessed. The cumulative characteristics and residues of insecticide POPs in the pesticide POPs contaminated sites and its surrounding environment and the organisms in the organisms are also carried out. The retention mechanism is of great significance to accurately assess the health risks of insecticide contaminated sites, to carry out site remediation and management and to guarantee the urban environment. This study takes HCHs and endosulfan 2 typical new pesticides POPs contaminated sites as the research object, and the soil, atmosphere, groundwater and other environmental media and plants on the site and its surrounding areas. The residual levels of HCHs and endosulfan were systematically studied and the health risk assessment of the contaminated sites and its surrounding areas was further studied. The results showed that: (1) the concentration range of sigma HCHs (alpha, beta, gamma, Delta -HCH) in the surface soil of the 666 (HCHs) contaminated site is 2.0~148.5 mg/kg, and the sigma H in the soil profile The content of CHs is 0.05~21.27mg/kg, the detection rate of 4 isomers alpha -HCH, beta -HCH, gamma -HCH, and delta -HCH are all vertical in the 100%. section. The concentration of the sigma HCHs in the soil is high in the 1m depth range, and presents an uneven distribution. When the soil depth exceeds 1m, the Sigma HCHs content in the soil decreases rapidly and is stable at a lower level. In the atmosphere of the plant, HCHs concentration in the atmosphere is strong. The degree is 10.2~132.8 ng/m3, especially in the atmosphere near the storage area of the waste storage area, the concentration of HCHs in the 132.8 ng/m3. area of the plant has also been detected in the 1.4~2.6 mu g/L. plant. The concentration range of the sigma HCHs is 24.6~520.7 ng/g D.W., and the concentration is high. In the environment medium, HCHs is derived from historical production. (2) the concentration of sigma HCHs in the surface soil around the 666 (HCHs) contaminated site is 46~665 ng/g, 4 isomers, alpha -HCH, beta -HCH, gamma -HCH, and delta -HCH are all HCHs in the vicinity of 100%.. The concentration of HCHs in the soil has a peak value, and then decreases rapidly with the increase of distance. The content range of the sigma HCHs in the atmosphere is 1.52~13.79 ng/m3, and the HCHs content fluctuates with the distance from the factory area, which is higher in the range of 2.0KM range from the factory area, and then slowly decreases, which is consistent with the trend of HCHs in the surrounding soil and passes through the HCHs group. HCHs residues in soil and atmosphere mainly come from the historical production. The detection rate of four isomers in the surrounding vegetable samples is 100%, and the concentration range of the sigma HCHs is 3.71~85.1 ng/g F.W.. The content of sigma HCHs in the cowpea is beyond the maximum limit of our national standard (GB2763-2014). The analysis of HCHs composition in the surrounding environmental media shows that the HCHs residue is the main residue. (3) in the surface soil of the endosulfan contaminated site, the concentration of endosulfan near the endosulfan oil workshop is higher, 47.6mg/kg, and the concentration range of other points is 0.09~2.85 mg/kg. The concentration of endosulfan in the profile soil is 4.8~289.1 ng/m3 in the atmosphere of 0.01~114 mg/kg. plant, and the F a -endo value is calculated by calculating the F alpha -endo value. (F alpha -endo= alpha endosulfan / (alpha endosulfan + beta disulfide)), it is found that the degree of endosulfan degradation in the atmosphere is very small. The content of endosulfan in groundwater is very low. The detection rate of endosulfan in plants of 9.92~12.6 ng/L. plant is 100%, and the concentration range is 4.15~25.3 ng/g D.W., and endosulfan sulphate is the main proportion. (4) endosulfan contaminated surface soil around the site of endosulfan. The content range of endosulfan is 1.37~53.57 ng/g, at the same distance, from the wind direction to the downward wind direction from the factory area, the concentration of endosulfan is low in the upward wind direction and the downward wind direction is increasing gradually. With the increase of distance, the concentration is reduced, and the peak of the fluctuation in the distance from the factory area is 2.0KM. The content range of endosulfan in the surrounding atmosphere is 0.89~10.36 ng/m3, along with the factory area. The content of endosulfan in the atmosphere increased first and then decreased, and the rate of endosulfan in the atmosphere of 2.0KM from the factory area was up to 10.36ng/m3., and the detection rate of endosulfan was 100%. As far away from the distance from the factory area, the content of endosulfan was reduced. (5) the risk assessment study The results showed that the risk of carcinogenesis of HCHs in the 666 (HCHs) contaminated site was generally high, which exceeded the level of carcinogenic level (10-6) in the polluted site in China (10-6), the hazard index was less than 1, and the risk of peripheral carcinogenesis was within acceptable level, but the risk of carcinogenesis still exceeded the standard, and the hazard index was less than the harm of the emulsion workshop in the factory area of 1. endosulfan contaminated site. The index was over 1, other places met the requirements, and the perimeter endosulfan hazard index met the requirements. By calculating the risk of peripheral adults and children, children were found to be more sensitive people, and the risk of carcinogenesis and risk index were higher than those of adults.
【学位授予单位】：重庆交通大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X592

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