Passive dosing: an approach to control mutagen exposure in the Ames fluctuation test

By using dialysis equilibrium experiments, the sorption of a branched nonylphenol isomer [4-(1-ethyl-1,3-dimethylpentyl)-phenol] (NP111) on various humic acids (HAs) isolated from river sediments and two reference HAs was studied. The HAs were characterized by solid-state ¹³C direct polarization/magic angle spinning nuclear magnetic resonance (¹³C DP/MAS NMR) spectroscopy. Sorption isotherms of NP111 on HAs were described by a linear model. The organic carbon-normalized sorption coefficient (K_OC) ranged from 2.3 × 10³ to 1.5 × 10⁴ L kg⁻¹. Interestingly, a clear correlation between K_OC value and alkyl C content was observed, indicating that the aliphaticity of HAs markedly dominates the sorption of NP111. These new mechanistic insights about the NP111 sorption indicate that the fate of nonylphenols in soil or sediment depends not only on the content of HA, but also on its structural composition.     

两株壬基酚和双酚A高效降解菌株的筛选和降解特性

以桂林市上窑污水处理厂污泥脱水车间剩余污泥、上窑堆肥厂的堆肥堆料和桂林雁山镇森林土壤为菌源进行驯化,分离纯化并筛选得到2株能分别以壬基酚(NP)和双酚A(BPA)为唯一碳源和能源生长的降解菌株N-1和B-1。通过对菌株的16S r DNA序列同源性分析,初步鉴定N-1和B-1菌分别为Cupriavidus(贪铜菌属)、Acinetobacter(不动杆菌属)。通过两菌株分别降解NP和BPA的单因素实验,确定了降解动力学以及时间、温度、p H值对降解过程的影响。研究结果表明,细菌N-1,B-1的最佳初始目标污染物质量浓度为5~10 mg/L,降解40 h,N-1去除率可达49.63%,B-1去除率可达62.34%。细菌N-1对NP的去除半衰期t1/2为41.44~48.02 h;B-1对BPA的去除半衰期t1/2为35.23~37.33 h。细菌N-1,B-1的最佳降解温度均为30℃,最佳p H值均在6.5~7.5之间,即两种细菌在中温、中性条件下对NP和BPA降解效果最佳。     

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.     

光电催化降解壬基酚影响因素研究

采用sol-gel法制备TiO2薄膜光电极,以该电极为工作电极,铂丝作对电极,饱和甘汞电极为参比电极,对壬基酚的光电催化降解进行了研究。结果表明:该电极具有n型半导体的特征行为。在外加偏压为+0.8V、pH=5、、30mg/L的H2O2中对初始浓度为20mg/L的壬基酚溶液光照180min降解率达62.22%。讨论了氧的存在、外加偏压、pH等因素对光电催化反应的影响。     

壬基酚及其短链聚氧乙烯醚在污泥和土壤中的存在和降解

壬基酚聚氧乙烯醚(NPnEO)是广泛使用的表面活性剂．在污水处理厂中会降解为具有内分泌干扰效应的短链产物和最终产物壬基酚(NP)。剩余污泥是其进入环境的重要途径。介绍了NP和短链NPnEO在污泥中的存在情况、污泥处理过程对其存在的影响、以及这些物质随污泥处置过程进入土壤后的降解。     

夏季渤海表层沉积物中壬基酚和双酚A的分布特征与潜在生态风险

分析了渤海表层沉积物中壬基酚和双酚A的分布特征。结果表明,壬基酚的含量介于(3.16～13.6)×10-9(dw),高值区出现在渤海湾近岸,其次为辽东半岛近岸和莱州湾近岸,其它海区的含量均低于7.50×10-9(dw),且变化幅度较小。渤海沉积物中的双酚A含量普遍较低,介于(ND～1.44)×10-9(dw),高值区出现在辽东湾近岸。壬基酚和双酚A的含量分布受到陆源输入、环流体系及沉积环境等因素的共同影响。本文还讨论了渤海中壬基酚和双酚A的潜在生态风险。     

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge

IntroductionRecently ,nonylphenolpolyethoxylates (NPnEO (n :numberofethoxyunits(EOs) )havebecomeaproblematicissueforthereasonthatthesecompounds,animportantgroupofnonionicsurfactants ,havebeenusedwidelyinvariousindustriesasflocculants,dispersants,emulsifie…     

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.     

1株异养脱氮菌降解壬基酚聚氧乙烯醚的研究

研究了异养脱氮菌Bacillus sp.LY降解壬基酚聚氧乙烯醚(NPEOs)的性能.结果表明,该菌株具有较强地降解NPEOs的能力,且在实现NPEOs降解去除的同时表现出一定的异养脱氮性能.降解14d后, Bacillus sp.LY对NPEOs去除率达95.6%,对体系中的总氮去除率为43.9%.该菌株对NPEOs的降解去除符合一级动力学特征,其降解速率常数为0.224d-1.该菌株通过无氧化过程的乙氧基链的逐渐缩短的途径降解去除NPEOs,可避免产生危害性更大的NPEOs的羧酸化产物(NPECs).在分别以氨态氮(NH4C1)、硝态氮(NaNO3)和亚硝态氮(NaNO2)3种不同氮素为氮源的条件下,菌株对NPEOs均具有一定的降解效果,其中以氨态氮为氮源时菌株对NPEOs降解效果最好.研究结果可为消除壬基酚聚氧乙烯醚与氮素复合污染提供理论依据.