山东半岛典型海湾中烷基酚及双酚A的分布特征

烷基酚和双酚A是环境中最常见的内分泌干扰物。本研究对烟台四十里湾和套子湾以及青岛胶州湾表层海水中的壬/辛基酚(NP/OP)、壬/辛基酚单聚氧乙烯醚(NP1EO/OP1EO)以及双酚A(BPA)的浓度水平进行分析,结果显示:NP和NP1EO是最主要的污染物,河口和港口是海湾中污染物浓度最高的区域。总体而言,四十里湾中各污染物的浓度最高,其次为胶州湾,套子湾最低,与国内其他海湾区域相比,污染状况处于中等水平。相对于2005年,胶州湾水体中的烷基酚浓度明显降低。文章同时分析了几个湾的主要入海河流河水样品以及烟台污水处理厂出厂水样,发现污水处理厂出水是烟台四十里湾烷基酚的主要来源。在三个海湾中,烷基酚的分布主要受河流输入、生活污水排放和港口经济活动影响,同时,洋流和潮汐的稀释作用对污染物分布有明显影响。     

Peroxidase-mediated removal of endocrine disrupting compound mixtures from water

Several classes of oxidative enzymes have shown promise for efficient removal of endocrine disrupting compounds (EDCs) that are resistant to conventional wastewater treatments. Although the kinetics of reactions between individual EDCs and selected oxidative enzymes are well documented in the literature, there has been little investigation of reactions with EDC mixtures. This makes it impossible to predict how enzyme-mediated treatment systems will perform since wastewater effluents generally contain multiple EDCs. This paper reports pseudo-first order rate constants for a model oxidative enzyme, horseradish peroxidase (HRP), during single-substrate (k₁) and mixed-substrate (k_1-MIX) reactions. Measured values are compared with literature values of three Michaelis-Menten parameters: half-saturation constant (K_M), enzyme turnover number (k_CAT), and the ratio k_CAT/K_M. Published reports had suggested that each of these could be correlated with HRP reactivity towards EDCs in mixtures, and empirical results from this study show that K_M can be used to predict the sequence of EDC removal reactions within a particular mixture. We also observed that k_1-MIX values were generally greater than k₁ values and that compounds exhibiting greatest estrogenic toxicities reacted most rapidly in a given mixture. Finally, because K_M may be tedious to measure for every EDC of interest, we have constructed a quantitative structure-activity relationship (QSAR) model to predict these values. This model predicts K_M quite accurately (R² = 89%) based on two molecular characteristics: molecular volume and hydration energy. Its accuracy makes this QSAR a useful tool for predicting which EDCs will be removed most efficiently during enzyme treatment of EDC mixtures.     

壬基酚的环境生物地球化学研究进展及对新污染物管理的建议

近年来,我国大气环境、水环境和土壤环境质量得到一定的改善,“碧水蓝天”已经成为常态.但随着持久性有机污染物、内分泌干扰物、抗生素和微塑料等新污染物在环境中不断被检出,新污染物正逐步受到广泛的关注,壬基酚作为一种典型的内分泌干扰物也备受研究人员的关注.系统地概括了我国水体中壬基酚的环境行为和暴露水平,并基于风险商法和联合概率曲线法对壬基酚可能造成的生态风险进行了评估.结果表明,壬基酚对水生生物的毒性效应主要包括急性毒性、生长发育毒性、雌激素效应和繁殖毒性;壬基酚在我国主要流域水体中普遍存在,其浓度平均值在60～1 000 ng·L^-1,浓度最高值可达4 628 ng·L^-1;基于风险商法和联合概率曲线法的风险评估结果表明,壬基酚对我国主要流域里的水生生物均存在一定的风险.最后,总结了目前比较常用的壬基酚处理处置和风险管控技术,比较了国际上内分泌干扰物的监管方法,针对我国在新污染物环境管理中存在的问题,提出了针对性政策建议,研究结果可以为我国新污染物管理和管控提供参考.     

A monoclonal antibody against Lates calcarifer vitellogenin and a competitive ELISA to evaluate vitellogenin induction after exposure to xenoestrogen

A monoclonal antibody specific to sea bass(Lates calcarifer) vitellogenin(VTG) was developed,for use as a tool for monitoring endocrine disrupting chemicals(EDCs). VTG was induced in sea bass by intramuscular injection of 17β-estradiol(E_2: 2 mg/kg) every three days. Blood was collected three days after the last injection. Plasma VTG was then purified by chromatography in hydroxyapatite and a sephacryl-S300 column. Characterizations of purified VTG were done by phospholipoglycoprotein staining on a native-PAGE with confirmation by mass spectrometry(LC-MS/MS). Antibody was raised in mice by injection of purified VTG. After monoclonal antibody production, the hybridoma clone No. 41(MAb-sea bass VTG 41)was selected and developed for quantification of VTG by competitive enzyme-linked immunosorbent assay(ELISA). The ELISA method was sensitive with a detection limit of VTG 40 ng/mL. MAb-sea bass VTG 41 was specific to VTG from E_2-treated sea bass and others EDCs(Nonylphenol, Benzo[a]pyrene and CdCl_2). Moreover, cross-reactivity was also found in E_2-treated coral grouper(Epinephelus corallicola). The ELISA method obtained from this work can be further applied for the assessment of EDCs in Thailand and Southeast Asia's aquatic environment.     

改性无烟煤去除水中内分泌干扰物的性能探究

以KOH为改性剂对无烟煤改性,研究了改性前后无烟煤对3种内分泌干扰物EDCs(17α-乙炔基雌二醇EE2、双酚A BPA、磺胺甲噁唑SMZ)的吸附性能。结果表明,KOH改性对无烟煤的孔结构和表面性质产生影响,提高了无烟煤对3种EDCs的吸附量,其中对EE2的吸附量提高了近2倍。3种EDCs在改性前后2种无烟煤上的吸附过程均可用伪二级动力学描述,吸附等温线更符合Langmuir吸附等温方程,表现为化学吸附。改性前后2种无烟煤对EE2均表现出最高吸附能力,平衡吸附量(qe)分别为0.214 7μg/mg与0.622 9μg/mg;其次是BPA;最差是SMZ,qe仅为0.095 9μg/mg与0.124 2μg/mg。进一步研究表明,目标物的吸附情况与其憎水性质和分子结构有关,无烟煤吸附目标物的能力与其正辛醇/水分配系数正相关。     

O3/H2O2降解Atrazine效能研究

利用O3/H2O2降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5mg/L的O3单独氧化去除率为27.2%;相同O3投量下,H2O2/O3摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H2O2/O3体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H2O2/O3并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.     

土壤净化槽对农村污水中内分泌干扰物的去除效果

以土壤净化槽污水处理系统为研究对象,采用固相萃取-色谱质谱检测方法,分析了云南洱海流域农村污水中3种天然雌激素类内分泌干扰物〔E1(雌酮)、E2(雌二醇)和E3(雌三醇)〕和2种人工合成内分泌干扰物〔EE2(炔雌醇)和BPA(双酚A)〕的质量浓度与去除效果. 结果表明,洱海流域农村污水中天然雌激素的质量浓度远高于人工合成内分泌干扰物,E1与E2为污水中天然雌激素内分泌干扰物的主要成分,占87.1%~99.2%. 土壤净化槽对天然雌激素类内分泌干扰物、EE2和BPA的净化能力分别为1.42~168.21、0.64和3.48mg/(m2·a). E1、E2和E3在土壤中的平均残留率分别为4.3%、6.3%和3.8%,其中90%以上的雌激素物质在土壤净化槽系统中被降解或转化. 土壤净化槽对天然雌激素、EE2和BPA的平均去除率分别为70.3%、63.6%和77.8%,对常规污染物COD_Cr(69.8%)、TP(88.7%)、TN(57.2%)和NH₃-N(88.7%)的去除效果也较好. 土壤净化槽可以有效去除村落污水中的内分泌干扰物、有机物以及氮磷污染物,对削减村镇面源污染、减少入湖污染负荷以及改善流域内的水环境质量具有重要作用.      

典型环境内分泌干扰物的来源、环境分布和主要环境过程

内分泌干扰物(EDCs)作为一种新兴污染物,具有憎水性、低剂量效应和半衰期长等特征,在全球的土壤/沉积物中已被广泛检测到,并发现已给环境带来了严重的威胁。本文重点综合评述了近10年来土壤/沉积物中EDCs的来源、浓度水平、空间分布及吸附特性的研究。结果发现,EDCs来源涉及农业、工业和生活等多个方面;空间分布上,一般呈近海地区沉积物中EDCs浓度水平较河流底泥及土壤低,而高度工业化、城市化地区土壤/沉积物中EDCs浓度亦较高;EDCs的吸附受土壤/沉积物理化性质、EDCs自身性质和环境条件的共同影响,一般土壤有机质的含量和成熟度、土壤颗粒的比表面积与其吸附能力呈正相关,黏土矿物类型对EDCs的吸附也有重要的影响;EDCs的吸附能力与其自身的疏水性和结构特征有关;温度升高和溶液p H值增加都不利于EDCs的吸附,而溶液离子强度的增加对其吸附起着促进作用。土壤/沉积物对EDCs的吸附是一个复杂的过程,因此对其吸附特性需要进一步的探讨。     

多环芳烃（萘）对火腿许水蚤（Schmackeria poplesia）急性和慢性毒性效应的研究(A Study on the Acute and Chronic Effects of NAPH on Schmackeria poplesia)

为初步探讨内分泌干扰物多环芳烃对海洋桡足类生物所产生的生物效应,研究了萘对火腿许水蚤(Schmackeria poplesia)的急性毒性作用及其在1.6μg·L-1、16μg·L-1、160μg·L-1浓度下对火腿许水蚤变态率、存活率、繁殖力、性别比和体长的影响.结果显示,萘对火腿许水蚤48hLC50和96hLC50分别为4589.34μg·L-1和1559.55μg·L-1;各浓度萘均引起火腿许水蚤幼体的变态率显著降低;160μg·L-1萘条件下,火腿许水蚤的存活率、产卵率和抱卵雌体比率均显著降低;各浓度的萘对火腿许水蚤的性别比和体长均未造成显著影响.研究表明,在目前的环境浓度下,多环芳烃(萘)对海洋桡足类生物可能造成的生态风险较低.     

全氟辛磺酸（PFOS）对非洲爪蟾（Xenopus laevis）生长发育、甲状腺和性腺组织学的影响

为了揭示全氟辛磺酸(PFOS)的甲状腺激素和性激素干扰效应,并探索运用爪蟾动物模型同时检测多种环境内分泌干扰效应的可能性,将NF48阶段非洲爪蟾(Xenopus laevis)蝌蚪暴露于0.01、0.1和1mg·L-1PFOS中6个月,检测PFOS对爪蟾生长、变态、甲状腺和性腺的影响.结果表明,在各取样时间,PFOS组爪蟾体长、体重和蝌蚪尾长与对照组均无显著差异(p>0.05);2个月后,PFOS组比对照组平均慢1个发育阶段,4和6个月后,0.01mg·L-1PFOS组反而比对照组分别快1和2个发育阶段.6个月后,PFOS组甲状腺出现滤泡上皮细胞增生、胶质减少甚至空泡化等现象,且随着PFOS浓度的增加而加重;各组幼蛙性腺出现间性、睾丸珍珠状和先天性萎缩等畸形现象,外观为间性的性腺主要表现为睾丸组织中产生类似雌性个体的卵巢腔.对照组幼蛙的雌雄比为0.5:1,而暴露组分别为2.3:1(0.01mg·L-1组)、4.5:1(0.1mg·L-1组)和5:1(1mg·L-1组).上述结果表明,PFOS对爪蟾的变态过程具有小剂量刺激效应,能引起甲状腺组织结构的损伤,导致睾丸组织的雌性化和雌雄性比的异常升高,表现出明显的甲状腺激素和性激素干扰效应,可以认定为一种环境内分泌干扰物.实验同时表明非洲爪蟾可以用于多种环境内分泌干扰效应的同时检测.