壬基酚环境污染特性研究
发布时间：2019-06-08 15:23
【摘要】：我国是农药使用大国,农药助剂的环境污染问题日益受到关注。安全环保的新型农药助剂正在兴起,农药助剂的安全管理进程亟需推进。在此背景下,开展高风险农药助剂在水体、农田土壤和沉积物中的调查分析,研究其在土壤中的环境行为对加强我国农药助剂的使用管理和推动我国高效环保的新型农药助剂具有重要意义。本文利用超高液相色谱-质谱联用的方法研究分析了高风险农药助剂壬基酚在不同土壤中的降解、吸附和淋溶特性；太湖流域土壤、水体和沉积物中的残留状况,并对现有的污染水平进行了风险评价。主要研究结论如下：(1)建立了水、土壤和沉积物中壬基酚的分析检测方法,土壤样品经甲醇和乙酸乙酯(4：1,V：V)的混合溶液超声提取、二氯甲烷液液萃取后,UPLC-EIS-MS/MS检测分析,仪器检测限在2.90至24.3ng/L之间,回收率为73.6%-88.5%,RSD为3.7%～5.9%；水样用Oasis HLB固相萃取小柱富集、净化后,UPLC-EIS-MS/MS检测分析,回收率为76.1%～98.0%,RSD为5.9%-7.3%。(2)研究了壬基酚在5种不同土壤中的降解特性及吸附淋溶迁移特性。降解结果表明,壬基酚在好氧条件下,在5种土壤中的降解能较好的符合一级动力学方程,其降解趋势为前期快后期慢,最后稳定平衡,难以持续的降解,持久性增强。快速阶段降解半衰期分别为14.1、18.2、19.2、20.4、25.7d,慢速降解阶段半衰期分别为46.2、63.0、69.3、77.0、77.0d,相关系数γ为0.868～0.997之间。土壤有机质含量是影响其好氧降解的一个因素。微生物活性降低,并且不同异构体壬基酚在土壤中存在多种结合状态,是其降解由快变慢的可能原因。壬基酚在积水厌气条件下,在5种土壤中降解较慢。东北黑体、太湖水稻土和南京黄棕壤中,200d时降解率低于好氧状态；江西红壤与常熟乌栅土中壬基酚的降解半衰期分别为86.6d和90.0d,高于好氧状态下的半衰期。土壤中微生物种类和生物活性是影响壬基酚分别在好氧和积水厌气条件下降解的重要因素。吸附试验结果表明,壬基酚在南京黄棕壤、江西红壤、常熟乌栅土、太湖水稻土、东北黑土中较好的符合Freundlich方程,其Kd值分别为18.89、26.64、44.15、47.49、69.92。吸附系数Koc的值分别为：南京黄棕壤4860.65、江西红壤4064.37、常熟乌栅土2961.66、太湖水稻土2934.51、东北黑土3214.46。影响壬基酚在土壤中吸附性能的主要因素为土壤有机质含量,即土壤有机质含量越高,吸附性越强。次要因素为土壤阳离子代换量。吸附过程为自发的物理吸附。土柱淋溶结果表明,5种土壤中的壬基酚基本都集中在土柱顶段,尤其是1-3cm段,其余各段壬基酚的含量相对较少。其在土壤中的移动规律和土壤吸附性有明显的相关性。同时壬基酚难淋溶的特性与土壤中有机质含量相关。壬基酚在5种土壤中的淋溶状况,总体趋势与其在5种土壤中的吸附性结果相对应,吸附能力越强,淋溶性越弱。壬基酚在5种土壤具有难淋溶的特性。(3)对太湖流域农田土壤、入湖水体和湖水中的壬基酚进行调查分析,对该区域壬基酚的生态风险进行评价,研究结果表明：基于欧盟的NP环境风险评价报告,太湖流域环境水体中NP的RQwater值为0.006-0.691,沉积物中NP的RQsediment值为0.06-2.073。太湖流域有近68%水体处于低风险状态,有32%水体处于中度风险状态；有49%沉积物处于低风险状态,44%处于中度风险状态,17%处于高风险状态。基于美国环境总署颁布的关于NP的环境水质标准,属于淡水系统的太湖流域表层水体中检测出的NP浓度全部低于淡水中NP的慢性毒性浓度标准(6.6μg·L-1)和急性毒性浓度标准(28μg·L-1),说明太湖流域水体中NP的生态风险不高。
[Abstract]:The problem of environmental pollution of pesticide adjuvant is more and more attention in China, which is a major pesticide in China. The safe and environment-friendly pesticide adjuvant is rising, and the safety management process of the pesticide adjuvant is in urgent need of advance. In this background, the investigation and analysis of high-risk pesticide adjuvant in the water, farmland soil and sediment are carried out, and the environmental behavior of the high-risk pesticide in the soil is of great significance to strengthen the use and management of the pesticide adjuvant in China and to promote the efficient and environment-friendly pesticide adjuvant in China. In this paper, the degradation, adsorption and leaching characteristics of nonylphenol in different soils were studied by means of ultra-high liquid chromatography-mass spectrometry. The residual conditions of soil, water and sediment in Taihu Basin were analyzed and the existing pollution levels were evaluated. The main research results are as follows: (1) The method for the analysis and detection of nonylphenol in water, soil and sediment is established. The soil sample is extracted by ultrasonic extraction with mixed solution of methanol and ethyl acetate (4:1, V: V), and after liquid-liquid extraction of dichloromethane, the UPLC-EIS-MS/ MS detection and analysis are carried out. The detection limit of the instrument is between 2.90 and 24.3 ng/ L, the recovery rate is 73.6%-88.5%, the RSD is 3.7%-5.9%, the water sample is enriched and purified by the Oasis HLB solid-phase extraction column, and the recovery rate is 76.1%-98.0% and the RSD is 5.9%-7.3%. (2) The degradation characteristics of nonylphenol in five different soils and the characteristics of adsorption and leaching were studied. The results of the degradation show that the degradation of nonylphenol in five soils can meet the first-order kinetic equation in the aerobic condition, and the degradation trend of nonylphenol is slow in the early stage, the last stable equilibrium, the continuous degradation and the persistence. The half-life of the rapid-stage degradation was 14.1, 18.2, 19.2, 20.4, 25.7 d. The half-life of the slow-stage degradation stage was 46.2, 63.0, 69.3, 77.0, 77.0 d, and the correlation coefficient was between 0.868 and 0.997, respectively. The content of organic matter in soil is a factor that affects its aerobic degradation. The microbial activity is reduced, and the nonylphenols of different isomers have various binding states in the soil, which is the probable cause of the degradation of the nonylphenol in the soil. Nonylphenol is degraded in five soil under the condition of water-anaerobic condition. The degradation rate of nonylphenol in the black soil of the northeast, the paddy soil of Taihu Lake and the yellow-brown soil of Nanjing was lower than that of the aerobic state. The half-life of nonylphenol in the red soil and the normally-cooked black-brown soil of Jiangxi was 86.6 d and 90.0 d, respectively, and the half-life in the aerobic condition was higher. Microbial species and biological activity in soil are important factors that affect the degradation of nonylphenol in aerobic and water-anaerobic conditions, respectively. The results of the adsorption test show that nonylphenol in the yellow-brown soil of Nanjing, the red soil of Jiangxi, the normally-cooked black-grid soil, the paddy soil of the Taihu Lake and the black soil of the northeast are better with the Freundlich equation, and the Kd value is 18.89, 26.64, 44.15, 47.49, 69.92, respectively. The values of the adsorption coefficient Koc are: Nanjing Yellow-brown soil 4860.65, Jiangxi red soil 4064.37, Changshu black-grid soil 2961.66, Taihu rice soil 2934.51, and northeast black soil 3214.46, respectively. The main factors that affect the adsorption performance of nonylphenol in the soil are the soil organic matter content, that is, the higher the soil organic matter content, the stronger the adsorptivity. The secondary factor is the soil cation substitution. The adsorption process is a spontaneous physical adsorption. The results of the soil column leaching show that the nonylphenol in the five soils is mainly concentrated in the top section of the soil column, especially the 1-3cm section, and the content of nonylphenol in the remaining sections is relatively small. The movement rule of the soil and the adsorption of the soil have obvious correlation. At the same time, the insoluble property of nonylphenol is related to the content of organic matter in the soil. The water-leaching status of nonylphenol in five soils, the stronger the adsorption capacity and the weaker the leaching-solubility in the five soils. Nonylphenol has the characteristics of difficult leaching in five soils. (3) The ecological risk of nonylphenol in the Taihu basin is evaluated by the investigation and analysis of the farmland soil, the lake water body and the nonylphenol in the lake water. The results show that the RQwater value of NP in the Taihu basin is 0.006-0.691, based on the assessment report of the NP environmental risk in the European Union. The RQsdedvalue of NP in the sediment is 0.06-2.073. About 68% of the water in the Taihu Basin is in a low-risk state with 32% of the water in a moderate risk state;49% of the sediments are in a low-risk state and 44% are in a moderate-risk state and 17% are in a high-risk state. Based on the environmental water quality standard issued by the United States Environment Department on the NP, the NP concentration detected in the surface water body of the Taihu basin of the fresh water system is all lower than that of the NP in the fresh water (6.6. mu.g/ L-1) and the acute toxicity concentration standard (28. mu.g/ L-1). The paper indicates that the ecological risk of NP in the water of Taihu Lake is not high.
【学位授予单位】：南京信息工程大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：X592
，
本文编号：2495391
[Abstract]:The problem of environmental pollution of pesticide adjuvant is more and more attention in China, which is a major pesticide in China. The safe and environment-friendly pesticide adjuvant is rising, and the safety management process of the pesticide adjuvant is in urgent need of advance. In this background, the investigation and analysis of high-risk pesticide adjuvant in the water, farmland soil and sediment are carried out, and the environmental behavior of the high-risk pesticide in the soil is of great significance to strengthen the use and management of the pesticide adjuvant in China and to promote the efficient and environment-friendly pesticide adjuvant in China. In this paper, the degradation, adsorption and leaching characteristics of nonylphenol in different soils were studied by means of ultra-high liquid chromatography-mass spectrometry. The residual conditions of soil, water and sediment in Taihu Basin were analyzed and the existing pollution levels were evaluated. The main research results are as follows: (1) The method for the analysis and detection of nonylphenol in water, soil and sediment is established. The soil sample is extracted by ultrasonic extraction with mixed solution of methanol and ethyl acetate (4:1, V: V), and after liquid-liquid extraction of dichloromethane, the UPLC-EIS-MS/ MS detection and analysis are carried out. The detection limit of the instrument is between 2.90 and 24.3 ng/ L, the recovery rate is 73.6%-88.5%, the RSD is 3.7%-5.9%, the water sample is enriched and purified by the Oasis HLB solid-phase extraction column, and the recovery rate is 76.1%-98.0% and the RSD is 5.9%-7.3%. (2) The degradation characteristics of nonylphenol in five different soils and the characteristics of adsorption and leaching were studied. The results of the degradation show that the degradation of nonylphenol in five soils can meet the first-order kinetic equation in the aerobic condition, and the degradation trend of nonylphenol is slow in the early stage, the last stable equilibrium, the continuous degradation and the persistence. The half-life of the rapid-stage degradation was 14.1, 18.2, 19.2, 20.4, 25.7 d. The half-life of the slow-stage degradation stage was 46.2, 63.0, 69.3, 77.0, 77.0 d, and the correlation coefficient was between 0.868 and 0.997, respectively. The content of organic matter in soil is a factor that affects its aerobic degradation. The microbial activity is reduced, and the nonylphenols of different isomers have various binding states in the soil, which is the probable cause of the degradation of the nonylphenol in the soil. Nonylphenol is degraded in five soil under the condition of water-anaerobic condition. The degradation rate of nonylphenol in the black soil of the northeast, the paddy soil of Taihu Lake and the yellow-brown soil of Nanjing was lower than that of the aerobic state. The half-life of nonylphenol in the red soil and the normally-cooked black-brown soil of Jiangxi was 86.6 d and 90.0 d, respectively, and the half-life in the aerobic condition was higher. Microbial species and biological activity in soil are important factors that affect the degradation of nonylphenol in aerobic and water-anaerobic conditions, respectively. The results of the adsorption test show that nonylphenol in the yellow-brown soil of Nanjing, the red soil of Jiangxi, the normally-cooked black-grid soil, the paddy soil of the Taihu Lake and the black soil of the northeast are better with the Freundlich equation, and the Kd value is 18.89, 26.64, 44.15, 47.49, 69.92, respectively. The values of the adsorption coefficient Koc are: Nanjing Yellow-brown soil 4860.65, Jiangxi red soil 4064.37, Changshu black-grid soil 2961.66, Taihu rice soil 2934.51, and northeast black soil 3214.46, respectively. The main factors that affect the adsorption performance of nonylphenol in the soil are the soil organic matter content, that is, the higher the soil organic matter content, the stronger the adsorptivity. The secondary factor is the soil cation substitution. The adsorption process is a spontaneous physical adsorption. The results of the soil column leaching show that the nonylphenol in the five soils is mainly concentrated in the top section of the soil column, especially the 1-3cm section, and the content of nonylphenol in the remaining sections is relatively small. The movement rule of the soil and the adsorption of the soil have obvious correlation. At the same time, the insoluble property of nonylphenol is related to the content of organic matter in the soil. The water-leaching status of nonylphenol in five soils, the stronger the adsorption capacity and the weaker the leaching-solubility in the five soils. Nonylphenol has the characteristics of difficult leaching in five soils. (3) The ecological risk of nonylphenol in the Taihu basin is evaluated by the investigation and analysis of the farmland soil, the lake water body and the nonylphenol in the lake water. The results show that the RQwater value of NP in the Taihu basin is 0.006-0.691, based on the assessment report of the NP environmental risk in the European Union. The RQsdedvalue of NP in the sediment is 0.06-2.073. About 68% of the water in the Taihu Basin is in a low-risk state with 32% of the water in a moderate risk state;49% of the sediments are in a low-risk state and 44% are in a moderate-risk state and 17% are in a high-risk state. Based on the environmental water quality standard issued by the United States Environment Department on the NP, the NP concentration detected in the surface water body of the Taihu basin of the fresh water system is all lower than that of the NP in the fresh water (6.6. mu.g/ L-1) and the acute toxicity concentration standard (28. mu.g/ L-1). The paper indicates that the ecological risk of NP in the water of Taihu Lake is not high.
【学位授予单位】：南京信息工程大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：X592
，
本文编号：2495391
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