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。     

Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) and phenolic endocrine disrupting chemicals in South and Southeast Asian mussels

A comprehensive monitoring survey for polycyclic aromatic hydrocarbons (PAHs) and phenolic endocrine disrupting chemicals (EDCs) utilizing mussels as sentinel organisms was conducted in South and Southeast Asia as a part of the Asian Mussel Watch project. Green mussel (Perna viridis) samples collected from a total of 48 locations in India, Indonesia, Singapore, Malaysia, Thailand, Cambodia, Vietnam, and the Philippines during 1994–1999 were analyzed for PAHs, EDCs including nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), and linear alkylbenzenes (LABs) as molecular markers for sewage. Concentrations of NP ranged from 18 to 643 ng/g-dry tissue. The highest levels of NP in Malaysia, Singapore, the Philippines, and Indonesia were comparable to those observed in Tokyo Bay. Elevated concentrations of EDCs were not observed in Vietnam and Cambodia, probably due to the lower extent of industrialization in these regions. No consistent relationship between concentrations of phenolic EDCs and LABs were found, suggesting that sewage is not a major source of EDCs. Concentrations of PAHs ranged from 11 to 1,133 ng/g-dry, which were categorized as “low to moderate” levels of pollution. The ratio of methylphenanthrenes to phenanthrene (MP/P ratio) was >1.0 in 20 out of 25 locations, indicating extensive input of petrogenic PAHs. This study provides a bench-mark for data on the distribution of anthropogenic contaminants in this region, which is essential in evaluating temporal and spatial variation and effect of future regulatory measures.     

Contamination of nonylphenolic compounds in creek water, wastewater treatment plant effluents, and sediments from Lake Shihwa and vicinity, Korea: comparison with fecal pollution

Nonylphenolic compounds (NPs), coprostanol (COP), and cholestanol, major contaminants in industrial and domestic wastewaters, were analyzed in creek water, wastewater treatment plant (WWTP) effluent, and sediment samples from artificial Lake Shihwa and its vicinity, one of the most industrialized regions in Korea. We also determined mass discharge of NPs and COP, a fecal sterol, into the lake, to understand the linkage between discharge and sediment contamination. Total NP (the sum of nonylphenol, and nonylphenol mono- and di-ethoxylates) were 0.32-875 μg L⁻¹ in creeks, 0.61-87.0 μg L⁻¹ in WWTP effluents, and 29.3-230 μg g⁻¹ TOC in sediments. Concentrations of COP were 0.09-19.0 μg L⁻¹ in creeks, 0.11-44.0 μg L⁻¹ in WWTP effluents, and 2.51-438 μg g⁻¹ TOC in sediments. The spatial distributions of NPs in creeks and sediments from the inshore region were different from those of COP, suggesting that Lake Shihwa contamination patterns from industrial effluents differ from those from domestic effluents. The mass discharge from the combined outfall of the WWTPs, located in the offshore region, was 2.27 kg d⁻¹ for NPs and 1.00 kg d⁻¹ for COP, accounting for 91% and 95% of the total discharge into Lake Shihwa, respectively. The highest concentrations of NPs and COP in sediments were found in samples at sites near the submarine outfall of the WWTPs, indicating that the submarine outfall is an important point source of wastewater pollution in Lake Shihwa.     

Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (f_OC) ranging from 0.0035 to 0.082 g_OC g⁻¹. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.     

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.     

Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Metabolism of a nonylphenol isomer by Sphingomonas sp. strain TTNP3

For elucidation of the metabolism of the endocrine disruptor nonylphenol by Sphingomonas sp. strain TTNP3, the degradation of an isomer of nonylphenol, 4(2,6-dimethyl-2-heptyl)-phenol, has been studied. As in the case of 4(3,5-dimethyl-3-heptyl)-phenol, the metabolism of this nonylphenol isomer leads to the formation of the NIH-shifted product 2(2,6-dimethyl-2-heptyl)-1,4-benzenediol (NIH: National Institute of Health), but also to the alkoxy derivative 4(2,6-dimethylheptan-2-yloxy)phenol as additional metabolite. To the best of our knowledge, this is the first report describing the formation of alkoxyphenol as a degradation product of nonylphenol. Additionally, these results provide for the first time evidence for slight differences in the biodegradation of the isomers of nonylphenol.     

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.     

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。     

天津野生鲫鱼体内壬基酚聚氧乙烯醚和壬基酚监测

采用GCB固相萃取作为净化方法 ,利用LC ESI MS技术测定鱼体内不同聚合度壬基酚聚氧乙烯醚 (NPnEO ,n≥ 3) ;用GC MS技术测定NP和NPnEO(n <3) .此方法与传统的氧化铝法相比较 ,GCB固相萃取作为净化方法的回收率较高 ,不同聚合度的NPnEO回收率为 70 4 %— 12 0 % ;方法检测限为 1ng g.用此方法调查了北京排污河中鲫鱼体内的NPnEO的残留情况 ,在所捕获的 12条鲫鱼中均检出了不同浓度的NPnEO和NP .NPnEO在北京排污河天津段鱼体内的残留浓度为 4 0— 6 80ng g ,NP的浓度在 30— 15 10ng g ,和水体中浓度之间的比值分别为 898和 94倍 .