Biotransformation of nonylphenol ethoxylates during sewage treatment under anaerobic and aerobic conditions

Biotransformation of nonylphenol ethoxylates （NPEOs） during continuous anaerobic sewage treatment was compared with the aerobic treatment of sewage spiked with 23 μmol/L technical NPEOs over a period of 90 d. Immediate degradation of NPEOs was observed under both anaerobic and aerobic conditions, indicating that the enzymes and bacteria required for NPEO degradation existed abundantly in both aerobic and anaerobic sludge. Both treatments achieved high removal （〉 92%） of the spiked NPEO9 mixture. Liquid chromatography-mass spectrometry （LC-MS） analysis showed that short-chain NPEOs （NPEO1-NPEO3） accumulated in anaerobic （2.01-2.56 μmol/L） and aerobic （1.62-2.03 μmol/L） effluents, with nonylphenol （NP） （0.24-0.31 μmol/L） as another group of metabolites in the anaerobic effluent, and nonylphenoxy carboxylates （NPECs） （2.79-3.30 μmol/L） in the aerobic effluent. Significant accumulation of NP in the anaerobic sludge and NPEO1-3 in the sludge of two reactors was observed. These results indicated that it was difficult to control these harmful metabolites in the conventional treatment processes. Denaturing gradient gel electrophoresis profiles of sludge samples support the speculation that the NPEO degradation bacteria might be the dominant indigenous species.

Mechanism study on UV-induced photodegradation of nonylphenol ethoxylates by intermediate products analysis

Photodegradation of nonylphenol ethoxylates （NPloEO） was investigated in laboratory scale under UV irradiation. The intermediate photodegradation products were analyzed by LC-ESI-MS. Three kinds of intermediate products including aldehydic compounds, carboxylic compounds and cyclohexanyl compounds were identified. Five main degradation routes involving the oxidation of the alkyl chain and ethoxylate unit, shortening of the alkyl chain and ethoxylate unit, hydrogenation of the benzene ring were proposed.

Vertical distribution of nonylphenol and nonylphenol ethoxylates in sedimentary core from the Beipaiming Channel, North China

The vertical profiles of nonylphenol （NP） and nonylphenol ethoxylates （NPEOs） were investigated in a sediment core from the Beipaiming Channel, North China using high sensitive LC-MS and GC-MS metthods In this core, relatively high concentrations of NP and NPEOs occurred in the surface sediment （≤40 cm）, with the maximum value of NP and NPEOs reaching 3539 and 12735 mg/g, respectively, whereas, no NP or NPEOs were detected in deeper sediments （〉40 cm）. The high concentrations of NP and NPEOs in the surface layers suggested recent inputs in this area. NPEOs with short ethoxy chains （NPnEO, n=0-3） were dominant in the NPEO mixture with percentages from 54% to 78%, which were similar to the distribution of homolog NPEO in effluents from nearby sewage treatment plants （STPs）, indicating that the channel received the effluents from these STPs. The sewage treatment ratio was quite similar to that found in North America before the 1980s. Finally, the concentrations of NP and NPEOs were related to the total organic carbon （TOC） （p〈0.001）, suggesting that TOC was an important factor for vertical distribution of NPEOs and NP from the Beipaiming Channel.

A novel associative latex thickener using ethoxylated behenyl methacrylate as functional monomer

Alkali-soluble associative latex thickeners modified with hydrophobic long chain alkyl groups were prepared using common acrylics and varying amount of a functional monomer,ethoxylated behenyl methacrylate(BEM),through emulsion polymerization.It was found that the size of the emulsion particle became larger with addition of BEM.The light transmittance of the thickener latex sharply increased with pH varied from 6 to 7.The associative latex thickener manifested a higher viscosity when solids in the latex thickeners were kept at 0.5 wt%or higher,and the optimal amount of BEM was found to be around 2.5 wt%,or 0.16 mol%.All thickener latexes modified with BEM have better shearing resistance than the BEM-free thickener.

Degradation behaviors of nonylphenol ethoxylates by isolated bacteria using improved isolation method

Nonylphenol ethoxylate (NPEO)-degrading bacteria were isolated from activated sludge using an improved isolation method, and the corresponding degradation behaviours were investigated. Eight NPEO-degrading strains distributed in genera Pseudomonas, Sphingomonas, Sphingobium, Cupriavidus, Ralstonia, Achromobacter, and Staphylococcus were acquired. The latter five genera have never been reported for the degradation of NPEOs. Four degradation patterns were observed for the eight pure strains. In pattern A, NPE...

Polyethoxylation and polypropoxylation reactions：Kinetics,mass transfer and industrial reactor design

Ethoxylation and propoxylation reactions are performed in the industry to produce mainly non-ionic surfactants and ethylene oxide(EO)–propylene oxide(PO) copolymers.Both the reactions occur in gas–liquid reactors by feeding gaseous EO,PO or both into the reactor containing a solution of an alkaline catalyst(KOH or Na OH).Non-ionic surfactants are produced by using liquid starters like fatty alcohols,fatty acids or alkyl-phenols,while when the scope is to prepare EO–PO copolymers the starter can be a mono-or multi-functional alcohol of low molecular weight.Both reactions are strongly exothermic,and EO and PO,in some conditions,can give place to runaway and also to explosive side reactions.Therefore,the choice of a suitable reactor is a key factor for operating in safe conditions.A correct reactor design requires:(i) the knowledge of the kinetic laws governing the rates of the occurring reactions;(ii) the role of mass and heat transfer in affecting the reaction rate;(iii) the solubility of EO and PO in the reacting mixture with the non-ideality of the reacting solutions considered;(iv) the density of the reacting mixture.All these aspects have been studied by our research group for different starters of industrial interest,and the data collected by using semibatch well stirred laboratory reactors have been employed for the simulation of industrial reactors,in particular Gas–Liquid Spray Tower Loop Reactors.

Reuse of Ferric Sludge by Ferrous Sulfide in the Fenton Process for Nonylphenol Ethoxylates Wastewater Treatment

In this paper, Fenton process was determined to be an effective technique to treat the refractory Nonylphenol ethoxylates (NPEOs) wastewater. The COD removal efficien-cies above 89% were obtained when the initial COD concentration was 12000mg/L. However, A large number of ferric sludge (SS=8.724g/L) would be produced after the Fenton oxidation of the wastewater and must be disposed appropriately. A novel process for Fenton sludge reused by low-cost ferrous sulfide (FeS) was also investi-gated. Experimental results show that the Fenton sludge could be reduced to produce a certain amount of Fe2+ in the acidic mixed liquor by ferrous sulfide. This mixed liquor from Fenton sludge could be used as the new catalyst in the Fenton process and was also highly effective for the NPEOs wastewater treatment. The residual ferrous sulfide from the mixed liquor could be used for the next batch of the

A novel application of horseradish peroxidase:Oxidation of alcohol ethoxylate to alkylether carboxylic acid

A novel application of horseradish peroxidase （HRP） in the oxidation of alcohol ethoxylate to alkylether carboxylic acid in the present of H2O2 was reported in this paper. We propose the mechanism for the catalytic oxidation reaction is that the hydrogen transfers from the substrate to the ferryl oxygen to form the α-hydroxy carbon radical intermediate. The reaction offers a new approach for further research structure and catalytic mechanism of HRP and production of alkylether carboxylic acid.

Treatment of the High Concentration Nonylphenol Ethoxylates (NPEOs) Wastewater by Fenton Oxidation Process

The Fenton oxidation process was applied in the treatment of an actual high concentration nonylphenol Ethoxylates (NPEOs) wastewater. The effects of H2O2 dosage, molar ratio of H2O2/Fe2+ (Fe2+ dosage), pH value and reaction time on the degradation of NPEOs were investigated. The orthogonal experiment indicated that the order of degree of influence on the COD removal was molar ratio of H2O2/Fe2+, reaction time, dosage of H2O2, and initial pH. The single-factor tests were carried out to determine the optimal conditions, and the results were H2O2 dosage of 76.32 mmol/L, molar ratio of H2O2/Fe2+ of 3, pH value of 5 and reaction time of 2 h. Under the optimum operation conditions, the COD removal efficiency was 85.6% and the effluent could be mixed with other wastewater into the large-scale biological treatment system.

The Colour Reaction of Mercury with 1-(6-Ethoxyl-2-benzothiazolyl)-3-(4-Nitrophenyl)-Triazene and its Application

A new triazene reagent 1-(6-ethoxyl-2-benzothiazolyl)-3-(4-nitrophenyl)-triazene (EtOBThTPT) has been synthesized. The colour reaction of EtOBTNPT with Hg(II) has been studied. At pH = 10.1-10.7, in the presence of Triton X-100, the reagent with Hg(II) forms an orange-yellow complex with high sensitivity. The molar absorptivity is 2.38 X 10(5) L.mol(-1).cm(-1). Beer's law is obeyed for Hg(II) in the range of 0-7 mu g/25 ml.

Investigation of Propoxylation and Ethoxylation of 2-Ethylhexanol in the Presence of an Alkaline and DMC Type Catalyst at Initial Stages of the Syntheses

This paper reports the results of monopropoxylation and monoethoxylation of ethylhexyl alcohol performed in the presence of KOH and a DMC type catalyst, respectively. The existing differences are discussed in terms of kinetic performance of the syntheses, as well as the obtained products＇ compositions. The investigated DMC type catalyst showed 60 to 70 times as high conversion rates, narrower homolog distributions and higher selectivity, in comparison with KOH. Interpretation of the experimental results was performed using kinetic parameters of the WeibulI-Nycander-Gold model and the Natta Mantica relationships. In spite of any differences between the reactivity of the investigated catalysts and alkylene oxides, a significant contribution ofpolymerisation parallel to the target polyaddition was determined, absorbing a major part of the converted adducts, both in the presence of DMC and KOH.

Biodegradation of Nonylphenol Ethoxylates in the Continuous Flow Activated Sludge Simulation Test

Biodegradation of representative nonylphenol ethoxylates, NP10EO, was investigated in the continuous flow activated sludge simulation test; the effect of hydraulic retention time （HRT） on its biodegradation was examined. The primary biodegradation degree of NP10EO was 96.5% at 3 hours hydraulic retention time and 96.2% at 6 hours hydraulic retention time; the ultimate biodegradation degree, which was 84.8% and 87.3%, respectively, indicated that the primary biodegradation of NP10EO was very easy and most NP10EO can be biodegraded ultimately, the prolonging of HRT had no infuence on the primary biodegradation and little infuence on the ultimate biodegradation. The possible biodegradation pathways of NPnEO, especially the biodegradation pathways of benzene ring in NPnEO, were proposed through Electrospray ionization-mass spectrometry analysis.

A Simplified Analytical Procedure for Simultaneous Determination of Alkylphenol Ethoxylates and Brominated Flame Retardants in Fish Tissue Samples from Vaal River,South Africa

In this study, the concentration of alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) were determined in fish samples, Labeo umbratus and Carp, collected from the Vaal River in South Africa. Ultrasonic-assisted extraction technique was used to extract the organic contaminants from fish samples, and the resulting extract was purified by sulphuric acid lipid removal followed by Strata X-cartridge SPE clean-up. The APEs and BFRs were derivatized using heptafluorobutyric anhydride before analysis with GC-MS. In both types of fish samples, lower oligomers of APEs were more abundant than the higher oligomers, while HBCD, BDE99 and PBB101 were the dominant BFRs. The concentrations of these pollutants ranged from 1.061 ng/g lipids (t-BP) in Labeo umbratus to 11.860 ng/g lipids (HBCD) in Carp.

Comparative toxicity study of a novel non-ionic surfactant,vanillin ethoxylates, and nonylphenol ethoxylates in Chinese hamster ovary cells in vitro

Surfactants such as alkylphenol polyethoxylates(APEOs) and nonylphenol ethoxylates(NPEOs) are commonly used worldwide, but the majority of these compounds, together with their metabolites, have been reported to induce severe biological toxicity. Here, we evaluated for the first time the cytotoxicity,genotoxicity and mitochondrial damage in Chinese hamster ovary(CHO-K1) cells caused by a novel non-ionic surfactant, vanillin ethoxylates(VAEOs), an alternative to APEOs. In parallel, the same in vitro bioassays were conducted on NPEOs along with their metabolic byproducts 4-nonylphenol(4-NP) and vanillin. The results showed that the cytotoxic potency order was NPEOs > 4-NP > VAEOs>vanillin using CCK-8 assays. Also, 4-NP showed potential direct DNA damage in SOS/umu tests, whereas NPEOs, VAEOs and vanillin showed no positive result with and without S9 addition. In addition, none of the test compounds showed obvious genotoxic effects with low olive tail moment value using comet assays. However, all test compounds were shown to cause mitochondrial impairment by increasing mitochondrial mass and decreasing mitochondrial membrane potential in a concentration-dependent manner. And further analysis of reactive oxygen species(ROS) and mitochondrial superoxide(MNSOD)measurement showed that mitochondrial impairment was induced by oxidative stress with intracellular ROS and MNSOD overproduction. It's worth noting that VAEOs and vanillin cause relative lower cytotoxic, genotoxic and mitochondrial damage effects than NPEOs and 4-NP, indicating that VAEOs have the potential to substitute NPEOs as suitable surfactants. Take together, this study elucidates the toxicity profiles of VAEOs and NPEOs relatively comprehensively, and further toxicity analyses are suggested in the population, community and ecosystem.

丁炔二醇乙氧基化合物对镍锰镀层的影响

为了获得平整的镍锰合金镀层,在瓦特型镀液中研究了糖精存在下丁炔二醇乙氧基化合物(BEO)对Ni-Mn镀层性能的影响规律。通过线性扫描伏安法探究了BEO对阴极极化的影响,并对电沉积Ni-Mn镀层的表面形貌、晶体结构和显微硬度进行了表征,讨论了Ni-Mn镀层结构和性能变化的可能机制。结果表明:BEO的加入使阴极极化电位向更负的方向偏移,显著抑制金属离子的阴极还原反应,细化了晶粒,有助于获得平整、高显微硬度的镀层。对比经300℃退火后Ni-Mn镀层的硬度和结构发现,从含BEO镀液中获得的镀层的晶粒粗化趋势较小,退火硬化更为明显。

羟乙基乙二胺的连续流制备工艺

以乙二胺和环氧乙烷为原料,在具有特殊微结构的连续流微反应器内发生乙氧基化反应合成羟乙基乙二胺。考察了原料物质的量比、乙二胺含水量、反应温度、停留时间对反应的影响。结果表明,在n(乙二胺)∶n(环氧乙烷)=3∶1、乙二胺含水量为0.96%(质量分数)、反应温度为80℃、停留时间为60 s的最佳工艺条件下,环氧乙烷转化率接近100%,羟乙基乙二胺的选择性为87.4%,二羟乙基乙二胺的选择性为9.2%。间歇釜式反应工艺在相同物料比和反应温度条件下,羟乙基乙二胺的选择性为83.5%,二羟乙基乙二胺的选择性为15.9%。连续流微反应器能有效提高羟乙基乙二胺的选择性,降低副反应的发生,同时大大缩短了反应时间,提高了反应效率。

脂肪胺窄分布乙氧基化物的合成及其性能研究

采用催化剂KOH、SnCl_(4)、实验室自制弱碱性非均相催化剂(NHGC)催化十二脂肪胺与环氧乙烷的乙氧基化反应,合成了加合数为5的十二胺聚氧乙烯醚(DAEO_(5))。根据文献报道,催化剂的种类会直接影响产物的分子量分布。因此通过分析不同催化体系制备的DAEO_(5),并对其分子量分布宽窄、表面活性剂溶液的表面张力、理化性质和应用性能进行了研究。研究结果表明,与传统的乙氧基化催化剂相比,NHGC制备的DAEO_(5)具有较窄的低聚物分布和较低的游离胺含量,且产品的黏度和水溶液的浊点较其他产品都较高。利用不同催化体系合成的DAEO_(5)的∆G_(mic)和∆G_(mic)均小于0,表明DAEO_(5)能在水中自发形成胶束和吸附层。NHGC合成产品的润湿性和乳化性能较好,其润湿时间远低于用KOH和SnCl4作为催化剂合成的产品。不同催化剂合成产品去污能力相差不大,但是不同催化体系合成的相同EO加合数的DAEO对于炭黑污布的去污能力比对皮脂污布的去污能力强。

Occurrence and fate of endogenous steroid hormones,alkylphenol ethoxylates, bisphenol A and phthalates in municipal sewage treatment systems

Steroid hormones, alkylphenol ethoxylates（APEOs） and phthalic acid esters（PAEs） are emerging endocrine disrupting chemicals（EDCs） that can interfere with the endocrine function in organisms at low concentrations. The occurrence, distribution behavior, removal rate and the fate of 31 target EDCs in sewage treatment plants, which consist of various treatment facilities and receiving water in Hong Kong, were investigated. Estrone,nonylphenol-di-ethoxylate and diethyl phthalate were found to be dominant in each group of influent samples with concentrations ranging from 11–33, 747–3945 and 445–4635 ng/L,respectively. Conversely, progesterone, nonylphenol-mono-ethoxylate and bis（2-ethylhexyl）phthalate were the most abundant in dewatered sludge, with concentrations ranging from 0.9–237, 75–19,743 and 4310–37,016 ng/g（dry weight）. The removal rates of primary sedimentation and disinfection approaches were lower than 30% for most of the chemicals,while those of activated sludge and reverse osmosis were greater than 80% for more than two-thirds of the compounds, noticeably decreasing the estrogenic risk of sewage discharged into the environment. Steroid hormones were removed via biological degradation, while some APEOs and PAEs adsorbed to the sludge. Victoria Harbor poses a low to medium estrogenic risk mainly contributed by estrone and estradiol and deserves attention.

壬基环己醇聚氧乙烯醚硫酸钠的合成及性能

壬基酚聚氧乙烯醚硫酸钠具有水生毒性而亟需开发其替代物。壬基环己醇聚氧乙烯醚由于安全性较高,且理化性能与壬基酚聚氧乙烯醚接近,是壬基酚聚氧乙烯醚潜在的替代物。以壬基环己醇聚氧乙烯醚为原料、氯磺酸为硫酸酯化试剂,合成了壬基环己醇聚氧乙烯醚硫酸钠,其中壬基环己醇聚氧乙烯醚(5)硫酸钠和壬基环己醇聚氧乙烯醚(9)硫酸钠(5和9分别为其环氧乙烷加成数)的酯化率分别可达90.91%和91.06%。结果表明,壬基环己醇聚氧乙烯醚(5)硫酸钠水溶液与脂肪醇聚氧乙烯醚(3)硫酸钠(AES)具有相近的表界面活性。合成产物壬基环己醇聚氧乙烯醚硫酸钠具有和壬基环己醇聚氧乙烯醚相当的润湿及泡沫性能,比AES具有更好的润湿、泡沫及乳化性能。

Seasonal variations in the concentration and removal of nonylphenol ethoxylates from the wastewater of a sewage treatment plant

In this study, we investigated the occurrence and fate of nonylphenol（NP）, nonylphenol monoethoxylate（NP1EO） and nonylphenol diethoxylate（NP2EO） in a full scale sewage treatment plant, which applied an Anaerobic/Oxic process. Concentrations of NP, NP1 EO and NP2 EO in the wastewater were measured during the period spanning a whole year.The results showed remarkable seasonal variation in the concentrations of the compounds.The NPn EO compounds were most abundant in winter, with the total concentrations of influent NP, NP1 EO and NP2 EO ranging from 3900 to 7000 ng/L, 4000 to 4800 ng/L and 5200 to 7200 ng/L, respectively. Regarding the total removal efficiencies of the three types of short-chain NPn EO compounds, different trends were exhibited according to different seasons. The average removal efficiency of NP for the different seasons ranked as follows：winter 〉 summer 〉 autumn 〉 spring; NP2 EO concentrations decreased as follows： summer 〉autumn 〉 winter 〉 spring, while NP1 EO concentrations reduced according to： spring 〉summer 〉 autumn 〉 winter. We also investigated the contribution ratio of individual treatment units in the A/O process, with the findings suggesting that the anaerobic treatment unit plays an important role in the elimination of short-chain NPn EOs from the wastewater.