壬基酚環(huán)境污染特性研究
發(fā)布時(shí)間：2019-06-08 15:23
【摘要】：我國(guó)是農(nóng)藥使用大國(guó),農(nóng)藥助劑的環(huán)境污染問(wèn)題日益受到關(guān)注。安全環(huán)保的新型農(nóng)藥助劑正在興起,農(nóng)藥助劑的安全管理進(jìn)程亟需推進(jìn)。在此背景下,開(kāi)展高風(fēng)險(xiǎn)農(nóng)藥助劑在水體、農(nóng)田土壤和沉積物中的調(diào)查分析,研究其在土壤中的環(huán)境行為對(duì)加強(qiáng)我國(guó)農(nóng)藥助劑的使用管理和推動(dòng)我國(guó)高效環(huán)保的新型農(nóng)藥助劑具有重要意義。本文利用超高液相色譜-質(zhì)譜聯(lián)用的方法研究分析了高風(fēng)險(xiǎn)農(nóng)藥助劑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、水體和沉積物中的殘留狀況,并對(duì)現(xiàn)有的污染水平進(jìn)行了風(fēng)險(xiǎn)評(píng)價(jià)。主要研究結(jié)論如下：(1)建立了水、土壤和沉積物中壬基酚的分析檢測(cè)方法,土壤樣品經(jīng)甲醇和乙酸乙酯(4：1,V：V)的混合溶液超聲提取、二氯甲烷液液萃取后,UPLC-EIS-MS/MS檢測(cè)分析,儀器檢測(cè)限在2.90至24.3ng/L之間,回收率為73.6%-88.5%,RSD為3.7%～5.9%；水樣用Oasis HLB固相萃取小柱富集、凈化后,UPLC-EIS-MS/MS檢測(cè)分析,回收率為76.1%～98.0%,RSD為5.9%-7.3%。(2)研究了壬基酚在5種不同土壤中的降解特性及吸附淋溶遷移特性。降解結(jié)果表明,壬基酚在好氧條件下,在5種土壤中的降解能較好的符合一級(jí)動(dòng)力學(xué)方程,其降解趨勢(shì)為前期快后期慢,最后穩(wěn)定平衡,難以持續(xù)的降解,持久性增強(qiáng)�？焖匐A段降解半衰期分別為14.1、18.2、19.2、20.4、25.7d,慢速降解階段半衰期分別為46.2、63.0、69.3、77.0、77.0d,相關(guān)系數(shù)γ為0.868～0.997之間。土壤有機(jī)質(zhì)含量是影響其好氧降解的一個(gè)因素。微生物活性降低,并且不同異構(gòu)體壬基酚在土壤中存在多種結(jié)合狀態(tài),是其降解由快變慢的可能原因。壬基酚在積水厭氣條件下,在5種土壤中降解較慢。東北黑體、太湖水稻土和南京黃棕壤中,200d時(shí)降解率低于好氧狀態(tài)；江西紅壤與常熟烏柵土中壬基酚的降解半衰期分別為86.6d和90.0d,高于好氧狀態(tài)下的半衰期。土壤中微生物種類和生物活性是影響壬基酚分別在好氧和積水厭氣條件下降解的重要因素。吸附試驗(yàn)結(jié)果表明,壬基酚在南京黃棕壤、江西紅壤、常熟烏柵土、太湖水稻土、東北黑土中較好的符合Freundlich方程,其Kd值分別為18.89、26.64、44.15、47.49、69.92。吸附系數(shù)Koc的值分別為：南京黃棕壤4860.65、江西紅壤4064.37、常熟烏柵土2961.66、太湖水稻土2934.51、東北黑土3214.46。影響壬基酚在土壤中吸附性能的主要因素為土壤有機(jī)質(zhì)含量,即土壤有機(jī)質(zhì)含量越高,吸附性越強(qiáng)。次要因素為土壤陽(yáng)離子代換量。吸附過(guò)程為自發(fā)的物理吸附。土柱淋溶結(jié)果表明,5種土壤中的壬基酚基本都集中在土柱頂段,尤其是1-3cm段,其余各段壬基酚的含量相對(duì)較少。其在土壤中的移動(dòng)規(guī)律和土壤吸附性有明顯的相關(guān)性。同時(shí)壬基酚難淋溶的特性與土壤中有機(jī)質(zhì)含量相關(guān)。壬基酚在5種土壤中的淋溶狀況,總體趨勢(shì)與其在5種土壤中的吸附性結(jié)果相對(duì)應(yīng),吸附能力越強(qiáng),淋溶性越弱。壬基酚在5種土壤具有難淋溶的特性。(3)對(duì)太湖流域農(nóng)田土壤、入湖水體和湖水中的壬基酚進(jìn)行調(diào)查分析,對(duì)該區(qū)域壬基酚的生態(tài)風(fēng)險(xiǎn)進(jìn)行評(píng)價(jià),研究結(jié)果表明：基于歐盟的NP環(huán)境風(fēng)險(xiǎn)評(píng)價(jià)報(bào)告,太湖流域環(huán)境水體中NP的RQwater值為0.006-0.691,沉積物中NP的RQsediment值為0.06-2.073。太湖流域有近68%水體處于低風(fēng)險(xiǎn)狀態(tài),有32%水體處于中度風(fēng)險(xiǎn)狀態(tài)；有49%沉積物處于低風(fēng)險(xiǎn)狀態(tài),44%處于中度風(fēng)險(xiǎn)狀態(tài),17%處于高風(fēng)險(xiǎn)狀態(tài)。基于美國(guó)環(huán)境總署頒布的關(guān)于NP的環(huán)境水質(zhì)標(biāo)準(zhǔn),屬于淡水系統(tǒng)的太湖流域表層水體中檢測(cè)出的NP濃度全部低于淡水中NP的慢性毒性濃度標(biāo)準(zhǔn)(6.6μg·L-1)和急性毒性濃度標(biāo)準(zhǔn)(28μg·L-1),說(shuō)明太湖流域水體中NP的生態(tài)風(fēng)險(xiǎn)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.
【學(xué)位授予單位】：南京信息工程大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：X592
，
本文編號(hào)：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.
【學(xué)位授予單位】：南京信息工程大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：X592
，
本文編號(hào)：2495391
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