酚类环境内分泌干扰物分析方法及滇池水系污染特征研究
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摘要
环境内分泌干扰物(EDCs)是指通过干扰生物体内保持自身平衡和调节发育过程中天然激素的合成、分泌、运输、代谢、结合、反应、消除等生物过程的外源性化学物质。这类物质的存在会干扰人类和野生动物的内分泌系统,带来生殖障碍、发育异常、免疫功能减弱等问题。EDCs,尤其是使用最为广泛的酚类EDCs,在水环境中的污染特征研究已是当前科学界和公众共同关注的热点问题之一。环境样品基质非常复杂,使得痕量酚类EDCs的分析检测难度较大。因此,建立完善的复杂环境介质中准确、灵敏的分析方法成为酚类EDCs污染特征研究亟需解决的问题。
鉴于滇池流域EDCs研究的紧迫性和滞后性,本文以酚类EDCs为研究对象,在建立完善的分析方法基础上,围绕滇池水系开展酚类EDCs的污染特征研究。由单一的滇池湖水研究拓展到包括滇池地表水水质国家重点监控断面、8根滇池柱状沉积物、22条主要环滇池河流和昆明市主城区八座污水处理厂在内的整个滇池水系的研究,研究内容由简单的水体含量深化到涵盖污染水平、分布特征、季节变化、污染历史、去除效率、污染负荷、迁移转化等多要素的分析,将滇池作为一个有机整体来探讨酚类EDCs的污染特征,为滇池流域该类污染物的风险评价和污染控制措施的制定提供基础资料。
(1)本文针对壬基酚二氧乙烯醚(NP2E0)、壬基酚单氧乙烯醚(NP1EO)、4-壬基酚(4-NP)、双酚A(BPA)、枯烯基酚(4-CP)和4-t-辛基酚(4-t-OP)六种典型的酚类EDCs,建立了不同环境介质中的分析方法,包括样品采集、微波辅助萃取(MAE)、凝胶渗透色谱净化(GPC)、固相萃取(SPE)、衍生化和气相色谱-质谱联用(GC-MS)检测。研究表明,酚类EDCs最佳的衍生化条件是以N,O-双三甲基硅基三氟乙酰胺(BSTFA)为衍生化试剂,在70℃条件下反应50min；SPE的最佳条件是选择Sep-Pak C-18柱,调节水样pH值至4.5,以10mL二氯甲烷为洗脱溶剂；MAE的最佳条件是以25mL甲醇为萃取溶剂,在110℃条件下萃取20min; GPC的流动相为乙酸乙酯/环己烷(1：1,v/v),目标化合物的最佳收集时间段为7-14min。该方法具有很好的重现性,相对标准偏差小于9.5%。酚类EDCs在水中的检出限为0.10～2.30ng/L,回收率为83.51-105.74%；在沉积物和污泥中的检出限为0.15～2.90ng/g dw,回收率为74.30%-105.04%。运用该方法对滇池水环境样品和污水处理厂样品中的酚类EDCs进行了分析检测,验证了该方法能够很好的应用于环境样品中痕量酚类EDCs的定量分析。
(2)研究了滇池水及表层沉积物中酚类EDCs的污染特征。结果表明,滇池草海湖区水及表层沉积物中总酚类EDCs的浓度分别为396.58～1338.74ng/L和888.85～1322.45ng/g dw,外海分别为103.89～686.59ng/L和59.08～230.94ng/g dw；丰水期草海水和表层沉积物中总酚类EDCs的平均浓度分别是外海的2.84倍和9.44倍,枯水期分别是2.28倍和7.45倍；NP2EO.NP1EO和BPA是滇池水环境中主要的酚类EDCs,占6种酚类EDCs的90%以上；滇池外海离城市较近的北部、东北部及南部水域中酚类EDCs的浓度相对于中部及西部水域较高。与其他地区湖泊相比,滇池外海水环境中酚类EDCs的浓度处于中等偏下水平,而滇池草海的浓度偏高,对湖区内的水生生物及周边居民构成了潜在危害。
(3)探讨了滇池8根柱状沉积物中酚类EDCs的污染特征。研究表明,滇池北部和西部湖区的柱状沉积物中酚类EDCs的含量,由表层至深层呈先降低后升高再降低的“S”型分布规律,而东部、东南部和南部湖区则随柱状沉积物深度的增加呈递减趋势；酚类EDCs在20cm至表层沉积物中的含量增加趋势较明显；C1和C2表层沉积物中酚类EDCs的含量约是C3-C7表层的1.9～6.0倍,而表层以下约25cm酚类EDCs的含量与C3-C6表层含量相当,从某种程度上印证了昆明城市沿着滇池向东环湖发展的进程；C7和C8沉积物中酚类EDCs含量的增加趋势明显,表明近几年晋宁县城区的快速发展加重了滇池南部的相关污染负荷；NP2EO、NP1EO和BPA是柱状沉积物中三种主要的酚类EDCs。此外,总有机碳对酚类EDCs在柱状沉积物中的分布、行为和归宿起着重要作用。
(4)对滇池21条主要入湖河流和唯一自然出湖河流(海口河)中酚类EDCs的污染特征进行了研究。结果表明,入湖河流水中总酚类EDCs的浓度为248.13～4650.39ng/L,表层沉积物为113.30～3575.80ng/g dw；NP2E0.NP1EO和BPA是环滇池河流中主要的酚类EDCs,与滇池中组分特征一致；流经昆明市主城区的新河、运粮河、船房河、采莲河、金家河、正大河和大清河中酚类EDCs的污染较严重,存在一定的环境风险；2010年通过河流输入到滇池草海酚类EDCs的量为156.33kg,输入到外海的量为313.76kg,由海口河外排约212.41kg；与其他地区河流相比,4-NP和4-t-OP在环滇池河流中的污染处于相对较低水平,而NP2EO、NP1EO和BPA则处于中等水平；以盘龙江为例,探讨了河流沿程酚类EDCs的污染特征,其上游浓度较低,中游污染较严重,中下游得到一定缓解后,浓度再次升高。
(5)研究了昆明市主城区八座污水处理厂中酚类EDCs的污染特征。结果表明,各污水处理厂进水中总酚类EDCs的浓度为2038.82～5066.14ng/L,出水中为420.28～1535.89ng/L,污泥中为1209.67～9464.87ng/g dw,总去除率为32.34%～88.88%；3AMBR和A2/O工艺对酚类EDCs的去除效果较好,而氧化沟和ICEAS工艺较差；降解是污水处理厂中酚类EDCs的主要去除方式；昆明市每天排入污水处理厂的酚类EDCs总量约为3770.92g,其中通过出水外排约21.43%。
Endocrine disrupting chemicals (EDCs) are defined as exogenous agents that interfere with the production, secretion, transportation, metabolism, binding, action, or elimination of natural hormones in the body. These compounds are responsible for the maintenance of homeostasis and the regulation of developmental processes. EDCs may disturb the function of endocrine system of human and wildlife and consequently cause adverse effects on development, reproduction and immune system of organism. Pollution characteristics of the widely used phenolic EDCs in aquatic environments have attracted a great deal of scientific and public attention. Because of the complexity of the environmental matrix, it is very difficult to monitor and analyze the trace phenolic EDCs in natural environment. Therefore, it is of crucial importance to develop an analytical method for the accurate determination of phenolic EDCs in the complex media.
In consideration of the urgency and hysteresis of study on EDCs in Dianchi Lake, phenolic EDCs are selected as target compounds and their pollution characteristics in Dianchi Lake catchment are studied on the basis of the improved analysis method. Research areas have been extended to the whole Dianchi Lake catchment including the national water quality monitoring sections, eight sediment cores in Dianchi Lake, twenty-two rivers around Dianchi Lake, as well as eight sewage treatment plants (STPs) in the main urban area of Kunming City; research contents have been deepened to contamination level, distribution characteristic, seasonal distribution, historical trend, elimination, pollution load, migration and so on. This paper integratedly clarified the pollution characteristic of phenolic EDCs in Dianchi Lake catchment, for the purpose of providing more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environment.
(1) An efficient and reliable method was improved for the analysis of six typical phenolic EDCs such as nonylphenol-diethoxylate (NP2EO), nonylphenol-mono-ethoxylate (NP1EO),4-nonylphenol (4-NP), bisphenol A (BPA),4-cumylphenol (4-CP) and4-tert-octylphenol (4-t-OP) in multiple environmental media (water, sediment, STPs influent, effluent and sludge). The proposed method was consisted of sample collection, microwave-assisted extraction (MAE), automated gel permeation chromatography (GPC), solid phase extraction (SPE), derivatization and gas chromatography-mass spectrometry (GC-MS) analysis. It provided a reliable technological approach to comprehensively study the pollution characteristic of phenolic EDCs in aquatic environment. The results showed that phenolic EDCs were derivatized with N, O-bis (trimethylsilyl)trifluoroacetamide (BSTFA) at70℃for50min; water samples (pH=4.5) were extracted by using Sep-Pak C-18cartridges, and the extracts were eluted by10mL of dichloromethane; sediment or sludge samples were extracted by using MAE with25mL of methanol at110℃for20min, respectively. The cleanup of extracts was carried out by GPC with cyclohexane/ethyl acetate (1:1, v/v) as mobile phase, and the target compounds were eluted in the fraction from7-14min retention time. The method achieved good repeatability and reproducibility with relative standard deviations lower than9.5%for all target EDCs in all the samples. The overall recoveries for spiked water and solid samples ranged from83.51to105.74%and74.30to105.04%, respecitively. The limits of detection ranged from0.10to2.30ng/L for water samples, and from0.15to2.90ng/g dry weight (dw) for sediment and sludge samples. The improved method was successfully applied to the analysis of phenolic EDCs in water and surface sediment and inflow samples collected from the Dianchi Lake and STPs, respectively. The developed method is a promising approach for the analysis of phenolic EDCs in environmental samples.
(2) Pollution characteristics of the phenolic EDCs in water and surface sediment samples collected from Dianchi Lake were investigated. The results showed that the concentrations of the phenolic EDCs in water and surface sediment in Caohai section were396.58-1338.74ng/L and888.85-1322.45ng/g dw, while from103.89-686.59ng/L and59.08～230.94ng/g dw in Waihai section, respectively. In the wet season, the average concentration of the total phenolic EDCs in water and surface sediment in Caohai section was2.84and9.44times of that in Waihai section, respectively; in the dry season, the average concentration in Caohai section was2.28and7.45times compared with Waihai section, respectively. Caohai section was the major receiving area of the domestic sewage and industrial wastewater discharged from the main urban area of Kunming City in the past decades. NP2EO, NP1EO and BPA were the three dominant compounds in the lake, which accounted for more than90%of the total six phenolic EDCs. The concentration of phenolic EDCs in the center and west of Waihai section were lower than that in north, northeast and south areas which adjacent to the urban city. Compared with other lakes, the concentrations of phenolic EDCs in the Waihai section of Dianchi Lake were at their medium-low level, however, the concentrations in the Caohai section were very high, which could pose a potential risk to aquatic organisms.
(3) Pollution characteristics of phenolic EDCs in the eight sediment cores in Dianchi Lake were illuminated. In the sediment cores in north and west of Dianchi Lake, the distribution of phenolic EDCs from the surface to the bottom is like "S" shape, while the concentrations of phenolic EDCs decreased in those from the east, southeast and south. With the depth increasing, from surface sediment to20cm, the concentration of phenolic EDCs showed obvious downtrend. The concentrations of phenolic EDCs in surface sediment of C1and C2were about1.9～6.0times than those of C3～C7, while the concentrations of25cm beneath the surface layer were roughly equivalent to those in surface sediment of C3-C6, indicating the developmental process of Kunming City around the east part of Dianchi Lake. The concentration of phenolic EDCs from the bottom to the surface in the sediment cores of C7and C8increased obviously, suggesting that with the development of Jinning County, the pollution load of Dianchi Lake was likely to increase. NP1EO, NP2EO and BPA were identified as the three predominant phenolic EDCs. Therefore, total organic carbon could play an important role in the distribution, fate and behavior of phenolic EDCs in those sediment cores.
(4) Twenty-one main inflow rivers and one natural outflow river were studied to clarify the pollution characteristics of phenolic EDCs. The results showed that the concentrations of the total phenolic EDCs in water and surface sediment were from248.13to4650.39ng/L and from113.30to3575.80ng/g dw, respectively. The composition of phenolic EDCs in the rivers were the same as those in Dianchi, NP2EO, NP1EO and BPA are the main compounds. The Xin River, Yunliang River, Chuanfang River, Cailian River, Jinjia River, Zhengda River and Daqing River, running through the main urban area of Kunming City, were seriously contaminated by phenolic EDCs. The concentration level in those rivers could pose potential environmental risks. In2010, the amount of phenolic EDCs discharged into Caohai section of Dianchi Lake by inflow rivers was156.33kg, while Waihai section was313.76kg, and discharging from Haikou river was212.41kg. Compared with other regions and countries, the concentration level of4-NP and4-t-OP in the rivers around Dianchi Lake was lower, while NP2EO, NP1EO and BPA were at their moderate levels. Pollution characteristics of phenolic EDCs along the Panlong River, from Songhuaba reservoir to Dianchi Lake, were discussed. The concentrations of phenolic EDCs were low in the upstream of Panlong River, while midstream of which were seriously polluted; the pollution of middle and lower reaches was relieved; however, the concentrations of phenolic EDCs in downstream were increased significantly.
(5) On the basis of the eight STPs of the main urban area of Kunming City, the pollution characteristics of phenolic EDCs were investigated. The concentrations of the total phenolic EDCs in the influent samples collected from the STPs were from2038.82to5066.14ng/L, in effluent samples from420.28to1535.89ng/L, and in sludge samples from1209.67to9464.87ng/g dw. The removal efficiencies of the total phenolic EDCs were from32.34%to88.88%.3AMBR and A2/O processes could eliminate the phenolic EDCs effectively, while Oxidation ditch and ICEAS processes were inferior to that of the former. Degradation was the main pathway to remove phenolic EDCs from STPs. The amount of phenolic EDCs discharged into the eight STPs was3770.92g/d, and24.43%of that was discharged into the water environment.
鉴于滇池流域EDCs研究的紧迫性和滞后性,本文以酚类EDCs为研究对象,在建立完善的分析方法基础上,围绕滇池水系开展酚类EDCs的污染特征研究。由单一的滇池湖水研究拓展到包括滇池地表水水质国家重点监控断面、8根滇池柱状沉积物、22条主要环滇池河流和昆明市主城区八座污水处理厂在内的整个滇池水系的研究,研究内容由简单的水体含量深化到涵盖污染水平、分布特征、季节变化、污染历史、去除效率、污染负荷、迁移转化等多要素的分析,将滇池作为一个有机整体来探讨酚类EDCs的污染特征,为滇池流域该类污染物的风险评价和污染控制措施的制定提供基础资料。
(1)本文针对壬基酚二氧乙烯醚(NP2E0)、壬基酚单氧乙烯醚(NP1EO)、4-壬基酚(4-NP)、双酚A(BPA)、枯烯基酚(4-CP)和4-t-辛基酚(4-t-OP)六种典型的酚类EDCs,建立了不同环境介质中的分析方法,包括样品采集、微波辅助萃取(MAE)、凝胶渗透色谱净化(GPC)、固相萃取(SPE)、衍生化和气相色谱-质谱联用(GC-MS)检测。研究表明,酚类EDCs最佳的衍生化条件是以N,O-双三甲基硅基三氟乙酰胺(BSTFA)为衍生化试剂,在70℃条件下反应50min；SPE的最佳条件是选择Sep-Pak C-18柱,调节水样pH值至4.5,以10mL二氯甲烷为洗脱溶剂；MAE的最佳条件是以25mL甲醇为萃取溶剂,在110℃条件下萃取20min; GPC的流动相为乙酸乙酯/环己烷(1：1,v/v),目标化合物的最佳收集时间段为7-14min。该方法具有很好的重现性,相对标准偏差小于9.5%。酚类EDCs在水中的检出限为0.10～2.30ng/L,回收率为83.51-105.74%；在沉积物和污泥中的检出限为0.15～2.90ng/g dw,回收率为74.30%-105.04%。运用该方法对滇池水环境样品和污水处理厂样品中的酚类EDCs进行了分析检测,验证了该方法能够很好的应用于环境样品中痕量酚类EDCs的定量分析。
(2)研究了滇池水及表层沉积物中酚类EDCs的污染特征。结果表明,滇池草海湖区水及表层沉积物中总酚类EDCs的浓度分别为396.58～1338.74ng/L和888.85～1322.45ng/g dw,外海分别为103.89～686.59ng/L和59.08～230.94ng/g dw；丰水期草海水和表层沉积物中总酚类EDCs的平均浓度分别是外海的2.84倍和9.44倍,枯水期分别是2.28倍和7.45倍；NP2EO.NP1EO和BPA是滇池水环境中主要的酚类EDCs,占6种酚类EDCs的90%以上；滇池外海离城市较近的北部、东北部及南部水域中酚类EDCs的浓度相对于中部及西部水域较高。与其他地区湖泊相比,滇池外海水环境中酚类EDCs的浓度处于中等偏下水平,而滇池草海的浓度偏高,对湖区内的水生生物及周边居民构成了潜在危害。
(3)探讨了滇池8根柱状沉积物中酚类EDCs的污染特征。研究表明,滇池北部和西部湖区的柱状沉积物中酚类EDCs的含量,由表层至深层呈先降低后升高再降低的“S”型分布规律,而东部、东南部和南部湖区则随柱状沉积物深度的增加呈递减趋势；酚类EDCs在20cm至表层沉积物中的含量增加趋势较明显；C1和C2表层沉积物中酚类EDCs的含量约是C3-C7表层的1.9～6.0倍,而表层以下约25cm酚类EDCs的含量与C3-C6表层含量相当,从某种程度上印证了昆明城市沿着滇池向东环湖发展的进程；C7和C8沉积物中酚类EDCs含量的增加趋势明显,表明近几年晋宁县城区的快速发展加重了滇池南部的相关污染负荷；NP2EO、NP1EO和BPA是柱状沉积物中三种主要的酚类EDCs。此外,总有机碳对酚类EDCs在柱状沉积物中的分布、行为和归宿起着重要作用。
(4)对滇池21条主要入湖河流和唯一自然出湖河流(海口河)中酚类EDCs的污染特征进行了研究。结果表明,入湖河流水中总酚类EDCs的浓度为248.13～4650.39ng/L,表层沉积物为113.30～3575.80ng/g dw；NP2E0.NP1EO和BPA是环滇池河流中主要的酚类EDCs,与滇池中组分特征一致；流经昆明市主城区的新河、运粮河、船房河、采莲河、金家河、正大河和大清河中酚类EDCs的污染较严重,存在一定的环境风险；2010年通过河流输入到滇池草海酚类EDCs的量为156.33kg,输入到外海的量为313.76kg,由海口河外排约212.41kg；与其他地区河流相比,4-NP和4-t-OP在环滇池河流中的污染处于相对较低水平,而NP2EO、NP1EO和BPA则处于中等水平；以盘龙江为例,探讨了河流沿程酚类EDCs的污染特征,其上游浓度较低,中游污染较严重,中下游得到一定缓解后,浓度再次升高。
(5)研究了昆明市主城区八座污水处理厂中酚类EDCs的污染特征。结果表明,各污水处理厂进水中总酚类EDCs的浓度为2038.82～5066.14ng/L,出水中为420.28～1535.89ng/L,污泥中为1209.67～9464.87ng/g dw,总去除率为32.34%～88.88%；3AMBR和A2/O工艺对酚类EDCs的去除效果较好,而氧化沟和ICEAS工艺较差；降解是污水处理厂中酚类EDCs的主要去除方式；昆明市每天排入污水处理厂的酚类EDCs总量约为3770.92g,其中通过出水外排约21.43%。
Endocrine disrupting chemicals (EDCs) are defined as exogenous agents that interfere with the production, secretion, transportation, metabolism, binding, action, or elimination of natural hormones in the body. These compounds are responsible for the maintenance of homeostasis and the regulation of developmental processes. EDCs may disturb the function of endocrine system of human and wildlife and consequently cause adverse effects on development, reproduction and immune system of organism. Pollution characteristics of the widely used phenolic EDCs in aquatic environments have attracted a great deal of scientific and public attention. Because of the complexity of the environmental matrix, it is very difficult to monitor and analyze the trace phenolic EDCs in natural environment. Therefore, it is of crucial importance to develop an analytical method for the accurate determination of phenolic EDCs in the complex media.
In consideration of the urgency and hysteresis of study on EDCs in Dianchi Lake, phenolic EDCs are selected as target compounds and their pollution characteristics in Dianchi Lake catchment are studied on the basis of the improved analysis method. Research areas have been extended to the whole Dianchi Lake catchment including the national water quality monitoring sections, eight sediment cores in Dianchi Lake, twenty-two rivers around Dianchi Lake, as well as eight sewage treatment plants (STPs) in the main urban area of Kunming City; research contents have been deepened to contamination level, distribution characteristic, seasonal distribution, historical trend, elimination, pollution load, migration and so on. This paper integratedly clarified the pollution characteristic of phenolic EDCs in Dianchi Lake catchment, for the purpose of providing more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environment.
(1) An efficient and reliable method was improved for the analysis of six typical phenolic EDCs such as nonylphenol-diethoxylate (NP2EO), nonylphenol-mono-ethoxylate (NP1EO),4-nonylphenol (4-NP), bisphenol A (BPA),4-cumylphenol (4-CP) and4-tert-octylphenol (4-t-OP) in multiple environmental media (water, sediment, STPs influent, effluent and sludge). The proposed method was consisted of sample collection, microwave-assisted extraction (MAE), automated gel permeation chromatography (GPC), solid phase extraction (SPE), derivatization and gas chromatography-mass spectrometry (GC-MS) analysis. It provided a reliable technological approach to comprehensively study the pollution characteristic of phenolic EDCs in aquatic environment. The results showed that phenolic EDCs were derivatized with N, O-bis (trimethylsilyl)trifluoroacetamide (BSTFA) at70℃for50min; water samples (pH=4.5) were extracted by using Sep-Pak C-18cartridges, and the extracts were eluted by10mL of dichloromethane; sediment or sludge samples were extracted by using MAE with25mL of methanol at110℃for20min, respectively. The cleanup of extracts was carried out by GPC with cyclohexane/ethyl acetate (1:1, v/v) as mobile phase, and the target compounds were eluted in the fraction from7-14min retention time. The method achieved good repeatability and reproducibility with relative standard deviations lower than9.5%for all target EDCs in all the samples. The overall recoveries for spiked water and solid samples ranged from83.51to105.74%and74.30to105.04%, respecitively. The limits of detection ranged from0.10to2.30ng/L for water samples, and from0.15to2.90ng/g dry weight (dw) for sediment and sludge samples. The improved method was successfully applied to the analysis of phenolic EDCs in water and surface sediment and inflow samples collected from the Dianchi Lake and STPs, respectively. The developed method is a promising approach for the analysis of phenolic EDCs in environmental samples.
(2) Pollution characteristics of the phenolic EDCs in water and surface sediment samples collected from Dianchi Lake were investigated. The results showed that the concentrations of the phenolic EDCs in water and surface sediment in Caohai section were396.58-1338.74ng/L and888.85-1322.45ng/g dw, while from103.89-686.59ng/L and59.08～230.94ng/g dw in Waihai section, respectively. In the wet season, the average concentration of the total phenolic EDCs in water and surface sediment in Caohai section was2.84and9.44times of that in Waihai section, respectively; in the dry season, the average concentration in Caohai section was2.28and7.45times compared with Waihai section, respectively. Caohai section was the major receiving area of the domestic sewage and industrial wastewater discharged from the main urban area of Kunming City in the past decades. NP2EO, NP1EO and BPA were the three dominant compounds in the lake, which accounted for more than90%of the total six phenolic EDCs. The concentration of phenolic EDCs in the center and west of Waihai section were lower than that in north, northeast and south areas which adjacent to the urban city. Compared with other lakes, the concentrations of phenolic EDCs in the Waihai section of Dianchi Lake were at their medium-low level, however, the concentrations in the Caohai section were very high, which could pose a potential risk to aquatic organisms.
(3) Pollution characteristics of phenolic EDCs in the eight sediment cores in Dianchi Lake were illuminated. In the sediment cores in north and west of Dianchi Lake, the distribution of phenolic EDCs from the surface to the bottom is like "S" shape, while the concentrations of phenolic EDCs decreased in those from the east, southeast and south. With the depth increasing, from surface sediment to20cm, the concentration of phenolic EDCs showed obvious downtrend. The concentrations of phenolic EDCs in surface sediment of C1and C2were about1.9～6.0times than those of C3～C7, while the concentrations of25cm beneath the surface layer were roughly equivalent to those in surface sediment of C3-C6, indicating the developmental process of Kunming City around the east part of Dianchi Lake. The concentration of phenolic EDCs from the bottom to the surface in the sediment cores of C7and C8increased obviously, suggesting that with the development of Jinning County, the pollution load of Dianchi Lake was likely to increase. NP1EO, NP2EO and BPA were identified as the three predominant phenolic EDCs. Therefore, total organic carbon could play an important role in the distribution, fate and behavior of phenolic EDCs in those sediment cores.
(4) Twenty-one main inflow rivers and one natural outflow river were studied to clarify the pollution characteristics of phenolic EDCs. The results showed that the concentrations of the total phenolic EDCs in water and surface sediment were from248.13to4650.39ng/L and from113.30to3575.80ng/g dw, respectively. The composition of phenolic EDCs in the rivers were the same as those in Dianchi, NP2EO, NP1EO and BPA are the main compounds. The Xin River, Yunliang River, Chuanfang River, Cailian River, Jinjia River, Zhengda River and Daqing River, running through the main urban area of Kunming City, were seriously contaminated by phenolic EDCs. The concentration level in those rivers could pose potential environmental risks. In2010, the amount of phenolic EDCs discharged into Caohai section of Dianchi Lake by inflow rivers was156.33kg, while Waihai section was313.76kg, and discharging from Haikou river was212.41kg. Compared with other regions and countries, the concentration level of4-NP and4-t-OP in the rivers around Dianchi Lake was lower, while NP2EO, NP1EO and BPA were at their moderate levels. Pollution characteristics of phenolic EDCs along the Panlong River, from Songhuaba reservoir to Dianchi Lake, were discussed. The concentrations of phenolic EDCs were low in the upstream of Panlong River, while midstream of which were seriously polluted; the pollution of middle and lower reaches was relieved; however, the concentrations of phenolic EDCs in downstream were increased significantly.
(5) On the basis of the eight STPs of the main urban area of Kunming City, the pollution characteristics of phenolic EDCs were investigated. The concentrations of the total phenolic EDCs in the influent samples collected from the STPs were from2038.82to5066.14ng/L, in effluent samples from420.28to1535.89ng/L, and in sludge samples from1209.67to9464.87ng/g dw. The removal efficiencies of the total phenolic EDCs were from32.34%to88.88%.3AMBR and A2/O processes could eliminate the phenolic EDCs effectively, while Oxidation ditch and ICEAS processes were inferior to that of the former. Degradation was the main pathway to remove phenolic EDCs from STPs. The amount of phenolic EDCs discharged into the eight STPs was3770.92g/d, and24.43%of that was discharged into the water environment.
引文
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