云南省某县农村居民尿液、土壤与水体中农药残留及其与防护措施的关系研究
发布时间:2018-05-06 23:32
本文选题:异菌脲 + 农药残留 ; 参考:《昆明医科大学》2017年硕士论文
【摘要】:[目的]通过采用超高效液相色谱串联质谱法(UHPLC-MS/MS)测定云南省某县农村居民尿液及其居住环境的土壤、水体中的农药残留情况,探讨居民尿液中农药残留量与农药使用情况、使用时采取防护措施的情况、自我报告与使用农药有关的症状及环境中农药残留之间的关系,为农药残留的体内暴露提供直接证据,为评估农药暴露健康风险提供依据。[方法]采用问卷调查和实验室检测两种研究方法,现场围绕居民农药使用情况、使用时采取防护措施以及不适症状的出现等情况对230名居民开展问卷调查并采集其尿样;同时采集29份土样、28份水样,采用UHPLC-MS/MS测定其中的17种农药。尿样经SPE(Waters Oasis MCX,3cc)柱固相提取,用甲醇和5%的氨水甲醇溶液洗脱后离心浓缩;水样经冷冻干燥;土样经甲醇提取,过滤后浓缩。所有样品经乙腈定容后,经0.22 μm过滤器过滤,以0.01%的甲酸乙腈溶液和0.01%的甲酸水溶液为流动相梯度洗脱,经Cosmosil packed column(4.6 mm × 150 mm)色谱柱分离,采用电喷雾离子源正离子模式进行质谱检测;用Analyst 1.6.2软件分析离子流图和质谱图,EpiData 3.1录入问卷,SPSS 17.0进行一般性描述分析和检验。[结果]UHPLC-MS/MS方法的线性范围为0.01-1.00 μg/mL,相关系数(r)均大于0.990;230份尿样中检测出多菌灵、异菌脲、百菌清、福美双、甲氰菊酯、高效氯氟氰菊酯、毒死蜱7种农药残留,本次共检出150人尿液中有农药残留,检出阳性率为65.22%,其中异菌脲的检出率最高,共检出102份,检出阳性率为44.35%。尚未发现居民尿液中农药残阳性率及残留浓度在性别、年龄等不同分组间有差别;两个乡镇的居民尿液中农药残留检出阳性率有差别(χ2=7.29,P0.05);五个村庄间居民尿液中农药残留及异菌脲残留检出阳性率均有差别(χ2=10.91,χ2=11.49,P0.05),阳性人群尿液中异菌脲残留浓度有差别(F =3.60,P0.01)。居民中最近一个月未使用农药的人群尿液中农药残留阳性率低于使用人群(χ2=10.59,P0.05);尿液中异菌脲残留阳性人群中,未使用农药人群尿液中异菌脲残留农药浓度低于使用人群(t=5.78,P0.05)。尿液中未检出农药残留人群在使用农药时佩戴口罩、橡胶手套、防护服、穿高筒雨鞋的频率高于检出人群(Z =-4.969,Z =-5.359,Z =-5.180,Z=-2.783,P0.01),防护频率高的人群尿液中异菌脲残留检出率(χ2=24.74,P0.001)、残留浓度(F=3.35,P0.05)均较低。没有出现农药意外皮肤接触的人群尿液中农药残留检出率低于有过农药意外皮肤接触的人群(χ2 =6.11,P0.05),农药皮肤意外接触后及时清洗的人群尿中农药残留检出率低于未处理者(χ2=10.45,P0.05)。农药残留检出阳性人群出现头晕/头昏、头疼、恶心、皮肤发痒的频率多于检出阴性人群(χ2=4.41,χ2=3.86,χ2=7.10,χ2 =6.25,P0.05)。土样中检出多菌灵、异菌脲、毒死蜱这3种农药残留,残留浓度范围为0.05-0.76 μg/mL,共检出12份土样中有农药残留,检出阳性率为41.38%,其中大田土检出阳性率为53.33%,自留地土样检出阳性率为28.57%。三种农药中检出例数最多的是异菌脲,检出8份,检出阳性率为27.58%。水样中检出多菌灵和甲氰菊酯2种农药残留,残留浓度范围为0.04-0.89μg/mL,共检出7份水样中有农药残留,检出阳性率为25.00%,其中灌溉水检出阳性率为35.71%,饮用水水样检出阳性率为14.29%。两种农药中检出例数最多的是异菌脲,检出5份,检出阳性率为17.85%。[结论]该地居民尿液及其居住环境的水体与土壤样本中均有农药残留检出,且都检出有异菌脲残留,残留例数均最多。居民尿液中农药残留检出率较高,找出了农药残留在体内暴露的直接证据,为评估农药暴露风险和环境影响提供了依据。使用农药时采取防护措施能有效的减少农药与人体的接触,减少农药进入人体,应促使居民合理使用农药,加强使用农药时的自身防护措施,从而减少农药进入人体,减少农药对健康的危害。
[Abstract]:[Objective] to determine the pesticide residues in the urine of the rural residents and their living environment in a county of Yunnan province by using the ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS), to discuss the situation of pesticide residues in the urine and the use of pesticides in the urine of the residents, and to take protective measures when used. Self reports are related to the use of pesticides. The relationship between the symptoms and the pesticide residues in the environment provides direct evidence for the exposure of pesticide residues in the body and provides the basis for assessing the health risk of pesticide exposure. [Methods] two research methods are adopted by questionnaire survey and laboratory testing. A questionnaire survey was conducted for 230 residents and their urine samples were collected; 29 samples and 28 samples were collected and 17 kinds of pesticides were measured by UHPLC-MS/MS. The urine samples were extracted by solid phase of SPE (Waters Oasis MCX, 3cc) column, and after elution of methanol and 5% ammonia methanol solution; water samples were frozen and dried; soil samples were extracted by methanol and filtered. After acetonitrile constant volume, all samples were filtered by 0.22 micron M filter, 0.01% formic acid acetonitrile solution and 0.01% formic acid solution were eluted as mobile phase, and separated by Cosmosil packed column (4.6 mm x 150 mm) column, the electrospray ion source positive ion mode was used for mass spectrometry detection, and the ion flow was analyzed with Analyst 1.6.2 software. Map and mass spectrogram, EpiData 3.1 entered the questionnaire, SPSS 17 carried out general description analysis and test. [results]UHPLC-MS/MS method has a linear range of 0.01-1.00 mu g/mL, correlation coefficient (R) is greater than 0.990; 230 samples of urine samples were detected by carbendazim, carbendazide, chlorothalonil, methylene thruthrin, cyhalothrin, chlorpyrifos, 7 pesticide residues. The positive rate of the urine in 150 people was 65.22%, and the positive rate of isocarbamide was the highest, and the positive rate was 102. The positive rate of 44.35%. was not found in the urine of the residents in the urine and the residual concentration in the sex, age and other groups, and the pesticide residues in the urine of the two townships were detected. The positive rates of the positive rates were different (x 2=7.29, P0.05). The positive rates of pesticide residues in urine and residual urea residues in the urine of the five villages were different (x 2=10.91, X 2=11.49, P0.05), and the residual concentration of urea in urine was different (F =3.60, P0.01). The positive rate of pesticide residues in urine of the population who had not been used in the last month of the population was found. In the urine, the concentration of urea residues in urine was lower than that of the use group (t=5.78, P0.05). The frequency of the pesticide residues in urine was higher than that of the detected population (t=5.78, P0.05). Z =-4.969, Z =-5.359, Z =-5.180, Z=-2.783, P0.01), the detection rate of isocarbamide residues in urine of high protective frequency population (x 2=24.74, P0.001), the residual concentration (F=3.35, P0.05) were lower. The rate of pesticide residue detection in urine of people who had no accidental skin contact was lower than that of the population with the accidental skin contact of pesticide (chi 2). The detection rate of pesticide residues in urine of people who were cleaned in time after accidental contact of drug skin was lower than that of untreated people (x 2=10.45, P0.05). The positive population of pesticide residues appeared dizziness / dizziness, headache, nausea, and skin itching more frequently than negative people (x 2=4.41, X 2=3.86, Chi 2=7.10, chi 2 =6.25, P0.05). The residual concentration of chlorpyrifos was 0.05-0.76 micron g/mL, and a total of 12 samples of soil samples were detected. The positive rate was 41.38%. The positive rate of field soil detection was 53.33%, and the positive rate of soil samples was 28.57%. and three kinds of pesticides, the most of them was carbamide urea, 8 samples were detected, positive rate was 27.58%. water. 2 pesticides residue of Carbendazim and fenprothrin were detected in the sample. The residual concentration range was 0.04-0.89 mu g/mL, and 7 samples were detected in the water samples. The positive rate was 25%. The positive rate of irrigation water was 35.71%, the positive rate of drinking water samples was 14.29%. and two kinds of pesticides were the most common bacteria urea, and 5 samples were detected. The positive rate is 17.85%.[Conclusion] there are pesticide residues in the water and soil samples of the residents' urine and their living environment, and all the residual urea residues are detected. The number of residual cases is the most. The detection rate of pesticide residues in the urine is high, and the direct evidence of pesticide residues in the body is found out to assess the risk and environment of pesticide exposure. The influence provides the basis. When using the pesticide, the protection measures can effectively reduce the contact between the pesticide and the human body and reduce the pesticide into the human body. It should encourage the residents to use the pesticide rationally and strengthen the self-protection measures when using the pesticide, thus reducing the pesticide entry to the human body and reducing the harm to the health of the pesticide.
【学位授予单位】:昆明医科大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:R12
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