壬基酚聚氧乙烯醚在污水处理过程中的迁移转化行为

用正相色谱－质谱联用法（NPLC－MS）分离分析高聚合度的NPnEO(n＞2）,用气相色谱－质谱联用方法（GC－MS）测定其中的NP,NP1EO和NP2EO浓度,对NPnEO在城市污水处理厂的迁移转化行为进行了研究。在污水处理厂的进水中,检测出NP和NPnEO(n=1-23）,总浓度为174nmol/L,其中NP2EO的浓度最高,为89．6nmol/L;其次分别为NP（42．2nmol/L）和NP1EO（12．2nmol/L）;出水中同样检测出NP和NPnEO(n=1-18),其中NP2EO的浓度最高,为37．2nmol/L;其次分别为NP（6．64nmol/L）和NP1EO（0．135nmol/L)。在城市污水处理过程中,NPnEO从高聚合度降妥成低聚合度,NP和NPnEO的总去降率为71％。另外,NP和NPnEO在污泥及污泥过滤水中的分配表明污泥对NPnEO有明显的吸附作用,并近似符合Dubinin-Astakhov等温吸附。     

水体中的微生物对壬基酚聚氧乙烯醚的生物降解

为有效控制水体中壬基酚聚氧乙烯醚的污染 ,以芽孢杆菌、假单胞菌、诺卡氏菌和假丝酵母为试验菌株 ,研究了其对壬基酚聚氧乙烯醚的生物降解特性。试验结果表明 ,4菌株在一定的条件下对水体中的壬基酚聚氧乙烯醚均有一定的降解率。若按体积比 1∶ 2∶ 1∶ 1的比例将四菌株组合成复合菌群 ,可大幅度提高处理效率 ,降解率可达 61 %。应用该复合菌对影响壬基酚聚氧乙烯醚降解的各种主要因素进行了研究 ,发现降解菌在θ为 2 5～ 30℃ ,p H值为 5.5～ 8.5及壬基酚聚氧乙烯醚初始质量浓度ρ(NP1 0 EO)为 0～ 1 0 0 mg/ L范围内保持高活性 ;当底物质量浓度大于 1 0 0 mg/ L 时 ,平均降解速率线性下降 ;当接种量标准为 1× 1 0 8CFU/ m L (即菌悬液 /反应液为1 0 % )时壬基酚聚氧乙烯醚的降解是高效与经济的     

含藻水中壬基酚的光降解转化研究

选取壬基酚(nonylphenol,NP)作为研究对象,研究了水中2种常见淡水藻(小球藻和鱼腥藻)对壬基酚的光降解促进作用,并对藻引发水中壬基酚的光降解途径进行了分析;同时也研究了天然水中普遍存在的物质成分(腐殖酸和铁离子)与藻协同引发壬基酚的光降解及其影响机制.结果表明,含淡水藻的水溶液经过光照后能引发其中壬基酚的光降解;藻、腐殖酸和铁离子的水溶液经过光照后,对壬基酚光降解的增强促进作用更大,在含藻、腐殖酸和铁离子的水溶液中,4 h光照后壬基酚的降解率可达58%.根据此结果推测藻/腐殖酸和铁离子体系光照后能产生更多的活性物质,从而促进水中有机污染物的光降解.     

壬基酚在污灌土壤中吸附行为研究

采用序批式室内实验研究了壬基酚(NP)在污灌土壤中的吸附行为,同时探讨了壬基酚在土壤中吸附行为的影响因素,包括pH、离子强度、黑炭和矿物质.水溶液中NP检测方法为液液萃取-高效液相方法(LLE-HPLC).研究结果表明,土壤中有机质含量在吸附过程中起决定作用,土壤自身矿物组成成分对NP吸附行为具有一定影响.NP在土壤中吸附反应6h后达到平衡,吸附动力学都符合准二级线性模式;吸附等温线符合线性模式.壬基酚在污灌和清灌土壤中有机质吸附系数(Koc)分别为3.1×104 L·kg-1和3.2 ×104 L·kg-1,在土壤中很难移动.pH改变对壬基酚在土壤中吸附行为影响程度要高于离子强度,碱性条件下影响结果更为显著.NP在土壤黑炭和矿物质中吸附行为均符合线性模式,分配系数都有所下降.     

一株壬基酚降解菌的分离鉴定及其对壬基酚同分异构体降解特性研究

壬基酚(NP)是典型的内分泌干扰物,具有雌激素效应.目前对NP的研究主要集中于微生物降解对其整体去除效果,而对各NP同分异构体的降解行为尚缺乏系统性研究.从钱塘江沉积物中筛选得到一株能够降解NP的细菌,命名为N-1,实验室条件下该菌能以NP为唯一碳源生长.经形态、生理生化及16S rRNA基因序列分析,N-1鉴定为假黄单胞菌(Pseudoxanthomonas sp.).通过正交试验确定N-1降解NP的最适条件为:温度30℃,p H=7.0,菌量10%,NP浓度5~10 mg·L~(-1).最适条件下,N-1对NP 16 d整体降解率可达88.0%,对10种NP异构体降解率在69.7%~100%之间,说明N-1对NP同分异构体的降解具有结构-降解特性,即不同结构NP异构体表现出不一样的降解能力.进一步研究发现,NP异构体降解率随着NP烷基C链长度增加而升高,随着烷基取代基结构越复杂而降低.NP降解选择性导致的难降解成分残留现象,为NP类异构体污染物的微生物修复提供了一定的理论依据.     

Metabolism of the Nonylphenol Isomer [Ring-U-14c]-4-(3′,5′-Dimethyl-3′-Heptyl)-Phenol by Cell Suspension Cultures of Agrostemma githago and Soybean

Abstract

The biotransformation of the nonylphenol isomer [ring-U-¹⁴C]-4-(3′,5′-dimethyl-3′-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [¹⁴C]-4-353-NP were 1 mg L^?1 (soybean), and 5 and 10 mg L^?1 (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19–22% (soybean) and 21–42% of applied ¹⁴C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6′-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

Rhodobacter sp. NP25b菌株缺氧降解壬基酚聚氧乙烯醚的研究

从城市污水处理厂活性污泥中分离得到一株能够在缺氧条件下以壬基酚聚氧乙烯醚(NPEOs)为惟一碳源和能源生长的菌株NP25b.经生理生化鉴定和16S rRNA基因序列分析,该菌株属于红细菌属(Rhodobacter sp.),对该菌株降解NPEOs的特性进行了研究.结果表明,在缺氧条件下,菌株NP25b在7 d内对初始底物浓度为400 mg/L NPEOs的降解率可达84%.利用液相色谱-质谱(LC-MS)和气相色谱-质谱(GC-MS)对NPEOs降解中间产物进行了分析,结果表明,主要降解产物为短链NPEOs和壬基酚聚氧乙烯醚乙酸(NPECs),其中包括具有较强内分泌干扰效应的NP1EO.该菌株能够代谢含有疏水基团的聚氧乙烯醚类表面活性剂,例如辛基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚.推测菌株NP25b降解NPEOs是通过乙氧基(EO)链末端氧化后逐步切割完成的.     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

3种增塑剂单独和联合暴露对MCF-7细胞增殖的影响

为了探究结构差异较大、应用较为广泛的几类增塑剂雌激素活性的联合效应,选择邻苯二甲酸二丁酯(DBP)、双酚A(BPA)和壬基酚(NP)作为邻苯二甲酸酯、双酚A类和烷基酚类增塑剂的代表物进行试验.用DBP、BPA和NP单独及两两混合处理MCF-7细胞.采用MTT法检测培养24h、48 h、72 h和96h时的细胞增殖情况.采用流式细胞术检测药物培养48h后的细胞生长周期分布,并计算细胞增殖指数(PI).运用效应叠加模型(ES)判定联合效应类型.结果表明,在单独暴露试验中,DBP、BPA和NP组PI均大于1,且均能提高S期(DNA合成期)细胞比例.因此,DBP、BPA和NP均能显著促进MCF-7细胞增殖.混合暴露试验中,1)DBP和BPA在MTT试验中24h、48h、72 h和96h时的效应叠加指数(ESI)分别为1.013 9、1.023 8、0.9999、1.010 8,在流式细胞仪试验中ESI为1.014 1.因此,DBP和BPA的雌激素活性联合效应为加和作用.2)DBP和NP在MTT试验中24 h、48 h、72 h和96 h时的ESI分别为1.004 0、1.008 6、1.011 5、1.010 3,流式细胞仪试验中ESI为0.997 0.因此,DBP和NP的雌激素活性联合效应为加和作用.3)BAP和NP在MTT试验中24h、48 h、72 h和96h时的ESI分别为0.980 6、0.981 8、0.977 7、0.973 3,流式细胞仪试验的ESI为0.912 8.由此可知,BPA和NP的雌激素活性联合效应为拮抗作用.因此,可以采用MCF-7细胞增殖试验研究环境污染物雌激素活性联合效应.     

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.