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.

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...

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.

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.

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 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.

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.

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.

Alkylphenols and alkylphenol ethoxylates in dust from homes, offices and computer laboratories: Implication for personal exposure via inadvertent dust ingestion

In the present study,the levels of alkylphenols(APs)and alkylphenol ethoxylates(APEs)in indoor dust of three different microenvironments were measured and daily intake via dust ingestion estimated.Alkylphenols and alkylphenol ethoxylates were extracted with the aid of sonication and analyzed by gas chromatography mass spectrometry after heptafluorobutyric anhydride derivatization.The concentration values of these pollutants ranged from 1918e10935 ng g
1;343e12438 ng g
1 and 1122 e15324 ng g
1 in dust samples from homes,computer laboratories and offices,respectively.In all the microenvironment studied,di-NPE and mono-NPE were the most abundant isomers suggesting widespread use of NPE-based consumer products in the studied microenvironments.The daily exposure dose(DED)was estimated using min,mean and max concentrations of APs and APEs detected in respected microenvironments.The worst case scenario for the exposure of APEs was highest for toddlers at 146 ng kg
1 bw day
1 followed by teenagers at 11.3 ng kg
1 bw day
1 and adults at daily exposure of 8.53 ng kg
1 bw day
1.Though the daily exposure doses are low,there is a cause for concern as these surfactants are not regulated in many developing countries and their use may be increasing.

Development of Anti-Wear/Antioxidant Additives for High Quality Metalworking Fluid from Waste Petroleum Products

Surfactants are used for formulation metal working fluids. These fluids are applied to the interface between a cutting tool and the metal working piece to provide friction reduction. In the present paper, poly aromatic ammonium sulphonate and polyaromatic benzyl triethanolamsonium ethoxylate with 6 ethylene oxide units were synthesized and blended with coupling agent like dodecyl alcohol and oleic acid to produce cutting fluid and evaluate as antiwear. Values of surface tension of these additives were measured in oil phase and consequently CMC was determined for all additives and their mixtures in oil phase. The efficiency of these additives depends on their chemical structure and the presence of ether oxygen brings about the association of the surfactant with metal surface, hence very good wetting properties. The antiwear characteristic of surfactants increases with increasing polar linkages in the aromatic moieties forming chelated and coordinated layer. This is due to the increase in the number of sites to chemisorption on the metal surface. The films formed are highly condensed ring aromatic layered structures. These films provide lower wear and depend on the type of surfactants concentration and sliding speed. The surface of metal was analyzed by SEM/EDX techniques. These studies have led to much clear evidence of the intimate relationship between the chemical structure of the surfactants and their film forming. More confirmation for suggested mechanism was investigated by measuring the area occupied per molecule of the surfactant in oil phase. The results indicate that the sulphonate group is less efficient than ethoxylate group. At the same time, the micelle of surfactants acts as oil dispersant and improves adsorption of oil on the metal surface.

Evaluation of Additives as Corrosion Inhibitors/Antioxidants for High Quality Nano Emulsifiable Oils of Metalworking Fluids

Surfactants used for formulation metal working fluids. In the present paper, the inhibitive effect of synthesized anionic surfactant P-decyloxy p-sodium sulphonateazobenzene with chemical structure H21C10O-Ph-N=N-Ph-SO3Na and 1-ethyl-1-dodecyl-2-sulphonate-4-(hydroxyl ethyl)-piprazine on the corrosion of carbon steel in sulphuric acid solution is measured by the weight loss method. The relationships between the concentrations of these inhibitors and their surface properties, thermodynamic properties, surface coverage and inhibiting efficiency, have been investigated. The results indicate that P-decyloxy p-sodium sulphonate azobenzene is superior to 1-ethyl-1-dodecyl-2-sulphonate-4-(hydroxyl ethyl)-piprazine at high acid concentration. These inhibitors blend with coupling agent to produce water miscible cutting fluid. Values of surface tension of these additives were measured in water phase and consequently CMC was determined for all inhibitors. The efficiency of these inhibitors depends on their chemical structure and the presence of hydrophilic group to association of the surfactant with metal surface, hence very good wetting properties. The anti-corrosion characteristic of surfactants increases with increasing polar linkages in the aromatic moieties forming chelated and coordinated layer. This is due to the increase in number of sites to chemisorption on the metal surface. These studies have led to much clear evidence of the intimate relationship between the chemical structure of the surfactants and their efficiency. More confirmation for suggested mechanism was investigated by measuring the area occupied per molecule of the surfactant at aqueous phase. The results indicate that the amphoteric surfactant more efficient than anionic surfactant. The antioxidants activities of different dosages of inhibitors were evaluated and suggested mechanism according to their thermodynamics parameters. The oxidation of the oil has been carried for different time intervals. The degradation of the oil has been monitored by total acid formation.

Disposition and fate of polyoxyethylene glycerol ricinoleate as determined by LC-Q-TOF MS coupled with MS^(ALL),SWATH and HR MS/MS techniques

Polyoxyethylene glycerol ricinoleate(PGR) serves as a solubilizer/emulsifier that is commonly used in pharmaceutical formulations despite being associated with severe anaphylactoid hypersensitivity reactions.Cremophor EL?(CrEL) is the most representative PGR produced from reacting ethylene oxide with castor oil.To help clarify the cause of side effects and potentially improve the safety of PGR-based drug delivery vehicle,we have developed separate but related analytical methods for the quantitation of CrEL and its main metabolites,glycerol ethoxylate(GE) and ricinoleic acid(RA).Since CrEL and GE are highly disperse mixtures of polymers that are not amenable to analysis by conventional liquid chromatographytandem mass spectrometry(LC-MS/MS),we used liquid chromatography-triple-quadrupole-time-of-flight mass spectrometry(LC-Q-TOF MS) combined with product ion data acquisition by MSALLand sequential window acquisition of all theoretical fragments mass spectrometry(SWATH MS),respectively to perform the analysis.In contrast,RA is a single molecular entity that could be readily analyzed using conventional LC-HR MS/MS.Selection of specific fragment ions for CrEL,GE,RA and their internal standards enabled a precise quantitation of such a complex analytes system in rat plasma after a single and simple sample preparation method.Assay validation indicated linearity for CrEL,GE and RA over the concentration ranges 0.2~20.0 μg/mL,0.1~10.0 μg/mL and 0.1~20.0 μg/m L,respectively with satisfactory results for other validation parameters.A subsequent pharmacokinetic study involving single intravenous 200 mg/kg injections of CrEL to rats showed the methods enable comprehensive and high throughput quantitation of CrEL and its metabolites in a biological matrix.Our combination of assays provides effective application in investigating the cause of the hypersensitivity reaction of PGR and potentially to improve its safety for using as a vehicle in drug formulations.

Shale hydration inhibition characteristics and mechanism of a new amine-based additive in water-based drilling fluids

In this work,shale hydration Inhibition performance of tallow amine ethoxylate as a shale stabilizer in water based drilling fluid,was investigated through these tests:bentonite hydration inhibition test,bentonite sedimentation test,drill cutting recovery test,dynamic linear swelling test,wettability test,isothermal water adsorption test,and zeta potential test.The results showed that bentonite particles are not capable of being hydrated or dispersed in the mediums containing tallow amine ethoxylate;tallow amine ethoxylate had shown a comparable and competitive inhibition performance with potassium chloride as a common shale stabilizer in drilling industry.Some amine functional groups exist in tallow amine ethoxylate structure which are capable of forming hydrogen bonding with surfaces of bentonite particles.This phenomenon decreased the water adsorption on bentonite particles'surfaces which results in reduction of swelling.Tallow amine ethoxylate is also compatible with other common drilling fluid additives.

简单低聚物交联法获得20.32%效率的高机械稳定性和高工作稳定性柔性倒置钙钛矿太阳能电池

钛性钙钛矿太阳能电池因其在柔性可穿戴电子领域的巨大应用潜力而备受关注.然而,钙钛矿薄膜对水氧、温度和光照等外界环境敏感,同时柔性钙钛矿电池的反复弯折也会加速钙钛矿薄膜光电性能的退化,导致柔性钙钛矿太阳能电池的工作稳定性和机械稳定性还远不能满足实际应用需求.本文提出了一种简单的低聚物交联方法,将三羟甲基丙烷乙氧基化物三丙烯酸酯(TET)作为掺杂剂掺入钙钛矿薄膜,交联聚合物在钝化和加固钙钛矿晶界的同时,也促进了钙钛矿晶粒的生长,柔性钙钛矿电池的效率、工作稳定性和机械稳定性获得了同步提升.倒置柔性钙钛矿太阳能电池的效率达到20.32%,85℃高温500 h、连续光照900 h或4 mm弯曲半径下弯折两万次,效率均能维持初始值85%以上.

Ethoxylation of Phenols Catalyzed by Metal-Free Lewis Pairs:Living/Controlled Polymerization in a Slow-lnitiation Mode

Phenols,in stead of con venti onal alcoholic compounds,are used to in itiate ring-openi ng polymerizati on(ROP)of ethyle neoxide and propyle ne oxide in bulk at room temperature in cooperati on with the recently prevaili ng bicompone nt metal-free catalyst comprising an organobase and triethylborane.Experimental and DFT calculation results both point out that due to the lower nucleophilicity of the initiating(phe no late)species than the propagating(alcoholate)species,chai n initiat ion is distinctly slower tha n propagation and the difference becomes eve n larger as the acidity of the phe nolic in itiator increases.Nevertheless,we 11-defi ned polyethers with expected molar mass,low dispersity,and high end-group fidelity are afforded substa ntiating that the ROP is living/c on trolled in spite of the slow initiation.Evolution of product composition indicates that the reaction on alcoholates(i.e.,propagation)is effectively inhib-ited by the unreacted phenols during the initiation step because of the adequately large acidity differenee,which is key to the success of the slow-initiation living/controlled polymerization.The acidity difference betwee n phe nol and alcohol also facilitates the fulfill-ment of highly selective phenolysis of epoxides,a"1+1"type addition reaction between phenol and epoxide(in excess)rather than the"1+n"type ROP reaction,by use of a milder organobase and decreased Lewis acid/base ratio.