珠江河流胶体中的典型内分泌干扰物

采用切向流超滤、固相萃取、气相色谱-质谱联用等分离和分析方法,研究了珠江2条河流中典型内分泌干扰物(EDCs)在胶体相中的含量分布、胶体/水相间的分配作用.结果发现:胶体中4-壬基酚(NP)、双酚A(BPA)、雌酮(E1) 的含量范围分别为23.2~108ng/L、2.3~97.6ng/L、n.d.(未检出)~0.32ng/L,平均值分别为70,31.4,0.3ng/L;17β-雌二醇(E2)、己烯雌酚(DES)、17α-乙炔雌二醇(EE2)、雌三醇(E3)则未在胶体样品中检出.除石龙外,其余各采样点表、底水层间的胶体EDCs浓度水平无显著差异.NP和BPA含量与胶体有机碳(COC)含量、紫外吸收强度(UV254)均呈正相关,说明COC是控制酚类雌激素在胶体相中分布的一个重要因素,NP、BPA和COC之间的相互作用与胶体有机碳的芳香性有关.计算发现,珠江河水中约21%~67% 的 NP、4%~74% 的BPA、24%~26% 的E1存在于胶体相,NP和BPA在胶体/水相间的有机碳归一化分配系数(Kcoc)分别为10 (5.69±0.50)、10 (5.51±0.77),高出各自的悬浮颗粒物/水分配系数(Koc)1个数量级,表明胶体的强吸附能力对EDCs在水环境介质间分配、迁移、转化发挥了重要作用.     

AnSBR法处理生活污水中典型环境雌激素的研究

为评价和考察厌氧序批式反应器(AnSBR)对生活污水中9种典型环境雌激素的去除效果和机制,采用固相萃取(SPE)——LC/MS/MS分析方法,分析所选环境雌激素的浓度和污泥吸附量. 结果表明:大豆苷元,4-t-辛基酚(OP),4-n-壬基酚(NP)和染料木素的检出浓度高于其他5种环境雌激素;厌氧污泥对NP,OP,雌酮(E1),17α-乙炔基雌二醇(EE2)和17β-雌二醇(E2)的吸附作用明显;大豆苷元和染料木素的去除率在60%以上;大豆苷元、染料木素和雌三醇(E3)的主要去除机制为生物降解作用,EE2,OP和NP的去除是生物降解、污泥吸附的共同作用.      

罗时江中5种环境内分泌干扰物的分布特征

以典型的农业面源污染河流——大理洱海罗时江作为研究对象,采用固相萃取、超声萃取和气相色谱质谱联用技术,对河流水体和表层沉积物样品中5种EDCs〔环境内分泌干扰物,包括BPA(双酚A)、E1(雌酮)、E2(17β-雌二醇)、EE2(乙炔基雌二醇)和E3(雌三醇)〕进行分析测定.结果表明,罗时江水体中普遍存在EDCs,其中ρ(BPA)为1.01～43.64 ng/L,ρ(E1)为2.54～20.53 ng/L,ρ(E2)为nd～23.18 ng/L,ρ(EE2)为1.16～13.74 ng/L,ρ(E3)为nd～26.55 ng/L.各采样点EDCs污染通量结果显示,右所、邓川2个乡镇对EDCs污染贡献量最为显著,之后由于湿地截留以及河流的自净作用EDCs污染通量有所削减.罗时江对洱海的入湖EDCs贡献量为1.35～3.70μg/s.在城镇下游处沉积物中E1和E3的富集倍数均为各采样点中最高,这与河流水体中的污染通量变化趋势一致,进一步说明该处污染负荷的加剧,并且说明EDCs会在污染发生时于下游就近沉积.沉积物中w(E3)最高(1.48～28.44μg/kg),其次为w(E1)(0.36～2.95μg/kg),E2因迅速降解不易富集.      

宁夏入黄排水沟中典型内分泌干扰物的污染特征与风险评价

利用固相萃取-超高效液相色谱质谱联用仪检测分析了9种典型内分泌干扰物(EDCs)在宁夏入黄排水沟中的污染水平,探讨了其空间分布特征,分析了其来源,并进行了风险评价.结果表明,宁夏入黄排水沟中33个采样点均有EDCs检出,各采样点∑EDCs浓度范围在82.28～1 730.09 ng·L^-1之间.其中,检出浓度最高的两种化合物是E2和OP,浓度最大值分别为1 367.41 ng·L^-1和787.80 ng·L^-1.酚类化合物中双酚A(BPA)和壬基酚(NP)的检出率均达到90%以上,雌激素类化合物中雌酮(E1)和雌三醇(E3)的检出率较高,均为79%.空间分布上,排水沟中∑EDCs浓度平均值呈现出石嘴山市和银川市远高于吴忠市和中卫市的分布特征,入黄口采样点∑EDCs浓度范围为82.28～979.82 ng·L^-1.来源分析显示,宁夏入黄排水沟中BPA主要来自于工业废水和生活污水,OP主要来源于工业废水,E1主要来自于畜禽养殖废水,E3主要来源于生活污水.风险评价结果表明,入黄排水沟中EDCs的生态风险...     

松花江水中13种内分泌干扰物的初步调查

用固相萃取(SPE)/高效液相色谱法(HPLC)同时测定了松花江水中的13种典型内分泌干扰物(EDCs).结果表明,哈尔滨段江水中雌三醇(E3)、雌二醇(E2)、雌酮(E1)、乙炔雌醇(EE2)及乙烯雌酚(DES)5种雌激素物质的浓度普遍较高.最高可达66 ng·L-1;酞酸二甲酯(DMP)、酞酸二乙酯(DEP)、酞酸二正丁酯(DnBP)及酞酸二(2-乙基己基)酯(DEHP)4种酞酸酯丰度最大,其中DnBP浓度最高可达330μg·L-1;4-正壬基酚(4-n-NP),带支链的对壬基酚(NP)及4-叔-辛基酚(4-t-OP)3种烷基酚的浓度范围为25-1261 ng·L-1;双酚A(BPA)浓度变化较小,保持在20-50 ng·L-1之间.经与相关报道比较,初步认为松花江水中雌激素类物质及酞酸酯污染较为严重,应当引起有关部门的警惕.     

利用再生水涵养地下水过程中3种典型内分泌干扰物的迁移转化特性

通过土柱模拟试验研究了3种典型的内分泌干扰物——17β-雌二醇(E2)、炔雌醇(EE2)和双酚A (BPA)在再生水涵养地下水过程中的吸附、生物降解和迁移特性。结果表明:3种EDCs的衰减效果为E2>EE2>BPA,3种不同运行方式下的衰减效果为干湿交替回灌(WDAR)>连续回灌(CR)>连续灭菌回灌(CSR)。在连续回灌条件下,E2、EE2和BPA的衰减速率常数分别为0.0783,0.0505,0.0479 m~(-1);总去除率为98%、96%和92%,其去除率受温度影响。土柱微生物的分析结果表明:土柱下层微生物群落结构的多样性明显高于上层。主要微生物群落为变形菌属,包括α、β变形菌,其对EDCs的降解起主要作用。     

松花江流域某自来水厂中内分泌干扰物的调查

利用固相萃取-高效液相色谱法调查了松花江流域某自来水厂原水、传统净水工艺各处理单元出水及管网水中的13种内分泌干扰物(EDCs).结果表明,固醇类雌激素物质除管网水中未检出外,其他各水样均有检出,浓度为4-44 ng·L-1;4种邻苯二甲酸酯(PAEs)、双酚A(BPA)及3种烷基酚(APs)在各水样中几乎100%检出,浓度为2～163 760 ng·L-1,其中以邻苯二甲酸二丁酯(DBP)与邻苯二甲酸二(2-乙基己基)酯(DEHP)为主.研究还发现,尽管有个别EDCs出水浓度高于进水浓度,但混凝沉淀工艺对EDCs的去除在该水厂中占主导作用,平均去除率为63%;砂滤与氯消毒工艺出水不稳定,只能对部分EDCs起到一定程度去除作用.此外,出厂水经管网输送后其中的绝大多数EDCs含量升高,说明进入管网水中的EDCs除水源水污染外,还有一个重要途径就是输水管材中相应污染物的渗析.     

广州市流溪河水体中6种内分泌干扰素时空分布特征与环境风险

以雌酮(E1)、雌二醇(E2)、双酚A(BPA)、壬基酚(4-NP)、辛基酚(4-t-OP)和三氯生(TCS)这6种内分泌干扰物(endocrine disrupting chemicals,EDCs)为对象,研究其在广州市流溪河水体中的时空分布特征,并对其雌激素活性进行风险评价.结果表明,14个监测点均有EDCs检出,总范围在26.07~7 109.5 ng·L-1,以4-NP贡献最高(78.62%),其次为BPA(11.91%),其他4种目标物浓度均较低(≤4.92%).时空变化上,EDCs浓度从上游至下游逐渐增加,尤其是下游支流中EDC浓度偏高;丰水期4-NP、4-t-OP浓度显著高于枯水期(P0.05),而E1、E2、BPA则呈相反趋势.相关性分析显示,DO与6种EDCs浓度变化呈显著负相关,高锰酸盐指数、EC、TN、TP、NH+4-N与E1、E2、BPA、TCS呈显著正相关,而与4-NP相关性不显著(P0.05),说明E1、E2、BPA、TCS可能与氮、磷营养盐污染同源.冗余分析(redundancy analysis,RDA)显示,流溪河水体中EDCs的季节性变化比空间变化更为明显(RDA1 56.14%RDA2 14.20%),丰水期水体中EDCs浓度变化主要受4-NP影响,而枯水期则主要受BPA影响.与世界范围内水体中EDCs浓度相比,流溪河中下游河段4-NP、BPA和TCS浓度处于较高水平,其他3种目标物处于中低水平.风险评价结果显示,流溪河中下游河段风险熵值RQ值均大于1,说明该区域具有高雌激素活性风险.     

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.     

辽东湾野生四角蛤蜊性畸变调查

为揭示辽东湾近海海域环境内分泌干扰物(EDCs)的生物效应与潜在生态风险,利用组织学方法系统调查辽东湾近海海域野生四角蛤蜊性畸变发生情况,并利用GC-MS/MS分析了组织体内典型酚类污染物包括壬基酚(NP)、辛基酚(Op)和双酚A(BPA)的浓度水平.调查结果表明:5月、6月和8月野生四角蛤蜊雌雄同体发生率分别为30%,20%和14%,软体部组织中NP浓度则分别为410.70,254.95,227.15ng/g dw(干重), BPA浓度分别为7.60,4.30,7.05ng/gdw,但是没有检出OP.研究结果表明环境EDCs已经影响了辽东湾海洋生物繁殖系统、并对区域海洋生态系统造成潜在风险.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.