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.      

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.     

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.      

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.     

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.     

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.     

环境内分泌干扰物在人工湿地中的去除研究

考查了水平潜流人工湿地对城市生活污水中的8种内分泌干扰物去除效果。结果表明:在水力负荷为0.17m/d,水力停留时间为4.6 d情况下,水平潜流人工湿地对雌激素酮(E1)、雌激素三醇(E3)、双酚A(BPA)、辛基酚(OP)、17β-雌二醇(E2)、17a-雌二醇(17a-E2)、17α-乙炔基雌二醇(EE2)的平均去除率分别为81.4%、39.3%、73.9%、44.1%、69.7%、82.2%、65.2%。其中,4-正壬基酚(4-n-NP)在湿地出水中未检测到。人工湿地中内分泌干扰物去除效果沿程变化结果表明,湿地前段对内分泌干扰物的去除效果优于后段,说明人工湿地前段微生物的降解更有效。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

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.     

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.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

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.     

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.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.