Alkylphenol Ethoxylates Research Articles

Chemical monitoring and occurrence of alkylphenols, alkylphenol ethoxylates, alcohol ethoxylates, phthalates and benzothiazoles in sewage treatment plants and receiving waters along the Ter River basin (Catalonia, N. E. Spain)

This study presents a quantitative estimation of the analysis and fate of several emerging pollutants, some of them endocrine-disrupting compounds, in surface water samples collected at several locations along the Ter River and two of its tributaries. Influent and effluent waters and particulate matter from five sewage treatment plants (STP) that discharge into these rivers were also studied. The target compounds analyzed were: nonylphenol ethoxylates (NPEO), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), phthalates, alcohol ethoxylates (AEO) and benzothiazoles. Chemical analysis by liquid chromatography-mass spectrometry using an electrospray interface (LC-ESI-MS) revealed the presence of low amounts (between 0.06 and 17.5 microg L(-1)) of the target compounds NPE(1+2)O and NP, which were detected in 100% and 84% of the samples respectively. Maximum concentrations occurred in the STPs associated with the municipalities of Vic and Girona. From the fate and behavior data obtained for the various compounds analyzed in the STP influent and effluent, we can conclude that the STPs are effective at removing large amounts (more than 70%) of the compounds studied from the water.

Estrogen-Like Response to p-Nonylphenol in Human First Trimester Placenta and BeWo Choriocarcinoma Cells

p-Nonylphenol (p-NP) is a metabolite of alkylphenol ethoxylates used as surfactants in the manufacturing industry. Although it is reported to have estrogenic activity and to be transferred from the mother to the embryo, no data are available on its effects on the development of the human placenta. In the present study, we investigated estrogen receptors' (ERs) expression in the first trimester human placenta. Using an in vitro model of chorionic villous explants, we then compared the effects of p-NP and 17beta-estradiol (17beta-E2). Finally, a trophoblast-derived choriocarcinoma cell line, BeWo, was used as a model of trophoblast cell differentiation. Our results showed that the first trimester placenta expresses three ER-alpha isoforms of 67, 46, and 39 kDa and one ER-beta isoform of 55 kDa. Immunohistochemistry revealed the expression of ER-alpha in the villous cytotrophoblast, whereas ER-beta was mainly expressed by the syncytiotrophoblast. Treatment of explant cultures with p-NP (10(-9)M) and 17beta-E2 (10(-9)M) significantly increased beta-hCG secretion and cell apoptosis but did not modify ER expression. After 72 h of exposure, hormone release was significantly higher in p-NP- than 17beta-E2-treated explant cultures. By this time, cleavage of caspase-3 was evident in cultures treated with 17beta-E2 and p-NP. In BeWo cells, a caspase-3 band of 20-16 kDa was evident after 1 h of treatment with p-NP and after 24 h of treatment with 17beta-E2 or forskolin. These findings suggest that the human trophoblast may be highly responsive to p-NP and raise concern about maternal exposure in early gestation.

EDTA, NTA, Alkylphenol Ethoxylate and DOC Attenuation during Soil Aquifer Treatment

Removals of dissolved organic carbon (DOC), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and carboxylated alkylphenol polyethoxylate metabolites (APECs) were studied at the Sweetwater (Tucson, Ariz.) soil aquifer treatment site that treated chlorinated secondary effluent. The site was operated in a first phase by flooding irregularly for weeks interrupted by days of drying and in a second phase by a regular schedule of flooding for 3 days and drying for 4 days. The average hydraulic loading rates were 0.13 and 0.17 m∕day in the first and second phases, respectively. During drying, oxygen intruded at least 3 m deep into the unsaturated subsurface causing nitrification of the ammonium that was retained in the top layer during flooding. Nitrification increased nitrate concentrations to >200 mg∕L but most was removed to <10 mg∕L during transport to 38 m depth. At 38 m depth, removals of DOC, EDTA, NTA, and APECs during the first phase were 85, 80, 90, and 98%, slightly higher (<7%) than...

Characterization of Aircraft Deicer and Anti-Icer Components and Toxicity in Airport Snowbanks and Snowmelt Runoff

Snowbank samples were collected from snowbanks within a medium-sized airport for four years to characterize aircraft deicer and anti-icer (ADAF) components and toxicity. Concentrations of ADAF components varied with median glycol concentrations from individual sampling periods ranging from 65 to 5940 mg/L. Glycol content in snowbanks ranged from 0.17 to 11.4% of that applied to aircraft. Glycol, a freezing point depressant, was selectively removed during melt periods before snow and ice resulting in lower glycol concentrations after melt periods. Concentrations of ADAF components in airport runoff were similar during periods of snowmelt as compared to active ADAF application periods; however, due to the long duration of snowmelt events, greater masses of glycol were transported during snowmelt events. Alkylphenol ethoxylates (APEO), selected APEO degradation products, and 4- and 5-methyl-1H-benzotriazole were detected in snowbank samples and airport snowmelt. Concentrations of APEO parent products were greater in snowbank samples than in runoff samples. Relative abundance of APEO degradation products increased in the downstream direction from the snowbank to the outfalls and the receiving stream with respect to APEO parent compounds and glycol. Toxicity in Microtox assays remained in snowbanks after most glycol had been removed during melt periods. Increased toxicity in airport snowbanks as compared to other urban snowbanks was not explained by additional combustion or fuel contribution in airport snow. Organic markers suggest ADAF additives as a possible explanation for this increased toxicity. Results indicate that glycol cannot be used as a surrogate for fate and transport of other ADAF components.

Aerobic biodegradation of alkylphenol ethoxylates

Primary aerobic biodegradation of alkylphenol ethoxylates (APEOs) was studied using a new simple and fast porphyrin method, which did not require the extraction step. Extent of primary biodegradation of a nonylphenol ethoxylates (NP-10) was excess of 92% after 1.5 days, and reached 99% after 2 days, which was similar to the results obtained using modified CTAS (thiocyanate active substances) method. Degradation of benzene ring of NP-10 was studied using UV-absorbance at 277 nm in chloroform. Results showed that only little of benzene ring was degraded.

Interaction behavior in ultrafiltration of nonionic surfactant micelles by adsorption

Adsorption of nonionic surfactant micelles onto ultrafiltration (UF), membranes was studied. Two homologous series of nonionic surfactants, namely, Tritons (alkylphenol ethoxylates) and Neodols (alcohol ethoxylates), were used to characterize surface properties of two polymeric ultrafiltration membranes with 20,000 nominal cutoff. Particularly, a cellulose acetate and a polysulfone membrane were investigated. Static adsorption experiments were carried out using surfactant solutions at concentrations above their critical micelle concentration. The characterization of surface properties of UF membranes was based on the adsorption behavior of surfactant species. The adsorption extent on UF membranes was affected by the hydrophobicity-to-hydrophilicity ratio mainly determining the interactions developed at the membrane–surfactant species interface. Adsorption experimental data seem generally to fit the Langmuir isotherm model. Atomic force microscopy was used to examine the alteration of the top membrane surface morphology.

Aplicação de ácido giberélico (GA&lt;sub&gt;3&lt;/sub&gt;) em précolheita de tangerina ‘Poncã’ (&lt;em&gt;Citrus reticulata&lt;/em&gt; blanco)

The experiment was carried out in a commercial orchard of ‘Ponkan’ mandarin ( Citrus reticulata Blanco), grafted on ‘Cleopatra’ mandarin ( Citrus reshni Hort. ex Tan.), in Pratânia, state of Sao Paulo, Brazil. The utilized experimental design was composed of randomized blocks of four replications. The treatments consisted of: 0 (control), 5, 10, 15 and 20 mg L 1 of Gibberellic acid (GA 3 ). Atomizer equipment was utilized for the application of the treatments. Each plant received 5.9 liters of solution, in which 0.03% of nonionic surfactant with 25% of alkylphenol ethoxylate was added, in order to change fruit coloration. The analyses of fruit quality were developed on the 13th, 45th, 75th and 111th days after the application of the treatments (DAT). Results showed that the application of GA 3 did not affect fruit fresh mass, total soluble solids content, total titulable acidity and ratio. However, a delay in fruit harvesting was verified, which was induced by the physiological effect of Gibberellic acid.

The Removal of Alkylphenol Ethoxylate Surfactants in Activated Sludge Systems

The Removal of Alkylphenol Ethoxylate Surfactants in Activated Sludge Systems

SEM studies of surfactant‐assisted micro‐mixing of melamine and wax particles

AbstractThe validity of the micro‐mixing phenomenon was investigated by mixing a melamine dispersion, stabilized by low molecular mass poly(acrylic acid) (∼5000 Daltons) and a wax emulsion, stabilized by an ethoxylated alkyl phenol surfactant. The wax particles were observed to be attached to the melamine surface because of the interaction between the poly(acrylic acid) dispersant and the ethoxylate group of the wax surfactant, resulting in the sedimentation of mixed particles. This phenomenon has potential application in the mixing of solid particles that require intimate contact and homogeneous mixing. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2554–2557, 2006

Development of an analytical method to determine phenolic endocrine disrupting chemicals in sewage and sludge by GC/MS

An analytical method has been developed to determine bisphenol A and five degradation products of alkylphenol ethoxylates in sewage and sludge. The parameters of accelerated solvent extraction (ASE) were optimized. C18 cartridge was used to clean up the sewage and the extract of sludge. The sensitivity of the mass detector was improved by adjusting the voltage of the lens manually. The instrumental detection limit was 3.2 – 17.8 pg. The method detection limits were 2.5–11.4 ng/L and 0.3–2.1 ng/g for sewage and sludge analysis respectively. The recovery and relative standard deviation for sewage analysis were 79.2% –111.4% and 6.9%–12.6%; for sludge analysis were 68.5%–114.0% and 8.9%–16.0%. Finally this method was applied to determining the phenolic endocrine disrupting chemicals in sewage and sludge from a sewage treatment plant in Beijing.

In vivo bioassay‐guided fractionation of marine sediment extracts from the Southern California Bight, USA, for estrogenic activity

The exposure and uptake of environmental estrogenic compounds have been reported in previous studies of demersal flatfish species in the central Southern California Bight (SCB), USA. The objective of this study was to evaluate the estrogenic or feminizing activity of marine sediments from the SCB by using in vivo vitellogenin (VTG) assays in male or juvenile fish. In 2003, sediments were collected near wastewater outfalls serving the counties of Los Angeles (LACSD) and Orange (OCSD), and the city of San Diego (SD), California, USA. Cultured male California halibut (CH; Paralichthys californicus) were either directly exposed to sediments for 7 d or treated with two intraperitoneal injections of sediment extract over 7 d. The 17beta-estradiol (E2) equivalent values ranged from 1 to 90 microg/kg with LACSD > SD > OCSD. Measurable concentrations of E2 were observed in all sediment extracts and ranged from 0.16 to 0.45 ng/g. Estrone (El) was only observed in sediments near the LACSD outfall (0.6 ng/g). Alkylphenols and alkylphenol ethoxylates were observed in all sediment samples, but were highest near the OCSD outfall, where concentrations of nonylphenol were 3,200 ng/g. Fractionation studies of the LACSD sediment extract collected in 2004 failed to demonstrate relationships between VTG expression and 62 analytes, including E2, which was observed in the whole extract (2.9 ng/g). Oxybenzone (1.6 ng/g) was identified in bioactive fractions as well as unknown compounds of relatively high polarity. These results indicate that estrogen receptor-based assays may underestimate environmental estrogenic activity and estrogenic compounds other than classic natural and xenoestrogens may contribute to estrogenic activity of sediments from the SCB.

Estuarine and coastal zone marine pollution by the nonionic alkylphenol ethoxylates endocrine disrupters: Is there a potential ecotoxicological problem?

The nonionic biodegradation-resistant (“hard”) alkylphenol ethoxylate (APEO) surfactants and their degradation products are known endocrine disrupting chemicals (EDCs). We report here the findings concerning the APEOs concentrations and homologic distribution profiles in Israel's estuarine and coastal zone seawater to serve as a case study. The concentrations in sewage-containing rivers, estuaries and 50–60-m offshore sea (Mediterranean) water were found to be 12.5–75.1, 4.2–25.0 and 0.9–2.6 μg/L, respectively. The corresponding homologic distribution profiles were found to be within the range of 1–10% each, somewhat skewing, as expected, towards the more toxic shorter-chain ethoxylates. Egg production by zebrafish, exposed to 75, 25 and 10 μg/L of a typical industrial APEOs was reduced up to 89.6%, 84.7% and 76.9%, respectively, between the 8th and 28th days of exposure. Apparently, there is a potential APEOs-related ecotoxicological health risk problem.

Full verification of the liquid exclusion-adsorption chromatography theory using monolithic capillary columns

Capillary electrochromatography (CEC) was used to separate alkyl phenol ethoxylates (APEs) as model diblock copolymers, with monolithic polymers as stationary phases. The order of elution indicate that the two polymer blocks follow distinct chromatographic modes: size-exclusion for the poly(oxyethylene) group and adsorption interaction for the alkyl part. Therefore, our experimental results were compared to the theory describing liquid exclusion-adsorption chromatography (LEAC). They were found in perfect agreement with the theory, which turned to be verified for the first time over the full range of polymer lengths.

Surfactants and interfacial phenomena

Surfactants and interfacial phenomena

Effects of nonylphenol on hepatic testosterone metabolism and the expression of acute phase proteins in winter flounder ( Pleuronectes americanus): Comparison to the effects of Saint John's Wort

4-Nonylphenol (4-NP), a major by-product of alkylphenol ethoxylates, is used in several industries and as a consequence is quite common in rivers, estuaries and other aquatic environments that receive sewage discharges or are near offshore oil platforms. 4-NP is an environmental estrogen that also binds human and rodent Pregnane X-receptor (PXR), the orphan nuclear receptor that controls the expression of several detoxication genes in mammals, including several CYP3A and CYP2B family members. These P450s preferentially hydroxylate testosterone in the 6β- and 16β-positions, respectively. In this study, the effects of 4-NP on testosterone metabolism and hepatic CYP3A induction were compared to the effects of St. John's Wort (SJW), a well established mammalian PXR agonist, in winter flounder. Male winter flounder ( Pleuronectes americanus) were injected with 100 mg/kg/day 4-NP or 500 mg/kg/day SJW or both (S and N) every 24 h. Forty-eight hours after the initial injections, flounder were euthanized. Western blots and testosterone 6β-hydroxylation indicated that CYP3A was increased 50% by 4-NP, but was not affected by SJW. Testosterone 16β-hydroxylase activity was also significantly increased in flounder treated with 4-NP (2.8×), but not with SJW. This is not consistent with our hypothesis that both SJW and 4-NP would induce CYP3A. Subtractive hybridization was performed between control and 4-NP treated hepatic mRNA samples to isolate differentially expressed genes. Subtractive hybridization indicated that several acute phase proteins were altered by 4-NP. Quantitative real-time PCR (Q-PCR) confirmed 4-NP altered the expression of complement components C8b, cathepsin L, C-type lectin domain, FK506 binding protein 2 precursor (FKBP2) and an EST (expressed sequence tag). SJW and 4-NP treated flounder demonstrated similar induction profiles for the EST, cathepsin L and FKBP2, suggesting that SJW was at a sufficient dose to alter gene expression but not induce P450s. In conclusion, testosterone hydroxylase activity and Western blots indicate that SJW did not activate detoxication pathways in a similar manner to 4-NP.

Determination of non-ionic polyethoxylated surfactants in wastewater and river water by mixed hemimicelle extraction and liquid chromatography–ion trap mass spectrometry

The capability of hemimicelles-based solid phase extraction (SPE)/liquid chromatography/atmospheric pressure chemical ionisation in positive mode, ion trap mass spectrometry (LC/(APCI +-IT)–MS) for the concentration, separation and quantitation of non-ionic surfactants has been investigated. Concentration was based on the formation of mixed aggregates of analytes [alkylphenol ethoxylates (APE, octyl and nonyl) and alkyl ethoxylates (AE, C 12–C 16)] with the anionic surfactant sodium dodecyl sulphate (SDS) that is adsorbed on alumina. Parameters affecting SPE were investigated on the basis that hemimicelles are dynamic entities in equilibrium with the aqueous phase. The performance of ion trap mass spectrometry for MS and MS/MS quantitation of non-ionic homologues was assessed. Recoveries of analytes from wastewater influent and effluent and river water samples ranged between 91 and 98% and were found independent on the length of the alkyl chain under the optimised conditions. Anionic surfactants did not interfere to the levels found in environmental samples. The detection limits ranged between 14 and 111 ng/l for wastewater influent, 10 and 40 for wastewater effluent and 4 and 35 for river water, after concentration of 250, 500 and 750 ml of sample, respectively. The approach was applied to the determination of AE and APE in influent and effluent samples from four wastewater treatment plants and four river samples. The concentrations of individual non-ionic surfactants found ranged between 0.3 and 373 μg/l.

The case of the nonionic alkylphenol ethoxylates in the Mediterranean Sea region: is there a problem?

The concentration profiles of the potential endocrine disrupting nonionic alkylphenol ethoxylate (APEO) surfactants in Israel's rivers, groundwaters and coastal water of the eastern Mediterranean Sea, were found to be within the range of 12.5-74.6, trace - 20.2 and 4.2-25.0 microg/L respectively. Determination of the APEO's homologic distribution revealed "skewing" towards the more toxic shorter-chain ethoxylates. Egg production of zebrafish, Danio rerio, exposed to these actually found the environmental concentrations range of the APEOs decreased, after 20 days, to 89.6+/-2.1, 84.7+/-3.9 and 76.9+/-2.2% of the baseline levels, compared with control, in concentrations of 10, 25 and 75 microg/L respectively. These results suggest that, (a) there is a potential health problem, particularly in countries in which the "hard"/environmentally persistent APEOs are still in use; and (b) the related health-risk is seasonally-dependent, particularly in semi-arid regions where the fluctuations in the water quantities in surface- and groundwater are substantial.

A Monitoring System for Selective Determination of Alkylphenol Ethoxylates by the Adsorptive Stripping‐Indirect Tensammetric Technique

AbstractA new monitoring system for the adsorptive stripping‐indirect tensammetric technique has been developed. The system responded selectively to alkylphenol ethoxylates having 5–14 oxyethylene subunits (APE) (being a fraction of nonionic surfactants). It consists of 20 ppm of Mannoxol OT and 20 ppb of tetrabutylammonium bromide (TBAB). In the presence of APE a tensammetric peak of the monitoring mixture is growing. A calibration plot has a slightly sigmoidal shape; the dynamic response range is from 0.5 to 2.0 μg and the detection limit is 0.075 μg. APE determination is highly tolerant to alcohol ethoxylates (AE) having a C18 hydrophobic part, however, the tolerance of AE having a C12 hydrophobic part is small (the APE signal is only three times higher than that of AE having a C12 hydrophobic part). An analytical response to a mixture consisting different nonionic surfactants (NS) is approximately additive. The developed monitoring system was applied to the determination of an APE fraction in 14 river water samples. NS were separated from the water matrix by liquid‐liquid extraction with chloroform. The recovery of Triton X‐100 spike was 102% and the precision 6.5%.

Immunoenzyme assay of nonylphenol: study of selectivity and detection of alkylphenolic non-ionic surfactants in water samples

Immunoenzyme assay (ELISA) is proposed and characterized for determination of alkylphenol ethoxylates, a primary class of manufactured non-ionic surfactants. The assay is based on the obtained polyclonal antibodies against nonylphenol (NP), the main stable intermediate of the decomposition of nonylphenol ethoxylates. A mixture of non-modified branched isomers of NP was applied as hapten coupled to protein carriers by Mannich reaction with the use of formaldehyde. The proposed ELISA format is based on immobilized NP–(soybean trypsin inhibitor) conjugate as a competitor of antigen molecules contained in the tested sample for binding with specific antibodies indirectly labeled via an anti-species immunoperoxidase conjugate. The developed ELISA allows to reveal NP with the limit of detection about 10 ng ml −1 and NP-related compounds such as octylphenol, alkylphenoletoxylates, alkylphenolcarboxylates and their halogenated derivatives. The ELISA was applied for assaying polluted water samples, namely influents and effluents from different wastewater treatment plants (WWTP) and tap water. ELISA and chromatographic data demonstrate good correlation ( r = 0.94), while ELISA gives higher values. Due to endocrine disrupting and other toxic activities of some metabolites of alkylphenolic non-ionic surfactants, the developed assay may be effectively used in ecological monitoring and sanitary control.

Degradation of Recalcitrant Surfactants in Wastewater by Ozonation and Advanced Oxidation Processes: A Review

ABSTRACT Surfactants are used in varieties of industrial cleansing processes as well as in consumer products. Spent surfactants normally enter domestic or industrial wastewater and are treated biologically. However, some of them are resistant to biodegradation and are released into the environment. Thus, the toxicity and environmental persistence of these surfactants are emerging concerns. Based on extensive review of the literature, ozonation and advanced oxidation using various combinations of ozone, hydrogen peroxide, ultraviolet light irradiation, and iron salts were found effective in degrading recalcitrant surfactants, including linear alkylbenzene sulfonates, alkylphenol ethoxylates, and quaternary ammonium surfactants. Biodegradability of these surfactants was improved after the treatment to some extent in the aqueous solution as well as in real wastewaters.