Nonylphenol Ethoxylates Research Articles

Identification of Non-ionic Surfactants in Elements of the Aquatic Environment

AbstractInformation concerning the use of non-ionic surfactants (NS) in household products is very scanty. Therefore, a qualitative determination of NS in raw sewage is an alternative source of information concerning the presence and manufacture of NS. The aim of this work was to identify NS in raw sewage (in Poznan and Blonie, both Poland) and treated sewage (in Blonie) and to compare the results with those obtained for river water (Warta in Poznan, Poland). LC-MS/MS was used for this purpose. The presence of 116 ethoxamers, being exclusively polydispersal alcohol ethoxylates (AE) containing alkyl moieties from C10 to C16 and C18, as well as 20 poly(ethylene glycols), was confirmed in the raw sewage, while 68 ethoxamers were found in the treated sewage, including 12 octylphenol ethoxylates. No nonylphenol ethoxylates were identified in the raw or treated sewage.

Visible Light Induced Emulsion Polymerization: An Improved Photoinitiation System Based on Amphiphilic Tertiary Amine N‐Oxides

A new method for visible‐induced emulsion polymerization is successfully demonstrated. Photo­initiators are used upon irradiation with visible light to undergo sequential photodecomposition, demonstrating an effective way to generate radicals with octadecylamine ethoxylates N‐oxide (AO‐1805, EO = 5). AO‐1805, acting both as a surfactant and mediator simultaneously, is proposed for free radical generation through synergistic effects with the photoinitiator, which differs greatly from organoboron compounds, especially in emulsions. Comparative experiments are carried out with nonylphenol ethoxylates (NP‐10, EO = 5) upon irradiation with UV and visible light in order to examine the nature of the photoinitiated emulsion polymerization with AO‐1805. The laser flash photolysis method is then used to study the interaction between AO‐1805 and free radicals. The emulsion photopolymerization of styrene may be successfully mediated by AO‐1805, with good control over molecular weight. A synergistic effect between radicals and AO‐1805 is observed in the UV irradiation process that can further mediate radical polymerization. In visible light‐induced emulsion polymerization, AO‐1805 also has a novel stabilizing role because of the interaction between D1 and AO‐1805. Moreover, it is hard to see such a trend with the NP‐10/D1 combination, indicating that the functional group (N‐oxide) of AO‐1805 plays an important role in photoinitiation and has an influence on the overall polymerization rate. image

TiO2 thick films supported on stainless steel foams and their photoactivity in the nonylphenol ethoxylate mineralization

The main interest in employing a structured catalyst for water treatment processes is to avoid an extra recovering-step of the powder catalyst after concluding the treatment. For this purpose, TiO2 powder (Degussa P25) was immobilized onto metallic foam walls (TiO2-foam) through the washcoating method and its photocatalytic activity was evaluated in the degradation of nonylphenol ethoxylate (NP4EO), which is considered an endocrine disrupter. The morphological and physicochemical characteristics of TiO2 films were studied by X-ray Diffraction, Laser Raman Spectroscopy and Scanning Electron Microscopy.The fast and easy washcoating method used in this work allowed the immobilization of the TiO2 powder onto a relatively inexpensive metallic substrate. The TiO2 layer was uniformly distributed, having a high adherence to the metallic foam walls, which were previously submitted to a passivation treatment. This pre-treatment hindered a further migration of cations from the foam core to the titania film and favored the subsequent film anchorage. Moreover, the catalytic film so obtained maintained the anatase and rutile phases with their original proportions, preserving the properties of the TiO2 powder. The photocatalytic activity of the TiO2-foam was similar to that of a commercial catalyst (TiO2–Ti mesh), i.e. both reduced the TOC of the NP4EO solution by about 91%, showing similar reaction kinetics and overall quantum yield (Фoverall). These results demonstrate that by means of the method under study, TiO2 can be successfully immobilized without decreasing its photocatalytic activity. These catalysts may be applied in water/wastewater treatment, reducing the process stages and the overall cost of the procedure.

Optimisation of Detergent Ingredients for Stain Removal Using Statistical Modelling

AbstractArtificially soiled test fabrics are widely used to study the cleaning performance of detergents formulations. In this study, artificial soiled cotton test fabrics were prepared in the laboratory using carbon black as a model soil. Design of experiments was used to optimise the concentration of detergent ingredients for stain removal. A multi‐factorial analysis of variance was used to model the effect of sodium dodecylbenzene sulfonate, nonylphenol ethoxylate, sodium silicate, sodium citrate and sodium carbonate as builders on soil removal. A colourimetric evaluation using the CIELAB system was used to measure soil removal. In general, performance increases with increasing concentration of surfactant, silicate and soda ash.

CO2 mobility control using CO2 philic surfactant for enhanced oil recovery

CO2 enhanced oil recovery by using newly synthesized CO2 philic surfactant as CO2 mobility control agent is reported. Nonyl phenol ethoxylate sulphonate (NPES) was prepared by the esterification of alcohol with maleic anhydride followed by its sulphonation. Effect of interfacial tension (IFT) between CO2 and brine using NPES was investigated to verify the CO2 philicity of the surfactant. The detailed account of effects of pressure and temperature on IFT between CO2/brine in the presence and absence of surfactant on specified pressure and temperature conditions is studied and discussed. NPES effectively lowered the IFT between CO2/brine (30 mN/m) to less than 5.23 mN/m. Foam quantity was improved by using betaine as foam booster. The static foam endurance properties in the presence and absence of oil were also examined prior to the actual performance test of surfactants using a reservoir core plug sample. It was noted that the foam stability was 900 s in the presence of oil at 90 °C in CO2 environment. The effect of foam by using synthesized NPES on mobility of CO2 is also presented. The CO2 mobility reduction factor was found to be 3.1. It is concluded that NPES has great potential for CO2-EOR applications.

Iodine Free Dye-Sensitized Solar Cells Using Nonyl Phenol Ethoxylate and Its Long-Term Stability

Iodine Free Dye-Sensitized Solar Cells Using Nonyl Phenol Ethoxylate and Its Long-Term Stability

In Situ Copolymerization of Silver Containing Nanocomposites of Pyrrole and Thienyl End-capped Ethoxylated Nonyl Phenol by Iron (III) Chloride

This study presents synthesis of novel block copolymers of thienyl end capped ethoxylated nonyl phenol and polypyrrole with silver nanoparticles via chemical oxidative polymerization by iron (III) chloride. Ethoxylated nonyl phenol (ENP) was reacted with 2-thiophenecarbonyl chloride (ThCCl) in order to synthesize a macromonomer containing thienyl end-group (ENP-ThC). Then copolymers of ENP-ThC and pyrrole were synthesized by chemical oxidative polymerization using iron (III) chloride as an oxidant. During this reaction, silver nitrate (AgNO3) solution was added in order to increase its conductivity and to give the copolymer anti-microbial property. The synthesized block copolymers (ENP-ThC-b-PPy) with silver nanoparticles were characterized by spectroscopic analysis and the electrical conductivities were investigated with 4-point probe technique. The obtained samples were also characterized morphologically by Scanning Electron Microscope (SEM).

Gamma radiation/H2O2 treatment of a nonylphenol ethoxylates: Degradation, cytotoxicity, and mutagenicity evaluation

Gamma radiation/H2O2 treatment of nonylphenol polyethoxylates (NPEO) was performed and treatment effect was evaluated on the basis of degradation, chemical oxygen demand (COD) and total organic carbon (TOC), and toxicity reduction efficiencies. The radiolytic by-products were determined by Fourier Transform Infrared Spectroscopy (FTIR), High-Performance Liquid Chromatography (HPLC), and Gas Chromatography–Mass Spectrometry (GC–MS) techniques. Low mass carboxylic acids, aldehyde, ketone, and acetic acid were identified as the by-products of the NPEO degradation. NPEO sample irradiated to the absorbed dose of 15kGy/4.58% H2O2 showed more than 90% degradation. Allium cepa (A. cepa), brine shrimp, heamolytic tests were used for cytotoxicity study, while mutagenicity was evaluated through Ames test (TA98 and TA100 strains) of treated and un-treated NPEO. The reductions in COD and TOC were greater than 70% and 50%, respectively. Gamma radiation/H2O2 treatment revealed a considerable reduction in cytotoxicity and mutagenicity. A. cepa, heamolytic and shrimp assays showed cytotoxicity reduction up to 68.65%, 77%, and 94%, respectively. The mutagenicity reduced up to 62%, 74%, and 79% (TA98) and 68%, 78%, and 82% (TA100), respectively of NPEO-6, NPEO-9, and NPEO-30 irradiated to the absorbed dose of 15kGy/4.58% H2O2. NPEO-6 detoxified more efficiently versus NPEO-9 and NPEO-30 and results showed that Gamma radiation/H2O2 treatment has the potential to mineralize and detoxify NPEO.

Production of mono- and di-carboxylated polyethylene glycols as a factor obstacle to the successful ozonation-assisted biodegradation of ethoxylated compounds

Ozonation is believed to improve the biodegradability of organic compounds. In the present study, degradation of nonylphenol ethoxylates (NPEOs) was monitored in hybrid treatment systems consisting of ozonation and microbial degradation processes. We found that ozonation of NPEOs decreased, rather than increased, the biodegradability under certain conditions. The timing of ozonation was a definitive factor in determining whether ozonation increased or decreased the biodegradation rates of NPEOs. Initial ozonation of NPEOs prior to biodegradation reduced the rate of dissolved organic carbon (DOC) removal during the subsequent 14d of biodegradation, whereas intermediate ozonation at the 9th day of biodegradation improved subsequent DOC removal during 14d of NPEO biodegradation. Furthermore, reduction of DOC removal was also observed, when initial ozonation prior to biodegradation was subjected to cetyl alcohol ethoxylates. The production of less biodegradable intermediates, such as mono- and dicarboxylated polyethylene glycols (MCPEGs and DCPEGs), was responsible for the negative effect of ozonation on biodegradability of NPEOs. DCPEGs and MCPEGs were produced by biodegradation of polyethylene glycols (PEGs) that were ozonolysis products of the NPEOs, and the biodegradability of DCPEGs and MCPEGs was less than that of the precursor PEGs. The results indicate that, if the target chemicals contain ethoxy chains, production of PEGs may be one of the important factors when ozonation is considered.

Characterization and Particle Size Control of Acrylic Polymer Latex Prepared with Green Surfactants

The application of green surfactants, which have low toxicity, excellent biodegradability in emulsion polymerization, has not been reported in the literature. In the present paper, alkyl polyglycosides (APG) and sodium alpha-olefin sulfonate (SAOS) were used as the nonionic emulsifier and anionic emulsifier, respectively to synthesize acrylic polymer latex. The acrylic polymer latex was prepared via semi-continuous seeded emulsion polymerization of butyl acrylate (BA) and methyl methacrylate (MMA) in water phase initiated with potassium persulfate (KPS) when nonylphenol ethoxylates (NPEOs) and sodium dodecyl-benzenesulfonate (SDBS) and are replaced with APG and SAOS, respectively. Both APG and SAOS have low toxicity, excellent biodegradability and outstanding properties. The structure of the acrylic polymer latex was confirmed with FTIR spectrum. Differential scanning calorimetry confirmed that the resultant latex is a kind of random copolymer. The unimodal distribution of particle size also confirmed that the acrylic polymer latex was prepared successfully. Factors, which have an influence on particle size of the resultant latex, were studied in detail. The optimum recipe of preparing the acrylic polymer latex with small particle size was obtained.

Nonylphenol diethoxylate inhibits apoptosis induced in PC12 cells.

Nonylphenol and short-chain nonylphenol ethoxylates such as NP2 EO are present in aquatic environment as wastewater contaminants, and their toxic effects on aquatic species have been reported. Apoptosis has been shown to be induced by serum deprivation or copper treatment. To understand the toxicity of nonylphenol diethoxylate, we investigated the effects of NP2 EO on apoptosis induced by serum deprivation and copper by using PC12 cell system. Nonylphenol diethoxylate itself showed no toxicity and recovered cell viability from apoptosis. In addition, nonylphenol diethoxylate decreased DNA fragmentation caused by apoptosis in PC12 cells. This phenomenon was confirmed after treating apoptotic PC12 cells with nonylphenol diethoxylate, whereas the cytochrome c release into the cytosol decreased as compared to that in apoptotic cells not treated with nonylphenol diethoxylates. Furthermore, Bax contents in apoptotic cells were reduced after exposure to nonylphenol diethoxylate. Thus, nonylphenol diethoxylate has the opposite effect on apoptosis in PC12 cells compared to nonylphenol, which enhances apoptosis induced by serum deprivation. The difference in structure of the two compounds is hypothesized to be responsible for this phenomenon. These results indicated that nonylphenol diethoxylate has capability to affect cell differentiation and development and has potentially harmful effect on organisms because of its unexpected impact on apoptosis. © 2015 Wiley Periodicals, Inc. Environ Toxicol 31: 1389-1398, 2016.

Requiem for the nonylphenol ethoxylates

Requiem for the nonylphenol ethoxylates

Photocatalytic degradation of nonylphenol by immobilized TiO2 in dual layer hollow fibre membranes

Nonylphenol (NP) is one of refractory degradation intermediates of nonylphenol ethoxylates (NPEO) surfactant and among the most toxic and prevalent endocrine disrupting compounds (EDCs) found in the environment. This paper reports an effort in removing nonylphenol in water using novel photocatalytic dual layer hollow fibre membrane, where the outer layer comprised of polyvinylidene fluoride (PVDF)/titanium dioxide (TiO2) while the inner layer was 100% PVDF. Single layer hollow fibre membrane which consists of PVDF/TiO2 was also fabricated as the control sample. The presence of TiO2 on the outer surface of both dual and single layer hollow fibres was confirmed by scanning electron microscopy (SEM), energy dispersion of X-ray (EDAX) and contact angles analysis. The removal of 85% in NP concentration was achieved for dual layer hollow fibre after 4h UVA irradiation in submerged membrane photoreactor, compared to 70% for the single layer one. The kinetic rate of dual layer membranes was calculated to be 0.0092min−1 against 0.0062min−1 for the single layer counterpart. In general, dual layer hollow fibre membranes exhibited superior photocatalytic performance in comparison to single layer hollow fibre membranes due to the better dispersion of TiO2 on the outer membrane surface.

A new stability index for characterizing the colloidal gas aphrons dispersion

Abstract Aphrons are surfactant stabilized microbubbles with thick soapy shells. Stability is a key feature of microbubbles. Colloidal gas aphrons (CGAs), with an average diameter of 50 μm, offer particular advantages where the stability of microbubbles is of interest. Various factors that affect on CGA stability such as surfactant type, concentration, and processing parameters have been extensively studied. However, there is no simple and accurate stability index for characterizing the stability of microbubbles dispersion. In this study, the stability of CGAs dispersion has been examined based on the drainage curve by four stability indexes. The surfactant of choice was nonyl phenol ethoxylate (NPE), a nonionic surfactant. The results show that the one-tenth of drained liquid life ( T 0.1 ), the time elapsed when the drained liquid from CGA dispersion reaches ten percent of its final height is the best indicator among the other stability indexes for characterizing the CGAs dispersion.

Direct Measurement of Anaerobic Biodegradability of Nonylphenol Ethoxylates (NPEOs)

The biodegradation of nonylphenol ethoxylates (NPEOs) surfactant often produces more refractory, toxic and estrogenic intermediates. In this study, simple analytical for NPEOs determination based on High Performance Liquid Chromatography (HPLC) was developed and complete biodegradation of NPEOs was evaluated by serum bottle method that uses direct measure of biogas production in anaerobic condition. The reversed phase C18 column was successfully used for detection of long chain NPEOave9 (having an average of 9 EO units) and short chain NPEOave1.5 (having an average of 1.5 EO units) and nonylphenol (NP) at short retention time. However, the coelution of oligomers in reversed phase chromatography is unavoidable, thus the distinction between NPEO oligomers is not possible. In biodegradation study study, the long chain NPEOave9 was partially mineralized at approximately 37% of the theoretical CH4 production in anaerobic condition. Nevertheless, the refractory intermediates of NPEOave1.5 and nonylphenol adversely affects the glucose- utilizing methanogens under anaerobic condition, thereby hampering CH4 formation. It can be concluded that the anaerobic biodegradation of nonylphenolic compounds proceeded at a very slow rate due to their complex physicochemical properties.

Oral exposure to low-dose of nonylphenol impairs memory performance in Sprague-Dawley rats.

Nonylphenol ethoxylate (NPE) is a non-ionic surfactant, that is degraded to short-chain NPE and 4-nonylphenol (NP) by bacteria in the environment. NP, one of the most common environmental endocrine disruptors, exhibits weak estrogen-like activity. In this study, we investigated whether oral administration of NP (at 0.5 and 5 mg/kg doses) affects spatial learning and memory, general activity, emotionality, and fear-motivated learning and memory in male and female Sprague-Dawley (SD) rats. SD rats of both sexes were evaluated using a battery of behavioral tests, including an appetite-motivated maze test (MAZE test) that was used to assess spatial learning and memory. In the MAZE test, the time required to reach the reward in male rats treated with 0.5 mg/kg NP group and female rats administered 5 mg/kg NP was significantly longer than that for control animals of the corresponding sex. In other behavioral tests, no significant differences were observed between the control group and either of the NP-treated groups of male rats. In female rats, inner and ambulation values for animals administered 0.5 mg/kg NP were significantly higher than those measured in control animals in open-field test, while the latency in the group treated with 5 mg/kg NP was significantly shorter compared to the control group in step-through passive avoidance test. This study indicates that oral administration of a low-dose of NP slightly impairs spatial learning and memory performance in male and female rats, and alters emotionality and fear-motivated learning and memory in female rats only.

Risk-based screening of selected contaminants in the Great Lakes Basin

A risk-based screening exercise was carried out to evaluate the significance of chemicals of emerging concern measured in water and sediment of the Great Lakes Basin. Chemical classes included pesticides, pharmaceuticals, organic wastewater constituents, nonylphenol ethoxylates, perfluorinated surfactants, chlorinated paraffins, synthetic musks and flame retardants. Maximum measured concentrations were compared to benchmarks selected or developed to reflect a conservative no-effect level and/or the lowest-effect level. These benchmarks reflected traditional effect information such as survival, growth and reproduction. From this analysis, several pesticides, pharmaceuticals, polycyclic aromatic hydrocarbons and nonylphenol ethoxylates were identified as potential concerns and needs for further work were identified. Five of these chemicals (all pesticides) were identified in waters of both the US and Canada (azinphos-methyl, chlorpyrifos, diazinon, malathion and metolachlor). Chlopyrifos, malathion and metolachlor are still registered for use in both jurisdictions; diazinon is registered for use only in the US and azinphos-methyl is not registered for use in either jurisdiction, reflecting the persistence of these chemicals. The results of this screening exercise also were compared to those of several other studies, revealing some common chemicals. Although there are several uncertainties and data gaps in the benchmarks and monitoring data used in the current screening exercise, the results of this risk-based screening can be used by agencies for priority setting, program development, and to support ongoing collaborative research and monitoring programs.

Exploring the impacts of two separate mixtures of pesticide and surfactants on estrogenic activity in male fathead minnows and rainbow trout.

In this study, male fathead minnows (FHM) (Pimephales promelas) and juvenile rainbow trout (RT; Oncorhynchus mykiss) were exposed to two different surfactant mixtures of analytical-grade nonlyphenol, 4-tert octyphenol, octylphenol ethoxylates, nonylphenol ethoxylates, and the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). After a 7-days exposure to environmentally relevant concentrations of these compounds, there was no difference in the relative mRNA expression of vitellogenin (VTG) in male juvenile RT exposed to individual compounds or the 2,4-D-surfactant mixture compared with the control. In male FHM, there was a significant increase in VTG mRNA expression in the high individual treatments of 2,4-D and the surfactants but not the 2,4-D-surfactant mixtures compared with the control. These results were compared with another study exposing male FHM to individual and a mixture of alkylphenols and alkylphenol ethoxylates in two different combinations with the herbicide diuron and the insecticide bifenthrin. There were no differences in the relative expression of VTG mRNA amongst individual exposures and the control. Interestingly, when the ethoxylate mixture was combined with diuron, there was a significant decrease in the relative mRNA expression of VTG compared with the control. However, when the ethoxylate mixture was combined with both diuron and bifenthrin, there was a significant increase in the relative mRNA expression of VTG in male compared with all other groups in the multichemical mixture. The results of this study highlight differences between species and measurements of VTG in assessing the risk of mixtures to aquatic organisms.

Novel reactive polymerizable nonyl phenol ethoxylate surfactants as emulsifier in non-aqueous emulsion polymerization

In this work, new series of modified nonionic polymerizable nonyl phenol ethoxylates (NPEs) were synthesized as organic solvent-soluble surfactants. The nonyl, phenyl and propenyl groups were acted as solvophilic segment. The modified polyoxyethylene, maleate chains were behaved as solvophobic segment. The new bifunctional surfmers were prepared by reacting polyoxyethylene 4-nonyl-2-propylenephenol nonionic reactive surfactant with maleic anhydride followed by esterification with poly(ethylene glycol). The chemical structure of the prepared surfactants was determined by 13C and 1H NMR analyses. The surface activities of these surfactants were determined in organic solvents including formamide, toluene and aqueous water solvent from surface tension measurements. The relationship between the surface activity and molecular structure of the organic solvent-soluble polymerizable NPE surfactants as well as the type and structure of organic solvents were discussed. The results showed that the prepared polymerizable NPE surfactants have been reduced the surface tension of both polar and non-polar organic solvents. Surface parameters such as surface excess concentration (Γmax), the area per molecule at interface (Amin) and the effectiveness of surface tension reduction were determined from the adsorption isotherms of the prepared surfactants. The prepared polymerizable surfactant used to prepare crosslinked N-isopropylacrylamide (NIPAAm) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) copolymer microgel based on nonaqueous emulsion copolymerization.

Liver histology and ultrastructure of the Italian newt (Lissotriton italicus): Normal structure and modifications after acute exposure to nonylphenol ethoxylates

We examined, from a morphological and ultrastructural point of view, the liver of the Italian newt (Lissotriton italicus), under basal conditions and after exposure to nonylphenol ethoxylates (NPEs). Nonylphenol ethoxylates are surfactants widely used in a variety of industrial and agricultural processes that may pose a significant risk to aquatic fauna. NPEs, and their degradation intermediates, are known to affect reproductive biology acting as endocrine disruptors; besides estrogenic effects, nonylphenolic compounds may induce organ toxicity, particularly in liver and gonads. We investigated the effects of a nonylphenol ethoxylate (NPE10-ETO) on L. italicus liver using two low concentrations, consistent with the environmental concentrations. For this purpose, animals were exposed to nominal concentrations of 50 and 100μg/L in a short-term experiment (96h). A morpho-functional analysis was performed in order to investigate the amphibian responses to NPEs thus contributing to elucidate other potential mode of action of these compounds; indeed very little attention has been dedicated to amphibians though they are often exposed to such contaminants in aquatic ecosystems. Pathological alterations on liver histology and ultrastructure were observed at both tested concentrations; the main effects recorded were: increase of intercellular spaces, accumulation of large lipid droplets, increase in melanin content, and a degeneration phenomenon. We also detected, through confocal analysis, the induction of caspase-3, a key mediator of apoptosis, and an up-regulation of cytochrome P450-1A. By using both ultrastructural and a morpho-functional approach, we found that a short-term exposure to NPEs negatively affected the amphibian liver.