【作者】 傅明珠；

【导师】 高会旺； 李正炎；

【作者基本信息】 中国海洋大学 ， 环境科学， 2007， 博士

【摘要】 烷基酚既是非离子表面活性剂烷基酚聚氧乙烯醚的合成原料又是后者在环境中较稳定的降解产物,具有毒性、生物累积性、持久性和雌激素活性,属于典型的环境内分泌干扰物,其在环境分布和行为以及生态风险评估现已成为环境科学领域的研究热点。I.本文首先建立了用气相色谱-质谱联用法同时检测环境样品中包括烷基酚、氯酚、双酚A等共11种酚类化合物的分析方法。以二氯甲烷为萃取溶剂,水样用液-液萃取的方法进行提取,加标回收率为77.2-103.6%,相对标准偏差为2.8-8.6%;固相基质(沉积物/淤泥)无需干燥,酸化后直接萃取湿样,加标回收率为72.0-94.7%,相对标准偏差为2.4-13.4%;用过量的BSTFA对样品进行衍生化处理,之后用GC/MS定性定量,在选定的色谱条件下各酚类目标化合物能够实现基线分离,在0-3000ng/ml范围内线性关系良好,变异系数为0.9927-0.9998,水样和固相基质中酚类化合物的检测限分别为2ng/l和2ng/g dw以下。该方法灵敏度高、选择性好、操作简单且成本较低,可以在常规实验室条件下满足环境样品中酚类化合物分析的要求。II.在建立上述分析方法的基础上,本文首次对胶州湾及其周围河流、黄河入海口和长江口临近海域各环境介质中酚类化合物的浓度分布特征和环境行为进行了较系统的研究:(1)对胶州湾及其入海河流冬季和夏季水体、悬浮物、表层沉积物各环境介质中酚类化合物的空间分布特征及季节变化进行了研究,结果表明壬基酚是胶州湾中浓度最高的酚类污染物,其次为双酚A、丁基酚、辛基酚和二氯酚;胶州湾水体中溶解态、悬浮物及表层沉积物中壬基酚的浓度分别为20.2-268.7ng/l、17.1-77.5 ng/l和3.6-299.3 ng/g dw,胶州湾入海河流水体中溶解态、悬浮物及表层沉积物中壬基酚的浓度分别为90.6-28656ng/l、52.5-27760ng/l和23.8-29723ng/g dw,墨水河中酚类化合物浓度最高,其次为海泊河,河流中壬基酚浓度远高于胶州湾,表明胶州湾周围河流是胶州湾中酚类污染物的主要污染源;胶州湾水体中溶解态和悬浮物中壬基酚的浓度水平表现出相似的季节分布特征,夏季浓度高于冬季,温度是研究区域影响NP季节分布的主要因素;由于胶州湾的沉积速率较低,表层沉积物中NP的浓度没有表现出明显的季节变化;从空间分布特征来看,胶州湾东北部墨水河、李村河、海泊河河口区酚类化合物浓度明显高于湾内其它区域,其空间分布受到污染源、湾内环流系统和水交换条件的共同影响;胶州湾水体中溶解态和悬浮颗粒物中NP的浓度呈正相关的关系,沉积物是其主要的归宿。胶州湾及其周围河流中烷基酚的浓度已经处于世界上污染水平最高的地区之一;(2)长江口及其临近海域夏季表层水、悬浮物和表层沉积物中壬基酚的浓度分别为14.09-173.09 ng/l,7.35-72.02ng/L及0.73-11.45 ng/g dw;长江冲淡水和悬浮物是研究区域壬基酚的主要来源,其它水系也对污染物的来源有一定贡献;表层水体中壬基酚的两个高值区均位于长江冲淡水的主轴线上,一个位于冲淡水中部悬沙峰的前缘,另一个位于1240E附近;表层沉积物中壬基酚的高值区位于长江口东南软泥区和浙江近岸软泥区;悬浮物高浓度区位于距长江口较远的浙江近岸;长江口海域壬基酚独特的的浓度分布特征是水动力条件、悬沙输送方向、微生物活性等环境因素共同影响的结果;研究海域与其它地区相比水体中壬基酚已达到中等污染水平;(3)黄河入海口地区枯水期水体中NP的浓度范围为15.7-148.6ng/l,表层水中NP平均浓度为45.8ng/l,底层水中NP平均浓度为31.0ng/l,表层水中NP平均浓度为底层水中的1.5倍;NP在8个表层沉积物采样站位中均被检测到,浓度范围为2.3-5.0ng/g dw,平均为3.6ng/g dw;黄河径流所携带的工业和生活污水是黄河口外海域中壬基酚的主要污染源,其中油田采出水也可能是污染源之一;黄河入海口地区水体中NP浓度由河道向外海方向浓度逐渐降低,且表层水中NP平均浓度高于底层水中NP浓度,海水的稀释作用是水体中NP分布特征的控制因素;黄河口水体中NP污染程度为中等偏低水平,沉积物中NP污染水平较低,除了与污染源的距离外,沉积物粒度是壬基酚在沉积物中分布的主要影响因子;III.在上述烷基酚暴露量研究的基础上,结合目前发表的壬基酚的剂量-效应浓度和生物富集系数,以及欧盟对壬基酚的风险评估报告和美国EPA对壬基酚的环境水质标准,用风险商的方法对胶州湾、长江口和黄河口地区主要酚类污染物壬基酚的污染现状进行了初步生态风险评估;由于胶州湾是重要的海水养殖基地,因此还估算了青岛地区居民通过海产品的壬基酚每日摄入量:(1)胶州湾水体和沉积物中NP的风险商RQwater和RQsediment值分别为0.12-1.05和0.19-7.67,沉积物中NP风险高于水体,可能会对某些无脊椎动物尤其是底栖类造成不同程度的生物效应,特别是内分泌干扰效应,胶州湾东北部和河口区的影响最为严重,从目前研究数据看,胶州湾水体中NP浓度还未达到鱼类的生物效应浓度;胶州湾入海河流中,除了白沙河外,其它河流的风险商值超过PNECwater和PNECsediment几倍甚至几百倍,会对水体和沉积物中的生物造成严重威胁,需要立即采取相关风险削减措施;通过已发表的不同生物对壬基酚的富集因子,计算胶州湾生物体内壬基酚的含量为0.08-0.74mg/kg,还远低于欧盟评估报告中壬基酚的PNECoral值(10mg/kg);估算青岛地区居民通过海产品冬季和夏季的每日壬基酚摄入量分别为9.20μg/day和7.04μg/day;(2)长江口地区壬基酚在水体和沉积物中的风险商RQwater和RQsediment值分别为0.08～0.56和0.02～0.29,水体中NP风险高于沉积物,可能会对牡蛎、藤壶等NP敏感物种造成潜在风险,泥质区中NP生态风险值得关注;(3)黄河口地区水体和表层沉积物中的风险商RQwater和RQsediment值分别为0.05～0.31和0.06～0.13,水体中NP风险高于沉积物,可能会对牡蛎、藤壶等NP敏感物种造成潜在风险,沉积物NP生态风险较低;IV.作为与近海环境的对照,本文选取长江三峡库区西陵峡段水体为研究对象,调查了受工农业污染较轻的偏远地区水体中烷基酚的背景浓度:三峡库区湖北秭归至大坝间的长江干流及香溪河枯水期表层水中壬基酚的浓度范围为24.2～167.6ng/l,绝大多数站位的浓度处于40.5～49.2ng/l之间,个别站位的浓度较高分别为137.1和167.6ng/l,已经超过了抑制甲壳类生物附着的浓度,个别站位的NP浓度已经超过了贝类幼苗的致死浓度;双酚A在此研究区域内的浓度范围为9.3～99.4ng/l,除A10站位的浓度为99.4ng/l外,其它站位的浓度均处于9.3～20.7ng/l之间,浓度总体上比壬基酚低一个数量级;由于自2003年6月三峡工程蓄水后,库区水体流速减缓,水体稀释自净能力减弱,水环境容量降低,另外库区污水处理设施严重不足,综合考虑各方面的影响因素,三峡库区水环境的污染状况,尤其是酚类等持久性有机污染物的污染状况不容乐观;V.由于污水处理厂排放水是环境中NP的重要来源之一,本文除了对烷基酚在近海和河口环境中的浓度分布的研究,还以青岛市采用AB工艺的海泊河污水处理厂和采用A2/O工艺的团岛污水处理厂为例,研究了壬基酚及其低聚物在污水处理流程中的分布及不同污水处理工艺对壬基酚的去除效率,结果表明:①海泊河STP进水和出水中壬基酚的浓度分别为0.94和0.25μg/l,表观去除率为73.4%,而团岛STP进水和出水中NP的浓度分别为0.12和0.29μg/l,出水中NP的浓度反而高于进水;壬基酚在海泊河污水处理厂和团岛污水处理厂的硝化后污泥中的含量分别为84.6和2.96μg/g dw;②壬基酚在污水处理厂的迁移转化行为由微生物降解和物理吸附两方面控制,经过二级生物处理后,污水中的NP没有得到完全去除,而且二级排放污水经过深度处理后,NP的浓度没有明显变化;在污水处理流程中,NP的累积主要产生于厌氧消化过程,污泥是NP在流程中的汇;③壬基酚在污水处理厂中的去除效率随处理工艺的不同而不同,但由于壬基酚的降解受温度、污泥泥龄、水力停留时间、微生物种群及多样性、营养条件(N、P含量)、壬基酚浓度、氧化还原条件等诸多方面因素的影响,至于哪种处理工艺对NP的去除效率更高,还有待于进一步研究。更多还原

【Abstract】 Alkylphenols are the stable degradation products of the ionic surfactant alkylphenol ethoxylates. They are toxic, bioaccumulative, persistent and estrogenic therefore recognized as a typical group of environmental endocrine disrupting chemicals. Much concern has been focused on their occurrence and environmental behavior and their ecological risk assessment is of urgent need.I. A sensitive and fast analytical method which can simultaneously determinates 11 phenolic compounds including alkylphenols, chlorophenols and bisphenol A by gas chromatography- mass spectrometry (GC-MS) in environmental samples was established. Using nonpolar dichloromethane as the extraction solvent, the water samples was extracted by liquid-liquid extraction with the spiked recoveries and relative standard deviations were 72.0-94.7% and 2.4-13.4% respectively; the solid phase samples (sediment /sludge) were directly extracted without drying after digested with HCl, and the spiked recoveries and relative standard deviations were 72.0-94.7% and 2.4-13.4% respectively; then the analytes were derivatized with an excess amount of bis(trimethylsilyl)trifluoroacetaminde (BSTFA) and finally the silyl derivetized products were determined by GC-MS. Under the selected chromatographic conditions, the various phenolic target compounds can get baseline separation and the linear correlations were good in the range of 0-3000ng/ml with the aberrance coefficients between 0.9927-0.9998. The detection limits for water and solid phase samples were below 2ng/l and 2ng/g dry weight respectively. The analytical method mentioned above is highly sensitive and selective for phenolic compounds as well as labour-saving and needless of extra expensive equipments, and can realize routine analysis in regular laboratories.Base on the established analytical method, the distribution characteristics and environmental behavior of the target phenolic compounds in various environmental matrices of Jiouzhou Bay and its adjacent rivers、Yangtze River and Yellow River Estuaries were systematically studied for the first time, and the main results are as follows:(1) The spatial distribution characteristics and seasonal variations of phenolic compounds in water、suspended particulates and surface sediments in Jiaozhou Bay and its adjacent rivers were studied. The results show that nonylphenol was the predominant phenolic pollutants in Jiaozhou Bay , with the next important pollutants in the sequence of bisphenol A, octylphenol, butylphenol, and 2,4-dichlorophenol; nonylphenol concentrations in surface water、suspended particulates and surface sediments were 20.2-268.7ng/l、17.1-77.5 ng/l and 3.6-299.3 ng/g dw respectively, and nonylphenol concentrations 90.6-28656ng/l、52.5-27760ng/l和23.8-29723ng/g dw; Moshui River was the most polluted one followed by Haipo River, and the nonylphenol concentrations in rivers were much higher that in Jiaozhou Bay indicating the inflowing rivers were the main source of alkylphenols to Jiaozhou bay;Nonylphenol concentrations in dissolve portion of water and suspended particulates showed similar seasonal variation with higher concentrations in warmer season, and temperature was recognized as the main influence factor; Sediment concentrations of NP in Jiaozhou Bay did not show obvious seasonal variation due to the low sedimentary rate of suspended particulates; Concerning the spatial distribution characteristics, the level of phenolic compounds in the northeast of part of Jiaozhou Bay were much higher than the other parts ,and this distribution pattern was affected by the pollutant sources, circulation system and water exchange conditions together;Nonylphenol concentrations in dissolved portion of water and the suspended particulates were positively correlated and the sediment was the main fate of NP. The contamination level of NP in Jiaozhou Bay and its adjacent rivers was among the highest concentrations of the world;(2) The concentrations of nonylphenol determined in dissolved portion of water, suspended solids and surface sediment in Yangtze River Estuary and its adjacent area ranged between 14.09-173.09 ng/L, 7.35-72.02ng/L and 0.73-11.45 ng/g dw, respectively;The high concentration zone in surface water was located along the direction of Yangtze River freshwater plume with the maximum concentration recorded at the rim of the Maximum Turbidity Zone. The high concentration zone in surface sediment was located in the muddy area to the southeast of Yangtze Estuary and in the coast of Zhejing province, coincided with the direction of suspended solid transportation. Freshwater and suspended solids of Yangtze River were the main sources of nonylphenol in the study area. The distribution pattern of nonylphenol was influenced by hydrodynamic conditions, suspended solid transportation and microbial activity. Compared with other estuarine areas of the world, nonylphenol concentration in surface water of this study is in moderate pollution level.(3)The concentration of nonylphenol in the Yellow River Estuary ranged between 15.7-148.6 ng/l, with the average conctentrations in the surface and bottom water was 45.8 ng/l and 31.0 ng/l respectively; NP was detected in all the sediment samples with the range of 2.3-5.0 ng/g dw;The industry and municipal wastewater carried by Yellow River was the main source of contamination but the produced water from the proximal oil field might be another source too; Seawater dilution and the granularity of the sediment were the dominant factors influencing the distribution of NP in water and the surface sediment respectively; the contamination level of NP was slightly below moderate in water and low in sediment;II. Based on the occurrence study of nonylphenol mentioned above , a primary ecological risk assessment of NP in Jiaozhou Bay, Yangtze River Estuary and Yellow River estuary was attempted by the calculation of risk quotients.(1) The value of RQwater and RQsediment in the water and sediment of Jiaozhou Bay was calculated as 0.12-1.05 and 0.19-7.67 respectively. The risk of NP in sediment was higher than that in water. Harmful biological effects especially endocrine disrupting effects might happen to some invertebrates particularly the benthos. The influence was most seriously in the northeast part of the bay and the NP concentrations had not reached the threshold level of biological effects for fish. The values of RQ in the inflowing rivers were much higher than the PNECwater and PNECsediment of NP except the Baisha River, the biota were seriously threatened by the phenolic compounds, and measures must be taken immediately to mitigate the risk potential. The NP contents in organisms of Jiaozhou Bay were estimated by the BCFs published as 0.08-0.74 mg/kg which were far below the PNECoral(10mg/kg)of NP . Daily ingest of NP through seafood was estimated as 9.20μg/d and 7.04μg/d in winter and summer respectively.(2) The value of RQwater and RQsediment in the water and sediment of Yangtze River Eatuary was calculated as 0.08-0.56和0.02-0.29 respectively whereas the water possessed the higer risk. The sensitive species such as oysters and barnacles may face more potential. Concerns should be paid to the risk potential of NP in the muddy area;(3) The value of RQwater and RQsediment in the water and sediment of Yellow River Eatuary was calculated as 0.05-0.31和0.06-0.13 respectively with the water possessed the higer risk. The sensitive species such as oysters and barnacles may face more potential. The risk potential of NP in the sediment was low. IV.In comparison to the alkylphenols levels in offshore areas, alkylphenols concentrations were investigated in the remote an rural area of Xiling Gorge in Yangtze River where not affected much by sewages.The main pollutants were nonylphenol and bisphenol A with the concentration ranges of 24.2-167.6ng/l and 9.3-99.4ng/l, respectively. The concentrations of nonylphenol at most sampling sites have exceeded the threshold level for undesirable effects to non-target organisms. The organcia pollution status in this area was not optimistic due to the self-purification capacity of the waterbody decreased significantly since the water was impounded by the Three Gorges Project. V.The effluent from sewage treatment plants(STPs) was a main exposure source of nonylphenol in the environment. The removal efficiency of NP and the NP distribution during the process of the wastewater in two STPs in Qingdao employing different techniques were studied as well. The results showed:①The NP concentrations in the influent and effluent of Haipo River STP was 0.94 and 0.25μg/l respectively while the value was 0.12 and 0.29μg/l respectively in Tuandao STP; the concentration of NP in the digested sluge were 84.6 and 2.96μg/g dw in the two STPs respectively;②The transfer and transform of NP during wastewater treatment process was controlled by physical-chemical sorption and microbial biodegradation together, further treatment did not increase the NP removal efficiency obviously; NP accumulated mainly in the anaerobic digestion and the sludge was the fate of NP ;③The removal efficiency of NP was different depending on the treatment processes and the biodegradation of NP was influenced by many factors such as temperature ,hydraulic retention time, diversity of microbes and the initialized concentrations of NP. Which kind of treatment process is more efficient in removing of NP remains further investigation.更多还原