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.

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 Study on Bisphenol A,Nonylphenol,and Octylphenol in Human Urine amples Detected by SPE-UPLC-MS

Objective To establish a comprehensive analytical method based on SPE‐UPLC‐MS for the simultaneous determination of bisphenol A （BPA）, nonylphenol （NP）, and octylphenol （OP） in urine samples. Methods Sixty urine samples collected from healthy subjects were analyzed for BPA, NP, and OP concentrations. The samples were de‐conjugated by adding β‐glucuronidase and sulfatase. After the enzymatic treatment, the samples were subjected to the OASIS HLB column solid phase extraction cartridges so as to be cleaned and concentrated. The UPLC separation was performed on a Acquity UPLCTM BEH C18 column （2.1×100 mm, 1.7 μm） with a gradient elution system of methanol‐water as the mobile phase. Triple‐quadrupole mass spectrometry analyzer was used for the qualitative and quantitative analysis of UPLC‐MS/MS system. Results The limit of detection of BPA, NP, and OP was 0.10, 0.10, and 0.15 ng/mL, respectively. The recoveries of BPA, NP and OP were 80.1%‐108%, 81.3%‐109%, and 81.5%‐98.7%, respectively. Among the 60 urine samples, BPA was detected in 8 samples at the level of 0.297‐32.7ng/mL, NP was detected in 29 samples at the level of 1.69‐27.8 ng/mL, and OP was detected in 17 samples at the level of 0.407‐11.1 ng/mL. Conclusion The method is simple with high sensitivity and selectivity, and is suitable for the determination of BPA, NP, and OP in urine. As shown by our analysis , BPA, NP, and OP appear to be prevalent in human urine. This is particularly true for NP. The results from our study is therefore valuable for future studies to assess the exposure to BPA, NP, and OP in the general population.

Spatial distribution and deposition history of nonylphenol and bisphenol A in sediments from the Changjiang River(Yangtze River) Estuary and its adjacent East China Sea

Nonylphenol（NP） and bisphenol A（BPA） are endocrine disruptors causing harmful effects including feminization and carcinogenesis to various organisms,and consequently,their contamination in natural environment has received wide concerns.This study reports the distribution characteristics of NP and BPA in surface sediments and their deposition history based on a dated sediment core in the Changjiang River（Yangtze River） Estuary and its adjacent East China Sea.The contents of NP and BPA in surface sediments ranged from 1.56-35.8 and 0.72-13.2 ng/g（dry mass）,respectively,with high values recorded in the two mud zones,the Changjiang River Estuarine Mud Zone and the Zhejiang Coastal Mud Zone.High values in the Zhejiang Coastal Mud Zone suggest the possibility of long distance transport of both contaminants through the Changjiang riverine plume.The contents were not correlated with the distance from the pollution source,indicating other factors including particle deposition rate and sediment grain size obviously affecting the distribution pattern.NP was also detected in a sediment core at layers deposited from the year of 1971 to 2001 with contents of up to 20.9 ng/g（dry mass）.The deposition fluxes of NP varied from 0.68 to 17.9 ng/（cm^2 · a） with peaks and valleys reflecting the traces of economic development history in China during the previous three decades.BPA was detected at sediment layers deposited from 1973 to 2001 with contents of up to 3.66 ng/g.The fluxes of BPA varied from 0.62 to 3.13 ng/（cm^2 · a） showing a similar pattern as NP.The contents of NP and BPA also indicated potential risks on benthic organisms in the study area.

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.

Distribution patterns of octylphenol and nonylphenol in the aquatic system at Mai Po Marshes Nature Reserve,a subtropical estuarine wetland in Hong Kong

Spatial and temporal distribution of octylphenol （OP） and nonylphenol （NP） in Mai Po Marshes, a subtropical estuarine wetland in Hong Kong, were investigated. Surface water samples were collected every month from 11 sites during the period of September- December 2004. Concentrations of OP and NP ranged from 11.3 to 348 ng/L and from 29 to 2591 ng/L, respectively. The high levels of NP and OP were found in November and December than in September and October. The levels of OP and NP have no significant spatial differences except September. Total organic matter in the sediments appeared to be an important factor in controlling the fate of these compounds in the aquatic environment.

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge

Nonylphenol(NP), nonylphenoxy acetic acid(NP1EC), nonylphenol monoethoxy acetic acid(NP2EC), nonylphenol monoethoxylate(NP1EO) and nonylphenol diethoxylate(NP2EO) are biodegradation end products(BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28℃ fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient(K F) and linear sorption coefficient(K D) showed that sorption capacity of the investigated compounds were in order NP>NP2EO>NP1EO>NP1EC≈NP2EC. For NP, NP1EO and NP2EO, high values of calculated K F and K D indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K F and K D absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.

Effects of Nonylphenol on Brain Gene Expression Profiles in F1 Generation Rats

Objective To explore the effects of nonylphenol on brain gene expression profiles in F1 generation rats by microarray technique. Methods mRNA was extracted from the brain of 2-day old F1 generation male rats whose F0 female generation was either exposed to nonylphenol or free from nonylphenol exposure, and then it was reversely transcribed to cDNA labeled with cy5 and cy3 fluorescence. Subsequently, cDNA probes were hybridized to two BiostarR-40S cDNA gene chips and fluorescent signals of cy5 and cy3 were scanned and analyzed. Results Two genes were differentially down-regulated. Conclusion Nonylphenol may disturb the neuroendocrine function of male rats when administered perinatally.

Simultaneous determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in Guanting Reservoir using gas chromatography-mass spectrometry with selected ion monitoring

The wide occurrence of estrogenic compounds 4-tert-octylphenol, 4-nonylphenol, bisphenol A in surface water of Guanting Reservoir was successfully determined. The target compounds in water samples were preconcentrated by liquid-liquid extraction with dichloromethane, derivatized by trifluoroacetic anhydride, and quantified by gas chromatography-mass spectrometry(GC-MS) with selected ion monitoring(SIM). In the selected seven sampling sites(S1\_S7), the concentration of NP in sample S7 was significantly higher than the other in reservoir. The status of pollution in S3 and S7 were much more serious. The concentrations of OP, NP and BPA were in the range of 44.5—48.8, 221.6—349.6 and 30.2—82.7 ng/L, respectively. The pollutants were mainly inputted from the upper river and released from sediments in Guanting Reservoir.

Sperm of rosy barb (Puntius conchonius) as an in vitro assay system of nonylphenol cytotoxicity

Nonylphenol （NP） is the final degradation product of alkylphenol polyethoxylates （APEs）, which are widely present in plastics, papers, pulp, detergents, pesticides, herbicides, paints and cosmetics. It is estimated that annual global production of APEs is about 500000 t, 60% of which eventually ends up in aquatic ecosystems primarily via wastewater （So16 et cd., 2000）. NP is resistant to biodegradation and persistent in the environment （Arukwe et al., 2000）.

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...

Cytotoxicity of nonylphenol on spermatogonial stem cells via phosphatidylinositol-3-kinase/protein kinase B/mammalian target of rapamycin pathway

BACKGROUND With continuous advancement of industrial society,environmental pollution has become more and more serious.There has been an increase in infertility caused by environmental factors.Nonylphenol(NP)is a stable degradation product widely used in daily life and production and has been proven to affect male fertility.However,the underlying mechanisms therein are unclear.Thus,it is necessary to study the effect and mechanism of NP on spermatogonial stem cells(SSCs).AIM To investigate the cytotoxic effect of NP on SSCs via the phosphatidylinositol-3-kinase/protein kinase B/mammalian target of rapamycin(PI3K/AKT/mTOR)pathway.METHODS SSCs were treated with NP at 0,10,20 or 30μmol.MTT assay was performed to evaluate the effect of NP on the proliferation of SSCs.Flow cytometry was conducted to measure SSC apoptosis.The expression of Bad,Bcl-2,cytochrome-c,pro-Caspase 9,SOX-2,OCT-4,Nanog,Nanos3,Stra8,Scp3,GFRα1,CD90,VASA,Nanos2,KIT,PLZF and PI3K/AKT/mTOR-related proteins was observed by western blot,and the mRNA expression of SOX-2,OCT-4 and Nanog was detected by quantitative reverse transcription polymerase chain reaction.RESULTS Compared with untreated cells(0μmol NP),SSCs treated with NP at all concentrations showed a decrease in cell proliferation and expression of Bcl-2,Nanog,OCT-4,SOX-2,Nanos3,Stra8,Scp3,GFRα1,CD90,VASA,Nanos2,KIT,and PLZF(P<0.05),whereas the expression of Bad,cytochrome-c,and pro-Caspase 9 increased significantly(P<0.05).We further examined the PI3K/AKT/mTOR pathway and found that the phosphorylation of PI3K,AKT,mTORC1,and S6K was significantly decreased by NP at all concentrations compared to that in untreated SSCs(P<0.05).NP exerted the greatest effect at 30μmol among all NP concentrations.CONCLUSION NP attenuated the proliferation,differentiation and stemness maintenance of SSCs while promoting apoptosis and oxidative stress.The associated mechanism may be related to the PI3K/AKT/mTOR pathway.

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

Toxicity of Nonylphenol on Microcystis aeruginosa Mediated by the Ascorbate-glutathione (AsA-GSH ) Cycle

Nonylphenol( NP) is a stable metabolic product of nonylphenol ethoxylates,which is widely used as an industrial surfactant. NP has been classified as an endocrine disrupter,and its toxicity to organisms can be biomagnified through the food chain. As compared with the endocrine disrupting effect,the toxicity of NP to organisms has not been studied intensively,and the toxicity mechanisms have often been ignored. In the present study,Microcystis aeruginosa,a freshwater alga belonging to the first level of the trophic chain,was chosen to detect the toxicity of NP. The mechanisms of toxicity mediated by the AsA-GSH cycle were explored. The acute toxicity of NP to M. aeruginosa within 96 h was studied and an EC_(50) concentration of 3. 45 mg/L was found. Further,the results showed that the toxicity of NP increased with the increase in concentration and exposure time. As compared with that in the control,the APX and MDHAR activities mostly increased,whereas DHAR activity fluctuated.However,the AsA content elevated at first,but decreased significantly after 72 h. For the GSH system,GR activity was always higher than that in the control. Nevertheless,the reduced GSH content was mostly inhibited. Therefore,the performance of AsA-GSH antioxidant defense system could explain the results of NP toxicity: the enzyme activities and antioxidant molecules increased initially,but an overall decline appeared after exposure for 24 h. This research is helpful for estimating the toxicity of NP integrally and improves people's understanding of mechanisms of NP toxicity in algae.

Purification and Characterization of a Nonylphenol （NP）-degrading Enzyme from Bacillus cereus.Frankland

An extracellular NP-degrading enzyme secreted by Bacillus cereus.Frankland was purified to homogeneity by a combination of ammonium sulfate precipitation,Phenyl-Sepharose hydrophobic-interaction chromatography and DEAE anion-exchange chromatography.On SDS（sodium dodecyl sulfate）-polyacrylamide gel electrophoresis analysis,the purified enzyme showed a relative molecular mass of 58.3 kDa.The depolymerzation of subunits was accompanied with the loss of NP-degrading enzyme activity,and removing denaturing factors by dialysis could restore the dimer structure and enzymatic activity.The enzyme had an isoelectric point of 5.5 and an optimal temperature of 60℃,and was the most active at pH 6.0.The enzymatic activity was stable at pH 4-8 and inhibited by Cu2＋.TenN-terminal amino acids were determined to be ASVNSIKIGY,demonstrating that the purified enzyme was a novel one.The hydrolysis pattern of the purified enzyme indicated that the NP-degrading enzyme was an endo NP-degrading enzyme.The extraordinary thermo-stability provided the enzyme with a good prospect to be used as a new tool for clean-production process for textile industry.

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.

Determination of bisphenol A and 4-nonylphenol in media samples for <i>in vitro</i>fertilization by high-performance liquid chromatography with tandem mass spectrometry

In vitro fertilization (IVF) is an important treatment for infertility, and in recent years, the delivery rate in IVF has increased markedly with the progress of reproductive medicine. However, chemical contaminants in IVF media have not been fully studied. A simple method using highperformance liquid chromatography coupled with tandem mass spectrometry was therefore investigated for quantitation of bisphenol A (BPA), 4nonylphenol (NP) and 4-n-nonylphenol (n-NP) in IVF media. Media samples were processed using the solid-phase extraction method. The quantitation limits of BPA, NP, and n-NP were 0.5, 5 and 0.5 ng·ml-1, respectively, and the recoveries for BPA, NP and n-NP added to the media samples were above 90%. Commercially available media samples for IVF including 15 media for incubation of ova, 9 sperm washing media (SWM), 4 human serum albumin (HSA) samples and 2 substitute serum (SS) samples were examined, with 2 lots for each sample. NP was detected in 3 media for incubation of ova, 12 SWM, 7 HSA samples and 4 SS samples, in ranges of 6.3 14.5, 5.3 21.7, 5.5 164.0 and 9.0 19.0 ng·ml-1, respectively. BPA and n-NP were not detected in any of the samples.

Stereological study of the effects of vitamin E on testis structure in rats treated with para-nonylphenol

This study was organized to see whether vitamin E, as a strong antioxidant, could affect the abnormalities of testis structure caused by para-nonylphenol （p-NP） during its development. A total of 32 female Wistar rats after mating were divided into four groups （n = 8）： control, vitamin E （100 mg kg^-1 per day）, p-NP （250 mg kg^-1 per day） and p-NP ＋ vitamin E. The rats were treated from the seventh day of pregnancy till the twenty-first day. After weaning, the male pups were divided into the same groups and were treated orally for 90 days. Finally, the right testis was fixed, processed, stained and studied using stereological methods. The weight and volume of testis, volume of seminiferous tubules and its diameter, thickness of the basement membrane, height of the germinal epithelium, total number of types A and B spermatogonia, spermatocyte, spermatid and Sertoli cells were significantly reduced in p-NP group when compared with other groups. Co-administration of vitamin E and p-NP compensated for the adverse effects of p-NP on the above parameters. In addition, treatment with only vitamin E caused a significant increase in diameter, basement membrane thickness and height of germinal epithelium, number of spermatogonia and spermatocytes. Co-administration of vitamin E with p-NP could prevent the adverse effects ofp-NP on the testis structure during its development.

Hydrothermal Carbonization of Nonylphenol Ethoxylates Waste Liquid for Energy Source Generation

Nonylphenol polyethoxylates (NPEOs) are widely used as nonionic surfactants in many industry fields. High concentration NPEOs waste water is produced in some production processes. It is often treated to realize reduction by distillation. Therefore, NPEOs waste liquid with higher concentration is produced and it is difficult to be treated by traditional water treatment process. In this study, hydrothermal carbonization process was used to convert NPEOs waste liquid to carbonaceous product (hydrochar) with sulfuric acid as additive in 24 h at 200°C. The hydrochar was characterized by scanning electron microscope, Fourier-transform infrared spectrometer and thermogravimetric analysis. The element composition and the high heat value of the hydrochar were similar to lignite, showing that it could be used as an alternative fuel.

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.