城市污泥与促腐剂堆肥中壬基酚类物质的研究

城市污泥中富含具有内分泌干扰活性的壬基酚(NP)和短链壬基酚聚氧乙烯醚(NP2EO、NP1EO)。污泥堆肥土地利用是国内外城市污泥最重要的处置方式。通过在污泥中添加促腐剂后堆肥发酵,进行了壬基酚类物质的变化研究,研究发现:从壬基酚二氧乙烯醚(NP2EO)、壬基酚单氧乙烯醚(NP1EO)和NP这3种物质总量的降解效果来看,好氧发酵优于厌氧发酵;好氧发酵过程中添加促腐剂对消除壬基酚和壬基酚聚氧乙烯醚(长链NPnEO,短链NP2EO、NP1EO)类物质是有利的。对污泥中壬基酚类物质的污染控制具有一定的指导意义。     

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.     

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。     

壬基酚聚氧乙烯醚在膜-生物反应器中的归趋

综述了环境内分泌干扰物壬基酚聚氧乙烯醚的化学性质、环境释放机制以及其对环境构成的危害,归纳了壬基酚及其短链聚氧乙烯醚（NPnEO）在膜-生物反应器（MBR）中的迁移转化规律,分析了其生物降解性和降解机理,探讨了MBR中活性污泥对其吸附能力和膜的截留能力,讨论了包括厌氧或好氧条件下的温度、水力停留时间、污泥停留时间等因素对于其降解过程的影响。     

预处理-水解酸化-厌氧-好氧工艺对玉米淀粉废水有机污染物的降解

采用气相色谱/质谱(GC/MS)、三维荧光光谱(EEM)等检测手段分析预处理/水解酸化/厌氧/好氧组合工艺对玉米淀粉废水有机污染物的降解情况。结果表明,竖流沉淀预处理阶段对TOC平均去除率36.7%,废水中主要为芳烃、烷烯烃以及杂环类物质,EEM产生的5个荧光峰均为芳香蛋白类有机物;水解酸化阶段大部分杂环以及芳烃类有机物水解成有机酸和醇类物质,TOC平均去除率22.7%;厌氧阶段TOC平均去除率最高,达到97.8%,废水中以芳烃和烷烯烃为主,荧光峰减少至2个且强度减弱;好氧阶段TOC平均去除率为61.3%,有机物主要为难降解的长链烷烃物质,芳香蛋白类有机物荧光峰全部消失,新生成了与微生物代谢相关的腐殖酸类物质。     

水解酸化工艺处理印染废水的机理

为了研究水解酸化工艺处理印染废水机理及其必要性,尝试用分子量及其分布和聚乙烯醇(PVA)降解程度作为论证指标,并综合后续好氧生物处理。提出以VFA产生和p H显著下降作为印染废水水解酸化的评判标准是不适用的;印染废水水解酸化的作用主要在水解阶段,COD虽没有明显降低,但分子量和PVA随着反应过程有显著下降;印染废水水解酸化可以大大降低好氧生物处理的难度,经过水解酸化的印染废水比未经水解酸化的印染废水好氧生物处理后COD去除率高40.2%,分子量下降率高66.2%。     

染料废水处理技术的研究与进展

概述了含染料废水处理方法的研究现状和最新进展 ,尤其是在物化法 (包括辐射法、吸附 萃取法、磁分离法、混凝沉降法和氧化法 )、生物法 (好氧 厌氧氧化 -还原序列反应器、固定化微生物降解、膜生物反应器 )及生物 -物化联合法 (生物吸附剂、生物活性炭、厌氧折流板反应池 -生物接触氧化池 -混凝沉淀 -砂滤池处理工艺、水解酸化 -接触氧化法等 )中的新技术的研究现状 ,新方法、材料、工艺的应用方面 ,对提高此类废水的处理效果有重要的理论和实际意义     

染料废水处理技术的研究与进展

概述了含染料废水处理方法的研究现状和最新进展，尤其是在物化法(包括辐射法、吸附，萃取法、磁分离法、混凝沉降法和氧化法)、生物法(好氧，厌氧氧化—还原序列反应器、固定化微生物降解、膜生物反应器)及生物—物化联合法(生物吸附剂、生物活性炭、厌氧折流板反应池—生物接触氧化池—混凝沉淀—砂滤池处理工艺、水解酸化—接触氧化法等)中的新技术的研究现状，新方法、材料、工艺的应用方面，对提高此类废水的处理效果有重要的理论和实际意义。     

厌氧滤池处理纺织印染废水的中试研究

对厌氧滤池反应器处理难降解印染废水进行中试研究。结果表明,厌氧滤池反应器水力停留时间(HRT)在8.1～14.6 h之间,进水COD浓度波动较大(500～1 000 mg/L)时,对COD平均去除率为20%。印染废水的BOD5/COD由0.23提高到0.35,废水可生化性明显改善。印染废水中硫酸根浓度略有下降,去除浓度为70 mg/L左右。厌氧滤池进出水颜色明显变化,由紫红色变为蓝黑色,紫外可见光谱分析表明废水中的有机物结构发生变化。     

印染废水处理过程中污染物及毒性分析

应用水解酸化-A/O(生物活性炭法(PACT))-混凝沉淀组合工艺处理印染废水,深入研究该组合工艺各反应段对印染废水污染物的处理情况,分别用电感耦合等离子光谱(AES/ICP)、气相色谱/质谱联用(GC/MS)以及发光细菌法对各反应段出水所含金属元素、有机物以及毒性进行检测.结果表明,水解酸化-A/O(PACT)-混凝沉淀组合工艺可以有效降解印染废水所含污染物,降低其毒性.     

Anaerobic degradation behavior of nonylphenol polyethoxylates in sludge

Anaerobic biodegradation behavior of nonylphenol polyethoxylates (NPEOs) was investigated. Results showed that terminal electron acceptors, organic matters, initial concentration, and temperature had great influence on the anaerobic biodegradation of NPEOs. Anaerobic biodegradation of NPEOs could be enhanced by adding sulfate or nitrate while this process could be inhibited by adding organic matters. The maximum removal rate increased 1.24 microM d(-1) for each ten micromoles increase in initial concentration. The decrease in temperature caused a sharp decrease in the removal efficiency of NPEOs. The temperature coefficient (PHI) for the anaerobic biodegradation of NPEOs was 0.01 degrees C(-1). Nonylphenol (NP), the typical intermediate of NPEOs, could inhibit the anaerobic biodegradation of NPEOs only at high concentration. However, these environmental factors had no effect on the anaerobic biodegradation pathway of NPEOs. The accumulation of NP and short-chain NPEOs during NPEO biodegradation led to a significant increase in the estrogenic activity during the biodegradation period.     

Biodegradation of nonylphenol polyethoxylates under Fe(III)-reducing conditions

Biodegradation behavior of nonylphenol polyethoxylates (NPEOs) under Fe(III)-reducing conditions was investigated. The study demonstrated that NPEOs could be rapidly biodegraded under Fe(III)-reducing conditions. Almost 60% of the total NPEOs were removed within three days and the maximum biodegradation rate was 34.95+/-0.84 microM d(-1). NPEOs were degraded via sequential removal of ether units under Fe(III)-reducing conditions. No nonylphenol polyethoxy-carboxylates (NPECs) were formed in this process. This ether removal process was coupled to Fe(III) reduction. Nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) slightly accumulated in the anaerobic biodegradation process. The accumulation of these estrogenic metabolites led to a significant increase in the estrogenic activity during the biodegradation period. The calculated estrogenic activity reached its top on day 14 when the total concentration of these estrogenic metabolites was maximal. This is the first report of the primary biodegradation behavior of NPEOs under Fe(III)-reducing conditions. These findings are of major environmental importance in terms of the environmental behavior of NPEO contaminants in natural environment.     

Determination of nonylphenol ethoxylates and octylphenol ethoxylates in environmental samples using 13C-labeled surrogate compounds

Alkylphenol polyethoxylates (APEOs) have been widely used as nonionic surfactants in a variety of industrial and commercial products. Typical compounds are nonylphenol polyethoxylates (NPEOs) and octylphenol polyethoxylates (OPEOs), which serve as precursors to nonylphenol (NP) and octylphenol (OP), respectively. NP and 4-t-OP are known to have endocrine disrupting effects on fish (medaka, Oryzias latipes), so it is important to know the concentrations of APEOs in the environment. Because the analytical characteristics of these compounds depend on the length of the ethoxy chain, it is necessary to use appropriate compounds as internal standards or surrogates. We synthesized two 13C-labeled surrogate compounds and used these compounds as internal standards to determine NPEOs and OPEOs by high-performance liquid chromatography (LC)-mass spectrometry. Method detection limits were 0.015 microg/L for NP (2)EO to 0.037 microg/L for NP(12)EO, and 0.011 microg/L for OP(3,6)EO to 0.024 microg/L for OP (4)EO. NPEO concentrations in water from a sewage treatment plant were less than 0.05-0.52 microg/L for final effluent and 1.2-15 microg/L for influent. OPEO concentrations were less than 0.05-0.15 microg/L for the final effluent and less than 0.05-1.1 microg/L for influent.     

Determination and distribution characteristics of degradation products of nonylphenol polyethoxylates in the rivers of Taiwan

Concentrations of degradation products of nonylphenol polyethoxylates (NPEOs) were analyzed in river water samples in order to determine the distribution characteristic of these alkylphenolic compounds in 18 major rivers of Taiwan. The degradation products of NPEOs were detected in all river samples, with the dicarboxylates alkylphenolic degradation products (CAPEC) being detected most frequently and at the highest concentrations. Concentrations of NP and NP1EO in rivers ranged from n.d. to 5.1 μg l⁻¹ and n.d. to 0.5 μg l⁻¹, respectively. The total concentrations of shortened carboxylates (i.e., NP1EC + NP2EC + NP3EC) and dicarboxylates alkylphenolic degradation products (CAP1EC + CAP2EC) ranged from n.d. to 63.6 μg l⁻¹ and n.d. to 94.6 μg l⁻¹, respectively. Concentrations of NP2EC, NP3EC and all CAPEC residues were determined semi-quantitatively by comparing with the internal standard. Significantly higher concentrations of CAPEC residues were detected in the river waters as compared to those of NP, NP1EO and NPEC degradation products and the average proportions of these compounds in the samples of the rivers were as follows: NP + NP1EO was 5 ± 2.5%, total NPEC was 25 ± 12%, and total CAPEC was 70 ± 12%. The high concentration ratios of CAPEC/NPEC illustrate that aerobic biodegradation plays a main route in the fate of NPEO in the rivers of Taiwan.     

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.     

Degradation pathways of low-ethoxylated nonylphenols by isolated bacteria using an improved method

Nonylphenol ethoxylates (NPEOs) with low ethoxylation degree (NP_av2EO; containing two ethoxy units on average) and estrogenic properties are the intermediate products of nonionic surfactant NPEOs. To better understand the environmental fate of low-ethoxylated NPEOs, phylogenetically diverse low-ethoxylated NPEO-degrading bacteria were isolated from activated sludge using gellan gum as the gelling reagent. Four isolates belonging to four genera, i.e., Pseudomonas sp. NP522b in γ-Proteobacteria, Variovorax sp. NP427b and Ralstonia sp. NP47a in β-Proteobacteria, and Sphingomonas sp. NP42a in α-Proteobacteria were acquired. Ralstonia sp. NP47a or Sphingomonas sp. NP42a, have not been reported for the degradation of low-ethoxylated NPEOs previously. The biotransformation pathways of these isolates were investigated. The first three strains (NP522b, NP427b, and NP47a) exhibited high NP_av2EO oxidation ability by oxidizing the polyethoxy (EO) chain to form low-ethoxylated nonylphenoxy carboxylates, and then further oxidizing the alkyl chain to form carboxyalkylphenol polyethoxycarboxylates. Furthermore, Sphingomonas sp. NP42a degraded NP_av2EO through a nonoxidative pathway with nonylphenol monoethoxylate as the dominant product.     

Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry

This work presents an LC–MS–MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [¹³C₆]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO’s behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 μg l⁻¹) to final effluent (4 μg l⁻¹), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 μg l⁻¹. In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 μg l⁻¹. Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 μg l⁻¹) and NP0-1EC (4.8 μg l⁻¹) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest.     

Solubility of nonylphenol and nonylphenol ethoxylates. On the possible role of micelles

The water solubility of nonylphenol (NP) has been estimated to be 4.9 +/- 0.4 mg/l corresponding to (2.22 +/- 0.18) x 10(-5) mol/l at 25 degrees C using shake flask and surface tension techniques. The low solubility in combination with an observed rather slow dissolution process will limit the leachability of NP in the terrestrial environment. Based on indirect evidence, it is suggested that NP, in contrast to nonylphenol ethoxylate (NPEO) with, e.g., 12 ethoxylate moieties, is not subject to micelle formation, and as such does not constitute a potential vehicle for the transport of hydrophobic pollutants in the environment. For NPEOs with a very high number of ethoxy moieties, e.g., 100, the compounds appear water soluble without micelle formation.     

Distribution characteristics of nonylphenolic chemicals in Masan Bay environments, Korea

To understand the distribution characteristics of nonylphenolics and sterols, samples such as in creek water, sea surface water, waste water treatment plant (WWTP) effluent water, sediment and mussel were collected and analyzed. The principal analytes are nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO), coprostanol (5beta) and cholestanol (5alpha). All these target pollutants showed 100% detection frequency in all of the samples analyzed. Total concentration of nonylphenolic compounds ranged from 334 to 3628ngl(-1) (average: 1331ngl(-1)) in creek water, from 15 to 36400ngl(-1) (average: 1013ngl(-1)) in sea surface water, from 131 to 2811ngg(-1) dry weight (average: 581ngg(-1) dry weight) in sediment and from 50.5 to 289ngg(-1) dry weight (average: 139ngg(-1) dry weight) in mussel. For water samples, levels of nonylphenolics determined in summer season were higher than those in spring season. Among them, nonylphenol and NP1EO was dominant in creek water and seawater, respectively. The highest concentration was recorded in sediment near a WWTP effluent outlet. And high levels of nonylphenolics and sterols were found in about 3km area surrounding WWTP effluent outlet. Coefficient of linear regression (R(2)) for NP in mussel and in sediment was 0.90. Similarly good correlation (R(2)=0.98) was obtained between concentration in water and in mussel indicating that a steady state has been reached in this bay. The calculated bio concentration factor (BCF=2990) for NP in Masan Bay agrees well with reported values in the literature.     

Removal of a broad range of surfactants from municipal wastewater--comparison between membrane bioreactor and conventional activated sludge treatment

Elimination of alkylphenol ethoxylates (APEO) and their degradation products (alkylphenols and alkylphenoxy carboxylates), as well as linear alkylbenzene sulfonates (LAS) and coconut diethanol amides (CDEA), was studied in a pilot plant membrane bioreactor (MBR) working in parallel to a full-scale wastewater treatment plant (WWTP) using conventional activated sludge (CAS). In the CAS system 87% of parent long ethoxy chain NPEOs were eliminated, but their decomposition yielded persistent acidic and neutral metabolites which were poorly removed. The elimination of short ethoxy chain NPEOs (NP(1)EO and NP(2)EO) averaged 50%, whereas nonylphenoxy carboxylates (NPECs) showed an increase in concentrations with respect to the ones measured in influent samples. Nonylphenol (NP) was the only nonylphenolic compound efficiently removed (96%) in the CAS treatment. On the other hand, MBR showed good performance in removing nonylphenolic compounds with an overall elimination of 94% for the total pool of NPEO derived compounds (in comparison of 54%-overall elimination in the CAS). The elimination of individual compounds in the MBR was as follows: 97% for parent, long ethoxy chain NPEOs, 90% for short ethoxy chain NPEOs, 73% for NPECs, and 96% for NP. Consequently, the residual concentrations were in the low mug/l level or below it. LAS and CDEA showed similar elimination in the both wastewater treatment systems that were investigated, and no significant differences were observed between the two treatment processes. Nevertheless, for all studied compounds the MBR effluent concentrations were consistently lower and independent of the influent concentrations. Additionally, MBR effluent quality in terms of chemical oxygen demand (COD), NH(4)(+) concentration and total suspended solids (TSS) was always superior to the ones of the CAS and also independent of the influent quality, which demonstrates high potential of MBRs in the treatment of municipal wastewaters.