Alkylphenol ethoxylates and alkylphenols--update information on occurrence, fate and toxicity in aquatic environment.

PubMed

Kovarova, J; Blahova, J; Divisova, L; Svobodova, Z

2013-01-01

Alkylphenols and their precursors, alkylphenol etoxylates, are a group of manmade chemicals used mainly as surfactants in domestic and industrial applications worldwide. It has been well established that they have endocrine disruption activity, hepatotoxic, genotoxic and other negative effects on animal and human health. In spite of the effort to reduce their use, they persist in the environment not only in industrial but also in remote regions, and were detected in the variety of natural matrices including air, water, soil as well as food products, and human blood and urine worldwide. This article summarizes their occurrence, fate in natural conditions, and toxicity including mode of action. A subject of our concern was the aquatic environment as the most important reservoir and target of their deleterious impact.

ANALYSIS OF ALKYLPHENOLS AND ALKYLPHENOL ETHOXYLATES WITH SEPARATION OF ETHOXYMERS USING REVERSED PHASE LC/MS

EPA Science Inventory

Alkylphenol polyethoxylates are non-ionic surfactants, widely used in detergents, paints, personal care products, etc., which enter the environment primarily through wastewater treatment systems. Their biodegradation during wastewater treatment leads to the formation of persisten...

Characterization of aircraft deicer and anti-icer components and toxicity in airport snowbanks and snowmelt runoff.

PubMed

Corsi, Steven R; Geis, Steven W; Loyo-Rosales, Jorge E; Rice, Clifford P; Sheesley, Rebecca I; Failey, Greg G; Cancilla, Devon A

2006-05-15

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.

Characterization of aircraft deicer and anti-icer components and toxicity in airport snowbanks and snowmelt runoff

USGS Publications Warehouse

Corsi, S.R.; Geis, S.W.; Loyo-Rosales, J. E.; Rice, C.P.; Sheesley, R.J.; Failey, G.G.; Cancilla, Devon A.

2006-01-01

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. ?? 2006 American Chemical Society.

Determination of nonylphenol ethoxylate and octylphenol ethoxylate surfactants in beehive samples by high performance liquid chromatography coupled to mass spectrometry.

PubMed

Chen, Jing; Mullin, Christopher A

2014-09-01

Nonylphenol and octylphenol ethoxylates (NP(EO)n and OP(EO)n) are major toxicants in agrochemicals used around beehives. Here we developed a LC-MS method for analysis of NP(EO)3-13 and OP(EO)3-13 oligomers in bee hive matrices. Less than 2 g of honey, pollen or wax were extracted using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach. Recoveries for each oligomer in all matrices are between 75% and 111% at three spiked concentrations. The method proved to be rapid, precise and sensitive. Five honey, 10 pollen and 12 wax samples were collected and analysed. NP(EO)n was detected in every sample with concentrations ranging from 26 ppb to 10,239 ppb. Much higher NP(EO)n residues levels were found in wax followed by pollen than in honey. OP(EO)n concentrations on average were more than 10 times lower in pollen and wax. This method demonstrates a probable wide occurrence of alkylphenol ethoxylates in USA beehives. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mass spectrometric behaviour of carboxylated polyethylene glycols and carboxylated octylphenol ethoxylates.

PubMed

Frańska, Magdalena; Zgoła, Agnieszka; Rychłowska, Joanna; Szymański, Andrzej; Łukaszewski, Zenon; Frański, Rafał

2003-01-01

Mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) are discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali metal cations) of carboxylated PEGs was compared with that of non-carboxylated correspondents by using both secondary ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral correspondents, PEGs. The B/E mass spectra were recorded, using secondary ion mass spectrometry as a method for generation, for deprotonated and protonated molecules and molecules cationised by alkali metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxylic groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H](-) ions proceed through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain leading to the octylphenoxy anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative ion mode were found to be more suitable for the determination of the average molecular weight of carboxylated ethoxylates than SI mass spectra.

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

PubMed

Mart'ianov, Andrey A; Dzantiev, Boris B; Zherdev, Anatoly V; Eremin, Sergei A; Cespedes, Raquel; Petrovic, Mira; Barcelo, Damia

2005-01-30

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 10ngml(-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.

Determination of free and ethoxylated alkylphenols in leather with gas chromatography-mass spectrometry.

PubMed

Ma, He-Wei; Cheng, Ya

2010-12-10

An analytical approach was developed to determine nonylphenol (NP), octylphenol (OP), nonylphenol ethoxylates (NPEO(n)) and octylphenol ethoxylates (OPEO(n)) in leather samples involving the conversion of NPEO(n) and OPEO(n) into the corresponding NP and OP. The four targets were extracted from samples using ultrasonic-assisted acetonitrile extraction. NP and OP in the extracts were directly isolated with hexane and quantitatively determined with 4-n-nonylphenol as internal standard by gas chromatography-mass spectrometry (GC-MS). For NPEO(n) and OPEO(n) in the extracts, they were first converted into NP and OP with aluminum triiodide as cleavage agent, and the yielded NP and OP were determined by GC-MS. The contents of NPEO(n) and OPEO(n) were calculated by normalizing to NPEO(9) and OPEO(9), respectively. This method was properly validated and the real sample tests revealed the pollution significance of leather by NPEO(n) and OPEO(n). Copyright © 2010 Elsevier B.V. All rights reserved.

Degradation of chlorophenols and alkylphenol ethoxylates, two representative textile chemicals, in water by advanced oxidation processes: the state of the art on transformation products and toxicity.

PubMed

Karci, Akin

2014-03-01

Advanced oxidation processes based on the generation of reactive species including hydroxyl radicals are viable options in eliminating a wide array of refractory organic contaminants in industrial effluents. The assessment of transformation products and toxicity should be, however, the critical point that would allow the overall efficiency of advanced oxidation processes to be better understood and evaluated since some transformation products could have an inhibitory effect on certain organisms. This article reviews the most recent studies on transformation products and toxicity for evaluating advanced oxidation processes in eliminating classes of compounds described as "textile chemicals" from aqueous matrices and poses questions in need of further investigation. The scope of this paper is limited to the scientific studies with two classes of textile chemicals, namely chlorophenols and alkylphenol ethoxylates, whose use in textile industry is a matter of debate due to health risks to humans and harm to the environment. The article also raises the critical question: What is the state of the art knowledge on relationships between transformation products and toxicity? Copyright © 2013 Elsevier Ltd. All rights reserved.

Tandem Extraction/Liquid Chromatography-Mass Spectrometry Protocol for the Analysis of Acrylamide and Surfactant-Related Compounds in Complex Matrix Environmental Water Samples

EPA Science Inventory

Ethoxylated alcohols, alkylphenols, and acrylamide are emerging contaminants with many different routes into the environment. Ethoxylated alcohols are used ubiquitously as surfactants in both industrial and household products. The use of ethoxylated alcohols and alkylphenols as s...

Occurrence of alkylphenolic substances in a Great Lakes coastal marsh, Cootes Paradise, ON, Canada.

PubMed

Mayer, T; Bennie, D; Rosa, F; Rekas, G; Palabrica, V; Schachtschneider, J

2007-06-01

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 microg g(-1). To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions.

Meta-analysis of environmental contamination by alkylphenols.

PubMed

Bergé, Alexandre; Cladière, Mathieu; Gasperi, Johnny; Coursimault, Annie; Tassin, Bruno; Moilleron, Régis

2012-11-01

Alkylphenols and alkylphenol ethoxylates (APE) are toxics classified as endocrine-disrupting compounds; they are used in detergents, paints, herbicides, pesticides, emulsifiers, wetting and dispersing agents, antistatic agents, demulsifiers, and solubilizers. Many studies have reported the occurrence of alkylphenols in different environmental matrices, though none of these studies have yet to establish a comprehensive overview of such compounds in the water cycle within an urban environment. This review summarizes APE concentrations for all environmental media throughout the water cycle, from the atmosphere to receiving waters. Once the occurrence of compounds has been assessed for each environmental compartment (urban wastewater, wastewater treatment plants [WWTP], atmosphere, and the natural environment), data are examined in order to understand the fate of APE in the environment and establish their geographical and historical trends. From this database, it is clear that the environment in Europe is much more contaminated by APE compared to North America and developing countries, although these APE levels have been decreasing in the last decade. APE concentrations in the WWTP effluent of developed countries have decreased by a factor of 100 over the past 30 years. This study is aimed at identifying both the correlations existing between environmental compartments and the processes that influence the fate and transport of these contaminants in the environment. In industrial countries, the concentrations observed in waterways now represent the background level of contamination, which provides evidence of a past diffuse pollution in these countries, whereas sediment analyses conducted in developing countries show an increase in APE content over the last several years. Finally, similar trends have been observed in samples drawn from Europe and North America.

Hydrophile-lipophile balance of alkyl ethoxylated surfactants as a function of intermolecular energies.

PubMed

Urbina-Villalba, G; Rogel, E; Márquez, M L; Reif, I

1994-06-01

The semiempirical MNDO method has been used in order to examine the variation of the molecular properties of hydrocarbons CnH2n + 2 (with 1 < or = n < or = 19) and ethylene oxide chains CH3(CH2CH2O)mCH3 (with 1 < or = m < or = 19) as a function of their molecular length. Least-square fits of those properties have been calculated, along with two mathematical relations between the hydrophile-lipophile balance of alkyl-phenol ethoxylated surfactants and (1) the ratio of molecular lengths between their lipophilic and hydrophilic branches; (2) the intermolecular energies between the molecules of surfactant, water and hexane.

Surfactants in aquatic and terrestrial environment: occurrence, behavior, and treatment processes.

PubMed

Jardak, K; Drogui, P; Daghrir, R

2016-02-01

Surfactants belong to a group of chemicals that are well known for their cleaning properties. Their excessive use as ingredients in care products (e.g., shampoos, body wash) and in household cleaning products (e.g., dishwashing detergents, laundry detergents, hard-surface cleaners) has led to the discharge of highly contaminated wastewaters in aquatic and terrestrial environment. Once reached in the different environmental compartments (rivers, lakes, soils, and sediments), surfactants can undergo aerobic or anaerobic degradation. The most studied surfactants so far are linear alkylbenzene sulfonate (LAS), quaternary ammonium compounds (QACs), alkylphenol ethoxylate (APEOs), and alcohol ethoxylate (AEOs). Concentrations of surfactants in wastewaters can range between few micrograms to hundreds of milligrams in some cases, while it reaches several grams in sludge used for soil amendments in agricultural areas. Above the legislation standards, surfactants can be toxic to aquatic and terrestrial organisms which make treatment processes necessary before their discharge into the environment. Given this fact, biological and chemical processes should be considered for better surfactants removal. In this review, we investigate several issues with regard to: (1) the toxicity of surfactants in the environment, (2) their behavior in different ecological systems, (3) and the different treatment processes used in wastewater treatment plants in order to reduce the effects of surfactants on living organisms.

Pharmaceuticals, alkylphenols and pesticides in Mediterranean coastal waters: Results from a pilot survey using passive samplers

NASA Astrophysics Data System (ADS)

Munaron, Dominique; Tapie, Nathalie; Budzinski, Hélène; Andral, Bruno; Gonzalez, Jean-Louis

2012-12-01

21 pharmaceuticals, 6 alkylphenols and 27 hydrophilic pesticides and biocides were investigated using polar organic contaminant integrative samplers (POCIS) during a large-scale study of contamination of French Mediterranean coastal waters. Marine and transitional water-bodies, defined under the EU Water Framework Directive were monitored. Our results show that the French Mediterranean coastal waters were contaminated with a large range of emerging contaminants, detected at low concentrations during the summer season. Caffeine, carbamazepine, theophilline and terbutaline were detected with a detection frequency higher than 83% in the coastal waters sampled, 4-nonylphenol (4-NP), 4-tert-octylphenol (4-OP) and 4-nonylphenol diethoxylate (NP2EO) were detected in all coastal waters sampled, and diuron, terbuthylazine, atrazine, irgarol and simazine were detected in more than 77% of samples. For pharmaceuticals, highest time-weighted average (TWA) concentrations were measured for caffeine and carbamazepine (32 and 12 ng L-1, respectively). For alkylphenols, highest TWA concentrations were measured for 4-nonylphenol mono-ethoxylate and 4-nonylphenol (41 and 33 ng L-1, respectively), and for herbicides and biocides, they were measured for diuron and irgarol (33 and 2.5 ng L-1, respectively). Except for Diana lagoon, lagoons and semi-enclosed bays were the most contaminated areas for herbicides and pharmaceuticals, whilst, for alkylphenols, levels of contamination were similar in lagoons and coastal waters. This study demonstrates the relevance and utility of POCIS as quantitative tool for measuring low concentrations of emerging contaminants in marine waters.

Attenuation of Selected Emerging Contaminants During River Transport

NASA Astrophysics Data System (ADS)

Reinhard, M.; Gross, B.; Hadeler, A.

2002-12-01

The ubiquitous occurrence of emerging (non-regulated) contaminants in the aquatic environment is of concern because some of these chemicals are biologically active at low concentrations and a potential threat to wildlife and human health.. Emerging contaminants include a diverse range of chemicals, including pharmaceuticals, natural and synthetic hormones and industrial surfactants, such as alkylphenol ethoxylates (APEO) and their metabolites. To address the ecotoxicological impact of these chemicals, it is necessary to know their sources, removal efficiencies during wastewater treatment, and their behavior in the environment. In this study, the fate of selected emerging contaminants in the Santa Ana River (SAR) in Southern California was investigated. The SAR originates in the San Bernardino Mountains and flows 80 miles into the Pacific Ocean. The SAR flow stems mainly from storm runoff, wastewater treatment effluents and several other minor sources. During the dry season, SAR flow is dominated by effluent from public wastewater treatment plants. Input into the SAR was studied by analyzing samples from four major treatment plants that employ different tertiary treatment processes. To assess the fate during river water transport and during wetland treatment, samples from six sites along the river were analyzed. Effluent samples were analyzed every two months, river water every four months. River samples were taken considering the flow velocity, which is approximately 1 mile per hour. The analytical method involves solid-phase extraction using C-18 cartridges and extraction of three fractions. Samples were analyzed with and without further derivatization using GC/MS and GC/MS/MS. Results indicate significant contaminant removal during river transport, presumably by photochemical oxidation. Within a distance of nine miles, pharmaceuticals, plasticizers, flame retardants, APEOs and metabolites were attenuated with removal rates ranging from 76% for a flame retardant

Mediated electrochemical oxidation (MEO) process: a study on nonylphenol ethoxylates (NPE) oxidation in batch mode using cerium (IV) oxidant

NASA Astrophysics Data System (ADS)

Setiyanto, H.; Adyatmika, I. M.; Syaifullah, M. M.; Zulfikar, M. A.; Buchari

2018-05-01

Nonylphenol ethoxylate (NPE-10) is one type of non-ionic surfactants from the class of alkylphenol ethoxylate (APE). This compound is already tightened their use in European Union countries. However, these surfactants are still used widely in Indonesia because the price is relatively cheap. Consequently, these compounds can accumulate in aquatic environments. NPE-10 can disrupt aquatic ecosystems. This study aimed to describe the electro-oxidation process of NPE-10 based on the parameters of a potential difference, concentration of NPE-10, concentration of Ce (III), and oxidation time. The result of oxidation NPE-10 was measured by the amount of current generated from voltammetry technique. Studies of cyclic voltammetry using carbon paste electrodes illustrates the potential value of the oxidation of Ce (III) / Ce (IV) of 1.25 V and the reduction potential value of Ce (IV) / Ce (III) of 1.192 V. NPE-10 are electroactive irreversible because it only provides the potential value of oxidation at 1.44 V. Percent of total degradation of 84.96% was obtained at electro-oxidation of 500 ppm NPE-10 by the addition of 0.015 M Ce (III) for 90 minutes at 0.2 M H2SO4and the use of potential of 6 V.

40 CFR 721.4365 - Substituted ethoxylated hydrocarbon (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted ethoxylated hydrocarbon... Specific Chemical Substances § 721.4365 Substituted ethoxylated hydrocarbon (generic). (a) Chemical... as Substituted ethoxylated hydrocarbon (PMN P-99-0313) is subject to reporting under this section for...

40 CFR 721.4365 - Substituted ethoxylated hydrocarbon (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted ethoxylated hydrocarbon... Specific Chemical Substances § 721.4365 Substituted ethoxylated hydrocarbon (generic). (a) Chemical... as Substituted ethoxylated hydrocarbon (PMN P-99-0313) is subject to reporting under this section for...

Partnership to Evaluate Alternatives to Nonylphenol Ethoxylates

EPA Pesticide Factsheets

The partnership alternatives assessment project on nonylphenol ethoxylates sought to address concerns about potential ecological and other effects from manufacturing, processing, and distribution of nonylphenol ethoxylates

Tissue concentrations of organic contaminants in fish and their biological effects in a wastewater-dominated urban stream

USDA-ARS?s Scientific Manuscript database

Data are presented on the fish tissue concentrations of persistent organic compounds and alkylphenol and alkylphenol ethoxylates (APEs) in large-mouth bass collected from a waste water dominated stream in downtown Chicago. The fish residue concentrations of APEs are compared to concentrations of th...

Alkylphenol and bisphenol A contamination of urban runoff: an evaluation of the emission potentials of various construction materials and automotive supplies.

PubMed

Lamprea, Katerine; Bressy, Adèle; Mirande-Bret, Cécile; Caupos, Emilie; Gromaire, Marie-Christine

2018-05-23

Alkylphenol (AP) and bisphenol A (BPA) contamination of urban runoff has already been established. Potential sources of these contaminants in runoff are endogenous to the urban watershed and are mainly related to traffic and leaching from construction materials. This article summarizes the results of experimental work carried out on a selection of building materials, automotive materials, and consumables, which can be in contact with rain, to assess their potential emission of alkylphenols, alkylphenol ethoxylates, and bisphenol A into runoff. 36 samples of materials, new and used, across 7 major families of building materials (PVC, concrete, polycarbonate, SBS-modified bitumen, drainage materials) and automotive materials (body, tires) were subjected to leaching tests with methanol and then, for a selection of them, with water. Automotive fluids were also directly analyzed. The results demonstrate the ubiquitous presence of APs and BPA in urban materials and their extractable character with water. The compounds with the strongest emission rates were bisphenol A and nonylphenol. The most important BPA emissions into water (10 to 300 ng/g) were measured for polycarbonate, tires, some car bodies, and PVC. Nonylphenol was leached in large quantities (1 to 10 ng/g) from PVC, some concretes, SBS-modified bitumen, and body samples. The tires were the only materials having a strong emission in octylphenol (1 to 10 ng/g). The analysis of automotive fluids confirmed the presence of BPA (0.3 to 5.5 g/L) and nonylphenol (2.3 to 2.9 mg/L) in brake fluids, while APs and BPA were found at trace levels in coolants and windscreen washer. Graphical abstract ᅟ.

Sodium dodecyl sulfate-ethoxylated polyethylenimine adsorption at the air-water interface: how the nature of ethoxylation affects the pattern of adsorption.

PubMed

Batchelor, Stephen N; Tucker, Ian; Petkov, Jordan T; Penfold, Jeffrey; Thomas, Robert K

2014-08-19

The strong interaction between ionic surfactants and polyelectrolytes of opposite charge results in enhanced surface adsorption at the air-water interface down to low surfactant concentrations and in some cases in the formation of ordered surface structures. A notable example which exhibits such properties is the mixture of polyethylenimine, PEI, and sodium dodecyl sulfate, SDS. However, the electrostatic interaction, around charge neutralization, between the surfactant and polymer often results in precipitation or coacervation. This can be mitigated for PEI-surfactant mixtures by ethoxylation of the PEI, but this can also result in a weaker surface interaction and a significant reduction in the adsorption. It is shown here that by localizing the ethoxylation of the PEI into discrete regions of the polymer precipitation upon the addition of SDS is suppressed, the strong surface interaction and enhanced adsorption of the polymer-surfactant mixture is retained. The adsorption of SDS in the presence of ethoxylated PEI is greatly enhanced at low SDS concentrations compared to the adsorption for pure SDS. The adsorption is equally pronounced at pH 7 and 10 and is largely independent of the degree of ethoxylation. Surface ordering, more than monolayer adsorption, is observed over a relatively narrow range of SDS concentrations and is most pronounced at pH 10 and for the polymers with the lower degree of ethoxylation. The results show that ethoxylated PEI's reported here provide a suitable route to enhanced surfactant adsorption while retaining favorable solution properties in which precipitation effects are minimized.

40 CFR 721.5970 - Phosphated polyarylphenol ethoxylate, potassium salt.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., potassium salt. 721.5970 Section 721.5970 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5970 Phosphated polyarylphenol ethoxylate, potassium salt. (a) Chemical... as phosphated polyarylphenol ethoxylate, potassium salt (PMN P-93-1222) is subject to reporting under...

40 CFR 721.5970 - Phosphated polyarylphenol ethoxylate, potassium salt.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., potassium salt. 721.5970 Section 721.5970 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5970 Phosphated polyarylphenol ethoxylate, potassium salt. (a) Chemical... as phosphated polyarylphenol ethoxylate, potassium salt (PMN P-93-1222) is subject to reporting under...

40 CFR 721.5970 - Phosphated polyarylphenol ethoxylate, potassium salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., potassium salt. 721.5970 Section 721.5970 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5970 Phosphated polyarylphenol ethoxylate, potassium salt. (a) Chemical... as phosphated polyarylphenol ethoxylate, potassium salt (PMN P-93-1222) is subject to reporting under...

40 CFR 721.5970 - Phosphated polyarylphenol ethoxylate, potassium salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., potassium salt. 721.5970 Section 721.5970 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5970 Phosphated polyarylphenol ethoxylate, potassium salt. (a) Chemical... as phosphated polyarylphenol ethoxylate, potassium salt (PMN P-93-1222) is subject to reporting under...

40 CFR 721.5970 - Phosphated polyarylphenol ethoxylate, potassium salt.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., potassium salt. 721.5970 Section 721.5970 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.5970 Phosphated polyarylphenol ethoxylate, potassium salt. (a) Chemical... as phosphated polyarylphenol ethoxylate, potassium salt (PMN P-93-1222) is subject to reporting under...

Improving the Qualities of the Alkylphenol Additive BFK,

DTIC Science & Technology

The additive BFK produced from alkylphenol subjected to preliminary purification by silica gel, aluminum silicate catalysts, and distillation under...The quality of the additive produced from purified alkylphenol is comparable to the quality of non-Soviet additives. (Author)

Utilization of quantitative structure-activity relationships (QSARs) in risk assessment: Alkylphenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beck, B.D.; Toole, A.P.; Callahan, B.G.

1991-12-01

Alkylphenols are a class of environmentally pervasive compounds, found both in natural (e.g., crude oils) and in anthropogenic (e.g., wood tar, coal gasification waste) materials. Despite the frequent environmental occurrence of these chemicals, there is a limited toxicity database on alkylphenols. The authors have therefore developed a 'toxicity equivalence approach' for alkylphenols which is based on their ability to inhibit, in a specific manner, the enzyme cyclooxygenase. Enzyme-inhibiting ability for individual alkylphenols can be estimated based on the quantitative structure-activity relationship developed by Dewhirst (1980) and is a function of the free hydroxyl group, electron-donating ring substituents, and hydrophobic aromaticmore » ring substituents. The authors evaluated the toxicological significance of cyclooxygenase inhibition by comparison of the inhibitory capacity of alkylphenols with the inhibitory capacity of acetylsalicylic acid, or aspirin, a compound whose low-level effects are due to cyclooxygenase inhibition. Since nearly complete absorption for alkylphenols and aspirin is predicted, based on estimates of hydrophobicity and fraction of charged molecules at gastrointestinal pHs, risks from alkylphenols can be expressed directly in terms of 'milligram aspirin equivalence,' without correction for absorption differences. They recommend this method for assessing risks of mixtures of alkylphenols, especially for those compounds with no chronic toxicity data.38 references.« less

40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethoxylated alcohol, phosphated, amine... Specific Chemical Substances § 721.643 Ethoxylated alcohol, phosphated, amine salt. (a) Chemical substance... alcohol, phosphated, amine salt (PMN P-96-1478) is subject to reporting under this section for the...

Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach.

PubMed

de Wild, P J; Huijgen, W J J; Kloekhorst, A; Chowdari, R K; Heeres, H J

2017-04-01

Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting pyrolysis oils. Pyrolysis yielded a mixture of guaiacols, catechols and, optionally, syringols in addition to alkylphenols. HDO with heterogeneous catalysts (Ru/C, CoMo/alumina, phosphided NiMO/C) effectively directed the product mixture towards alkylphenols by, among others, demethoxylation. Up to 15wt% monomeric aromatics of which 11wt% alkylphenols was obtained (on the lignin intake) with limited solid formation (<3wt% on lignin oil intake). For comparison, solid Kraft lignin was also directly hydrotreated for simultaneous depolymerisation and deoxygenation resulting in two times more alkylphenols. However, the alkylphenols concentration in the product oil is higher for the two-stage approach. Future research should compare direct hydrotreatment and the two-stage approach in more detail by techno-economic assessments. Copyright © 2017 Elsevier Ltd. All rights reserved.

40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethoxylated alcohol, phosphated, amine salt. 721.643 Section 721.643 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.643 Ethoxylated...

Wettability modification of Wender lignite by adsorption of dodecyl poly ethoxylated surfactants with different degree of ethoxylation: A molecular dynamics simulation study.

PubMed

Zhang, Lei; Li, Bao; Xia, Yangchao; Liu, Shengyu

2017-09-01

Lignite is an important and useful fossil fuel in the world and the strong hydrophilicity of it limits its applications. Surfactant adsorption on lignite is an effective way to make it hydrophobic. In this work, aiming to examine the effect of the degree of ethoxylation on the adsorption behavior of dodecyl poly ethoxylated surfactants on lignite and the wettability modification of modified lignite by surfactant adsorption, different combined systems formed by surfactants, water and a model surface of Wender lignite have been studied using molecular dynamics simulation. The adsorption configurations vary with the degree of ethoxylation. At the same adsorption amounts, increasing the degree of ethoxylation can make the adsorption layer more compactness and bring stronger adsorption strength. The results of binding energy and its components show that the adsorption of alkyl polyoxyethylene ethers surfactant on lignite is physically adsorbed rather than electrostatically or chemisorbed. Meanwhile, van der Waals interaction plays a dominant role in the adsorption. The addition of surfactant could reduce the possibility of the interaction between water and lignite. Compared to the original lignite, the interaction between them is weakened after surfactant adsorption in water/surfactant/lignite system, thus strengthening the hydrophobicity of lignite. Similar to the adsorption strength, hydrophobicity of modified lignite increases with the increase of the degree of ethoxylation. The lignite surface properties are changed due to surfactant adsorption by analyzing the compositions of interaction energy and the change of hydrogen bonds. Copyright © 2017 Elsevier Inc. All rights reserved.

40 CFR 721.10624 - Dicyclohexylmethane-4,4'-diisocyanate, polymer with ethoxylated, propoxylated polyethers (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

..., polymer with ethoxylated, propoxylated polyethers (generic). 721.10624 Section 721.10624 Protection of...,4'-diisocyanate, polymer with ethoxylated, propoxylated polyethers (generic). (a) Chemical substance... dicyclohexylmethane-4,4'-diisocyanate, polymer with ethoxylated, propoxylated polyethers (PMN P-12-326) is subject to...

40 CFR 721.10624 - Dicyclohexylmethane-4,4'-diisocyanate, polymer with ethoxylated, propoxylated polyethers (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

..., polymer with ethoxylated, propoxylated polyethers (generic). 721.10624 Section 721.10624 Protection of...,4'-diisocyanate, polymer with ethoxylated, propoxylated polyethers (generic). (a) Chemical substance... dicyclohexylmethane-4,4'-diisocyanate, polymer with ethoxylated, propoxylated polyethers (PMN P-12-326) is subject to...

Allergenic activity of an air-oxidized ethoxylated surfactant.

PubMed

Karlberg, Ann-Therese; Bodin, Anna; Matura, Mihaly

2003-11-01

Ethoxylated surfactants are used in household and industrial cleaners, topical pharmaceuticals, cosmetics and laundry products. Polyethers, e.g. ethoxylated surfactants and polyethylene glycols, are oxidized by atmospheric oxygen (autoxidized) when stored and handled. We have previously shown that a chemically well-defined non-ionic surfactant, the ethoxylated alcohol penta-ethylene glycol mono-n-dodecyl ether (C12E5), forms a complex mixture of autoxidation products when exposed to air. Predictive testing in guinea pigs showed that the surfactant itself is a non-sensitizer, but that oxidation products formed are skin sensitizers. The aim of this study was to investigate the sensitizing capacity of a total oxidation mixture of C12E5 obtained after autoxidation. The allergenic activity of different oxidation products is discussed as well as the clinical importance of the findings. This study shows that the non-ionic surfactant C12E5 containing 20% oxidation products is a sensitizing mixture. The result accords with what is observed for other compounds that are unstable when in contact with air, e.g. limonene and linalool, major fragrance terpenes. Studies regarding the clinical relevance of our findings should be performed. However, it is already clear from this study that precautions must be taken in handling and storage of ethoxylated surfactants to avoid formation of allergenic mixtures.

40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with maleic...

40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with maleic...

Results of Research in the Field of Alkylphenol Additives

DTIC Science & Technology

The preparation of Ba and Ca salts of alkylphenols and bis(2- hydroxyphenylalkyl) sulfides are discussed along with the condensation products of... alkylphenols with HCHO or HCHO and urea, an amine or NH3 as well as the dithiophosphates of the latter. The properties and performance of lubricating oils

Alkylphenols--potential modulators of the allergic response.

PubMed

Suen, Jau-Ling; Hung, Chih-Hsin; Yu, Hsin-Su; Huang, Shau-Ku

2012-07-01

The prevalence of allergic diseases has increased in recent decades. Allergic diseases, particularly asthma, are complex diseases with strong gene-environment interactions. Epidemiological studies have identified a variety of risk factors for the development of allergic diseases. Among them, endocrine-disrupting chemicals (EDCs) play an important role in triggering or exacerbating these diseases. 4-Nonylphenol (NP) and 4-octylphenol (OP)--two major alkylphenols--have been recognized as common toxic and xenobiotic endocrine disrupters. Due to their low solubility, high hydrophobicity, and low estrogenic activity, they tend to accumulate in the human body and may be associated with the adverse effects of allergic diseases. Recently, new evidence has supported the importance of alkylphenols in the in vitro allergic response. This review focuses on the effects of alkylphenols on several key cell types in the context of allergic inflammation. Copyright © 2012. Published by Elsevier B.V.

[Quantitative relationship between gas chromatographic retention time and structural parameters of alkylphenols].

PubMed

Ruan, Xiaofang; Zhang, Ruisheng; Yao, Xiaojun; Liu, Mancang; Fan, Botao

2007-03-01

Alkylphenols are a group of permanent pollutants in the environment and could adversely disturb the human endocrine system. It is therefore important to effectively separate and measure the alkylphenols. To guide the chromatographic analysis of these compounds in practice, the development of quantitative relationship between the molecular structure and the retention time of alkylphenols becomes necessary. In this study, topological, constitutional, geometrical, electrostatic and quantum-chemical descriptors of 44 alkylphenols were calculated using a software, CODESSA, and these descriptors were pre-selected using the heuristic method. As a result, three-descriptor linear model (LM) was developed to describe the relationship between the molecular structure and the retention time of alkylphenols. Meanwhile, the non-linear regression model was also developed based on support vector machine (SVM) using the same three descriptors. The correlation coefficient (R(2)) for the LM and SVM was 0.98 and 0. 92, and the corresponding root-mean-square error was 0. 99 and 2. 77, respectively. By comparing the stability and prediction ability of the two models, it was found that the linear model was a better method for describing the quantitative relationship between the retention time of alkylphenols and the molecular structure. The results obtained suggested that the linear model could be applied for the chromatographic analysis of alkylphenols with known molecular structural parameters.

40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene...

40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene...

Effects of alkylphenols on redox status in first spawning Atlantic cod (Gadus morhua).

PubMed

Hasselberg, Linda; Meier, Sonnich; Svardal, Asbjørn

2004-07-30

Offshore oil production releases large amounts of lipophilic compounds in produced water and into the ocean. The discharge of produced water from the Norwegian petroleum sector has increased from 26 million m3 in 1993 to 120 million m3 in 2001, and it continues to increase. Produced water contains significant amounts of alkylphenols, which have been reported to be estrogenic, causing endocrine disruption in fish. In year 2000, approximately 44 tons of alkylphenols were released on the Norwegian continental shelf in connection with discharge of produced water. Except from being estrogenic, relatively little is known about the effects of alkylphenols when released in the marine environment. Our objective was to study how alkylphenols affect the redox status in first spawning Atlantic cod (Gadus morhua) of both sexes. Model compounds tested included 4-tert-butylphenol (C4), 4-n-pentylphenol (C5), 4-n-hexylphenol (C6) and 4-n-heptylphenol (C7), all found in produced water. First spawning Atlantic cod were force-fed a mixture of these four alkylphenols, ranging between 0.02 and 80 ppm or 5 ppm 17beta-estradiol (E2), for 1 or 4 weeks. Increased hepatic total glutathione concentration in response to alkylphenol exposure was detected in female fish compared to control group after 1-week exposure, an effect not seen after 4 weeks. Furthermore, hepatic total glutathione concentration was sex dependent, where male fish sampled after 4 weeks had higher levels of glutathione than female fish. Increased glutathione reductase catalytic activities in both male and female fish were seen after exposure to 0.02 ppm alkylphenol mixture in 4 weeks. The glutathione S-transferase activity was only affected in male fish exposed to 0.02 ppm alkylphenols, and glucose-6-phosphate dehydrogenase activity increased in female fish exposed to 0.02 ppm alkylphenol mixture for 1 week. The increase of hepatic total glutathione content as well as the effects on glutathione reductase activities

40 CFR 721.10007 - Alcohols, C12-14-secondary, ethoxylated propoxylated.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohols, C12-14-secondary... New Uses for Specific Chemical Substances § 721.10007 Alcohols, C12-14-secondary, ethoxylated... identified as alcohols, C12-14- secondary, ethoxylated propoxylated (PMN P-00-11; CAS No. 103331-86-8) is...

40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

Code of Federal Regulations, 2011 CFR

2011-07-01

... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction...

40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

Code of Federal Regulations, 2010 CFR

2010-07-01

... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction...

Determination and residual characteristic of alkylphenols in household food detergents of Taiwan.

PubMed

Pan, Yi-Ping; Tsai, Shih-Wei

2009-07-01

The non-ionic surfactants are mostly composed of alkylphenols for the ingredients of synthetic food detergents. Due to the ability to mimic hormones, it has been noticed that the exposures of alkylphenols might cause a variety of adverse effects. To assess the associate risks from possible exposures, concentrations of alkylphenols, including 4-nonylphenol (4-NP), technical nonylphenol isomers (t-NP(S)), and 4-tert-octylphenol (4-t-OP), in household food detergents of Taiwan were determined. Gas chromatography with mass spectrometer (GC/MS) was used to analyze alkylphenols in samples. The Taguchi experimental design was utilized to study the possible factors that might affect the residual characteristics of alkylphenols from detergents on dishware and fruits. By the analysis of variance, the orders of importance of different parameters were determined. The results showed that the concentrations of alkylphenols in food detergents ranged from 1.71 x 10(-5) to 2.13 x 10(-3) (APs/detergent, mgg(-1)). For residual characteristics, the cleaning temperature was found to be the only significant factor that will affect the 4-t-OP left on the dishware, while the concentrations of detergents used will affect the left of t-NPs and 4-NP on dishware as well. On the other hand, the varieties of fruits, the concentrations of detergents, and the concentrations of alkylphenols were found to have significant effects for the t-NPs left on fruits. As for the exposure assessments, the maximum dose of APs exposures from the use of household food detergents in Taiwan was also estimated in the study.

Environmental Alkylphenols Modulate Cytokine Expression in Plasmacytoid Dendritic Cells

PubMed Central

Hung, Chih-Hsing; Yang, San-Nan; Wang, Ya-Fang; Liao, Wei-Ting; Kuo, Po-Lin; Tsai, Eing-Mei; Lee, Chin-Lai; Chao, Yu-Shen; Yu, Hsin-Su; Huang, Shau-Ku; Suen, Jau-Ling

2013-01-01

Background Alkylphenols, such as nonylphenol (NP) and 4-octylphenol (4-OP), have the potential to disturb immune system due to their weak estrogen-like activity, an effect with potential serious public health impact due to the worldwide distribution of these substances. Plasmacytoid dendritic cells (PDCs) can secrete large amounts of type I IFNs and are critical in immune regulation. However, there has been limited study about the influence of alkylphenols on the function of pDCs. Objective The aim of this study was to examine the effect of alkylphenols on pDC functions in vitro and in vivo and then further explored the involved signaling pathways and epigenetic changes. Methods Circulating pDCs from human peripheral blood mononuclear cells were treated with alkylphenols with or without CpG stimulation. Alkylphenol-associated cytokine responses, signaling events, histone modifications and viral activity were further examined. In NP-exposed mice, the effect of NP on splenic pDC function and allergic lung inflammation were also assessed. Results The results showed that NP increased the expression of TNF-α, but suppressed IL-10 production in the range of physiological doses, concomitant with activation of the MKK3/6-p38 signaling pathway and enhanced levels of acetylated histone 3 as well as histone 4 at the TNFA gene locus. Further, in CpG-stimulated pDCs, NP suppressed type I IFNs production, associated with down-regulation of IRF-7 and MKK1/2-ERK-Elk-1 pathways and led to the impaired anti-enterovirus 71 activity in vitro. Additionally, splenic pDCs from NP-exposed mice showed similar cytokine changes upon CpG stimulation under conditions relevant to route and level of exposure in humans. NP treatment also enhanced allergic lung inflammation in vivo. Conclusion Alkylphenols may influence pDCs’ functions via their abilities to induce expression of a pro-inflammatory cytokine, TNF-α, and to suppress regulatory cytokines, including IL-10, IFN-α and IFN

Environmental alkylphenols modulate cytokine expression in plasmacytoid dendritic cells.

PubMed

Hung, Chih-Hsing; Yang, San-Nan; Wang, Ya-Fang; Liao, Wei-Ting; Kuo, Po-Lin; Tsai, Eing-Mei; Lee, Chin-Lai; Chao, Yu-Shen; Yu, Hsin-Su; Huang, Shau-Ku; Suen, Jau-Ling

2013-01-01

Alkylphenols, such as nonylphenol (NP) and 4-octylphenol (4-OP), have the potential to disturb immune system due to their weak estrogen-like activity, an effect with potential serious public health impact due to the worldwide distribution of these substances. Plasmacytoid dendritic cells (PDCs) can secrete large amounts of type I IFNs and are critical in immune regulation. However, there has been limited study about the influence of alkylphenols on the function of pDCs. The aim of this study was to examine the effect of alkylphenols on pDC functions in vitro and in vivo and then further explored the involved signaling pathways and epigenetic changes. Circulating pDCs from human peripheral blood mononuclear cells were treated with alkylphenols with or without CpG stimulation. Alkylphenol-associated cytokine responses, signaling events, histone modifications and viral activity were further examined. In NP-exposed mice, the effect of NP on splenic pDC function and allergic lung inflammation were also assessed. The results showed that NP increased the expression of TNF-α, but suppressed IL-10 production in the range of physiological doses, concomitant with activation of the MKK3/6-p38 signaling pathway and enhanced levels of acetylated histone 3 as well as histone 4 at the TNFA gene locus. Further, in CpG-stimulated pDCs, NP suppressed type I IFNs production, associated with down-regulation of IRF-7 and MKK1/2-ERK-Elk-1 pathways and led to the impaired anti-enterovirus 71 activity in vitro. Additionally, splenic pDCs from NP-exposed mice showed similar cytokine changes upon CpG stimulation under conditions relevant to route and level of exposure in humans. NP treatment also enhanced allergic lung inflammation in vivo. Alkylphenols may influence pDCs' functions via their abilities to induce expression of a pro-inflammatory cytokine, TNF-α, and to suppress regulatory cytokines, including IL-10, IFN-α and IFN-β, suggesting the potential impact of endocrine disrupting

Is drinking water a major route of human exposure to alkylphenol and bisphenol contaminants in France?

PubMed

Colin, Adeline; Bach, Cristina; Rosin, Christophe; Munoz, Jean-François; Dauchy, Xavier

2014-01-01

The main objective of this study was to evaluate potential exposure of a significant part of the French population to alkylphenol and bisphenol contaminants due to water consumption. The occurrence of 11 alkylphenols and bisphenols was studied in raw water and treated water samples from public water systems. One sampling campaign was performed from October 2011 to May 2012. Sampling was equally distributed across 100 French departments. In total, 291 raw water samples and 291 treated water samples were analyzed in this study, representing approximately 20 % of the national water supply flow. The occurrence of the target compounds was also determined for 29 brands of bottled water (polyethylene terephthalate [PET] bottles, polycarbonate [PC] reusable containers, and aluminum cans [ACs]) and in 5 drinking water networks where epoxy resin has been used as coating for pipes. In raw water samples, the highest individual concentration was 1,430 ng/L for bisphenol A (BPA). Of the investigated compounds, nonylphenol (NP), nonylphenol 1-carboxylic acid (NP1EC), BPA, and nonylphenol 2-ethoxylate (NP2EO) predominated (detected in 18.6, 18.6, 14.4, and 10 % of samples, respectively). Geographical variability was observed with departments crossed by major rivers or with high population densities being more affected by contamination. In treated water samples, the highest individual concentration was 505 ng/L for NP. Compared with raw water, target compounds were found in lower amounts in treated water. This difference suggests a relative effectiveness of certain water treatments for the elimination of these pollutants; however, there is also their possible transformation by reaction with chlorine. No target compounds were found in drinking water pipes coated with epoxy resin, in PET bottled water, or in water from ACs. However, levels of BPA in PC bottled water ranged from 70 to 4,210 ng/L with greater level observed in newly manufactured bottles. 4-Tert-butylphenol was

Titania/CnTAB Nanoskeleton as adsorbent and photocatalyst for removal of alkylphenols dissolved in water.

PubMed

Sakai, Toshio; Da Loves, Albar; Okada, Tomohiko; Mishima, Shozi

2013-03-15

We report here on the removal of alkylphenols (phenol, 4-n-propylphenol, 4-n-heptylphenol and 4-nonylphenol) dissolved in water using the composite particles of nanocrystalline titania and alkyltrimethylammonium bromide (CnH2n+1N(CH3)3Br, CnTAB; n=12, 14, 16 and 18) (named as TiO2/CnTAB Nanoskeleton) as adsorbents and photocatalysts. In particular, the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton in water was investigated in terms of hydrophobic interaction between alkylphenols and CnTAB, surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton. We revealed that CnTAB incorporated in the TiO2/CnTAB Nanoskeleton promotes the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton due to the hydrophobic interaction between alkylphenols and CnTAB. On the other hand, the surface area, pore structure and crystal size of TiO2/CnTAB Nanoskeleton did not affect the adsorption of alkylphenols onto TiO2/CnTAB Nanoskeleton. We also found that the alkylphenols dissolved in water were completely removed by the combination of adsorption and photocatalytic degradation by the TiO2/CnTAB Nanoskeleton under UV irradiation. These results prove that the TiO2/CnTAB Nanoskeleton acts as in tandem an adsorbent and a photocatalyst for removal of alkylphenols dissolved in water. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of process conditions on carboxylation of higher alkylphenols by Kolbe-Schmidt reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gordash, Yu.T.; Voloshin, N.L.; Prusak, A.G.

1987-01-01

The authors present experimental data on the carboxylation of higher alkylphenols prepared by alkylating phenol with a 240-320/sup 0/C alpha-olefin cut obtained by thermal cracking of the paraffins, on KU-2 catalyst. Experiments were performed to determine the influence of temperature and pressure on the conversion of sodium alkylphenolate to alkylsalicylate. The content of alkylphenols in the carboxylated products was demonstrated by solubilizing the carboxylate in water, subsequently centrifuging the water-organic mixture that was obtained. From the data presented here, it follows that in the carboxylation of sodium alkylphenolate, side reactions can be minimized if the process is performed at 130-135/supmore » 0/C with a CO/sub 2/ pressure no lower than 2 MPa.« less

Cytotoxicity of alkylphenols and alkylated non-phenolics in a primary culture of rainbow trout (Onchorhynchus mykiss) hepatocytes.

PubMed

Tollefsen, K-E; Blikstad, Camilla; Eikvar, Sissel; Farmen Finne, Eivind; Katharina Gregersen, Inger

2008-01-01

Alkylphenols are common aquatic pollutants originating from industrial use of the compounds themselves or as biodegradation products of alkylphenol polyethoxylates. The cytotoxicity of a range of alkylphenols and alkylated non-phenolics were assessed in a primary culture of rainbow trout (Onchorhynchus mykiss) hepatocytes to construct a structure-toxicity relationship for this group of ubiquitous aquatic pollutants. Metabolic inhibition and loss of membrane integrity were used as cytotoxic endpoints through use of the cellular markers Alamar blue and 5-carboxyfluorescein diacetate acetoxymethyl ester, respectively. The results show that cytotoxicity increased with the hydrophobicity of the alkylphenols for compounds with logK(OW)<4.9. Normal chained alkylphenols, branched alkylphenols and multi-substituted alkylphenols with logK(OW)4.9 deviated clearly from this relationship. The alkylphenols displayed greater cytotoxicity than alkylated non-phenolics and it is proposed that most alkylated non-phenolic caused non-polar narcosis (baseline toxicity) whereas the alkylphenols caused polar narcosis. Observations that metabolic inhibition occurred at lower concentrations than loss of membrane integrity for most chemicals indicated that interference with cellular metabolic functions was the main cause of cytotoxicity. Metabolic inhibition corresponded better than loss of membrane integrity to reported acute toxicity to fish, although the in vivo acute toxicity of hydrophobic compounds (logK(OW)>2-3) was clearly underestimated by both endpoints.

Controls on the distribution of alkylphenols and BTEX in oilfield waters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dale, J.D.; Aplin, A.C.; Larter, S.R.

1996-10-01

Controls on the abundance of alkylphenols and BTEX in oilfield waters are poorly understood, but are important because these species are the main dissolved pollutants in produced waters and may also be used as indicators of both the proximity and migration range of petroleum. Using (1) measurements of alkyl phenols and BTEX in oilfield waters and associated petroleums, and (b) oil/water partition coefficients under subsurface conditions we conclude that: (1) The distribution of alkylphenols and BTEX in formation waters are controlled by partition equilibrium with petroleum. Phenol and benzene typically account for 50% of total phenols and total BTEX respectively.more » (2) The concentrations of alkylphenols and BTEX in produced waters equilibriated with oil in reservoirs or in separator systems vary predictably as a function of pressure, temperature and salinity. This suggests that oil/water partition is the primary control influencing the distribution of alkylphenols and BTEX in oilfield waters and that other processes such as hydrolysis processes at the oil-water contact are secondary.« less

Alkylphenolic compounds and bisphenol A contamination within a heavily urbanized area: case study of Paris.

PubMed

Cladière, Mathieu; Gasperi, Johnny; Lorgeoux, Catherine; Bonhomme, Céline; Rocher, Vincent; Tassin, Bruno

2013-05-01

This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP₁EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP1EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.

Environmental analysis of alcohol ethoxylates and nonylphenol ethoxylate metabolites by ultra-performance liquid chromatography-tandem mass spectrometry.

PubMed

Lara-Martín, Pablo A; González-Mazo, Eduardo; Brownawell, Bruce J

2012-03-01

Surfactants and their metabolites can be found in aquatic environments at relatively high concentrations compared with other micropollutants due in part to the exceptionally large volumes produced every year. We have focused our attention here on the most widely used nonionic surfactants, alcohol ethoxylates (AEOs), and on nonylphenol ethoxylate (NPEO) degradation products (short-chain nonylphenol ethoxylates, NP1-3EO, nonylphenol, NP, and nonylphenol ethoxycarboxylates, NP1-2EC), which are endocrine-disrupting compounds. Our main objective in this work was to develop a methodology aimed at the extraction, isolation, and improved analysis of these analytes in environmental samples at trace levels. Extraction recoveries of target compounds were determined for sediment samples after ultrasonic extraction and purification using HLB or C18 solid-phase extraction minicolumns. Recovery percentages were usually between 61 and 102% but were lower for longer AEO ethoxymers. Identification and quantification of target compounds was carried out using a novel ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS-MS) approach, a combination that provides higher sensitivity and faster analysis than prior methods using conventional high-performance liquid chromatography-mass spectrometry. Limits of detection were usually below 0.5 ng/g, being higher for monoethoxylate species (>5 ng/g) because of poor ionization. The method was used for analyzing surface sediment samples collected at Jamaica Bay (NY) in 2008. The highest values (28,500 ng/g for NP, 4,200 ng/g for NP1-3EO, 22,400 ng/g for NP1-2EC, and 1,500 ng/g for AEOs) were found in a sampling station from a restricted water circulation area that is heavily impacted by wastewater discharges.

Liquid chromatographic-tandem mass spectrometric method for the simultaneous determination of alkylphenols polyethoxylates, alkylphenoxy carboxylates and alkylphenols in wastewater and surface-water.

PubMed

Ciofi, L; Ancillotti, C; Chiuminatto, U; Fibbi, D; Checchini, L; Orlandini, S; Del Bubba, M

2014-10-03

Four different pellicular stationary phases (i.e. octadecylsilane, octasilane, Phenyl-Hexyl and pentafluorophenyl) were investigated for the chromatographic resolution of alkylphenols (APs), alkylphenols polyethoxylates (APnEOs) and alkylphenoxy carboxylates (APECs) using mixtures of water and organic solvents (i.e. methanol, acetonitrile and tetrahydrofuran) as eluents, in order to obtain their determination by a single LC-MS/MS run. In fact, alkylphenols and alkylphenoxy carboxylates must be analysed in negative ion mode, whereas alkylphenols polyethoxylates undergo ionisation only in positive ion mode, and therefore, two distinct LC-MS/MS analysis are commonly adopted. The best resolution among the aforementioned target analytes was achieved on the pentafluorophenyl column, eluting with an acidified water-acetonitrile-tetrahydrofuran mixture and using the post column addition of an ammonia solution in methanol for the detection of positively ionisable compounds. Under these optimized chromatographic conditions the investigated compounds were determined via a single chromatographic run, with only one polarity switch, in 15min, achieving the following instrumental detection limits: 600pg for AP1EOs, 0.8-14pg for AP2EOs, 10.4-150pg for APs and 4.4-4.8pg for APECs. The chromatographic method was coupled with solid-phase extraction and clean-up procedures and successfully applied to the analysis of wastewater and surface water samples, highlighting mean concentration ranging from 6ng/L for 4-t-OP1EC to 1434ng/L for 4-NP1121EC, depending on the sample analysed. Copyright © 2014 Elsevier B.V. All rights reserved.

Binding of alkylphenols and alkylated non-phenolics to rainbow trout (Oncorhynchus mykiss) hepatic estrogen receptors.

PubMed

Tollefsen, Knut-Erik; Julie Nilsen, Anja

2008-02-01

Alkylphenols are well-known endocrine disrupters, mediating effects through the estrogen receptor (ER). In the present work, the interaction of alkylphenols and alkylated non-phenolics with hepatic rainbow trout (Oncorhynchus mykiss) estrogen receptors (rtERs) was determined. The role of alkyl chain length and branching, substituent position, number of alkylated groups, and the requirement of a phenolic ring structure was assessed. The results showed that the rtERs bound most alkylphenols, although with 20,000 to 2 million times lower affinity than the endogenous estrogen 17beta-estradiol. Mono-substituted alkylphenols with moderate (C4-C6) and long (C8 and C12) alkyl chain length in the para position exhibited the highest affinity for the rtERs. Substitution with multiple alkyl groups, presence of substituents in the ortho- and meta-position, and lack of a hydroxyl group on the benzene ring reduced the binding affinity. The rtERs resembled the reported binding specificity of the human ER for alkylphenols, although some exceptions were identified.

New chalcones bearing a long-chain alkylphenol from the rhizomes of Alpinia galanga.

PubMed

Yang, Wan-Qiu; Gao, Yuan; Li, Ming; Miao, De-Ren; Wang, Fei

2015-01-01

Three novel chalcones bearing a long-chain alkylphenol, galanganones A-C (1-3), were isolated from the rhizomes of Alpinia galanga. Their structures were elucidated by extensive spectroscopic analysis including 2D NMR experiments. Compounds 1-3 represent the first examples of long-chain alkylphenol-coupled chalcone.

Removal of p-alkylphenols from aqueous solutions by combined use of mushroom tyrosinase and chitosan beads.

PubMed

Yamada, Kazunori; Inoue, Tomoaki; Akiba, Yuji; Kashiwada, Ayumi; Matsuda, Kiyomi; Hirata, Mitsuo

2006-10-01

Enzymatic removal of p-alkylphenols from aqueous solutions was investigated through the two-step approach, the quinone conversion of p-alkylphenols with mushroom tyrosinase (EC 1.14.18.1) and the subsequent adsorption of quinone derivatives enzymatically generated on chitosan beads at pH 7.0 and 45 degrees C as the optimum conditions. This technique is quite effective for removal of various p-alkylphenols from an aqueous solution. The % removal values of 97-100% were obtained for p-n-alkylphenols with carbon chain lengths of 5 to 9. In addition, removal of other p-alkylphenols was enhanced by increasing either the tyrosinase concentration or the amount of added chitosan beads, and their % removal values reached >93 except for 4-tert-pentylphenol. This technique was also applicable to remove 4-n-octylphenol (4NOP) and 4-n-nonylphenol (4NNP) as suspected endocrine disrupting chemicals. The reaction of quinone derivatives enzymatically generated with the chitosan's amino groups was confirmed by the appearance of peaks for UV-visible spectrum measurements of the chitosan films incubated in the p-alkylphenol and tyrosinase mixture solutions. In addition, 4-tert-pentylphenol underwent tyrosinase-catalyzed oxidation in the presence of hydrogen peroxide.

Alkylphenols in Surface Sediments of the Gulf of Gdansk (Baltic Sea).

PubMed

Koniecko, Iga; Staniszewska, Marta; Falkowska, Lucyna; Burska, Dorota; Kielczewska, Joanna; Jasinska, Anita

2014-01-01

The widespread use of alkylphenols in European industry has led to their presence in the environment and the living organisms of the Baltic Sea. The present study (2011-2012) was designed to determine the concentrations of alkylphenols, 4-nonylphenol (NP) and 4- tert -octylphenol (OP), in surface sediments of the Gulf of Gdansk, a section of the Baltic that lies in close proximity to industrial and agricultural areas and borders with an agglomeration of nearly one million inhabitants. It is also where the Vistula, the largest Polish river, ends its course. In spring, large concentrations of 4-nonylphenol and 4- tert -octylphenol were washed off into the coastal zone with meltwater. In summertime, sediments near the beach had the highest alkylphenol concentrations (NP-2.31 ng g -1 dw, OP-13.09 ng g -1 dw), which was related to tourism and recreational activity. In silt sediments located off the coast, the highest NP (1.46 ng g -1 dw) and OP (6.56 ng g -1 dw) amounts were observed in autumn. The origin of OP and NP at those test stations was linked to atmospheric transport of black carbon along with adsorbed alkylphenols.

Determination of alkylphenols by gas chromatography, elution liquid chromatography, and gel permeation chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wittmann, S.; Decsy, Z.; Regensperger, S.

1984-01-01

The separation and determination of groups of alkylphenols with C/sub 15/-C/sub 33/ isoalkane chains by gas chromatography, elution liquid chromatography, and gel permeation chromatography are described. Paraffinic hydrocarbons, monoalkylphenols, dialkylphenols, and bis(hydroxyphenyl)alkanes were identified in industrial alkylphenols by mass spectrometry. 7 references, 3 figures, 2 tables.

Fast determination of alkylphenol ethoxylates in leafy vegetables using a modified quick, easy, cheap, effective, rugged, and safe method and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry.

PubMed

Jiang, Ze-Jun; Cao, Xiao-Lin; Li, Hui; Zhang, Chan; Abd El-Aty, A M; Jin, Fen; Shao, Hua; Jin, Mao-Jun; Wang, Shan-Shan; She, Yong-Xin; Wang, Jing

2017-11-24

In the present study, a quick and sensitive method was developed for simultaneous determination of nonylphenol ethoxylates (NPxEOs) and octylphenol ethoxylates (OPxEOs) (x=2-20) in three leafy vegetables, including cabbage, lettuce, and spinach using a modified "QuEChERS" method and ultra-high performance supercritical fluid chromatography-tandem mass spectrometry (UHPSFC-MS/MS) with scheduled multiple reaction monitoring (MRM). Under optimized conditions, the 38 target analytes were analyzed within a short period of time (5 min). The linearities of the matrix-matched standard calibrations were satisfactory with coefficients of determination (R 2 )>0.99 and the limits of detection (LOD) and quantification (LOQ) were in between 0.02-0.27 and 0.18-1.75μgkg -1 , respectively. The recovery of all target analytes spiked at three (low, medium, and high) fortification levels in various leafy vegetables were ranged from 72.8-122.6% with relative standard deviation (RSD) ≤18.3%. The method was successfully applied to market samples and the target analytes were found in all monitored samples, with total concentrations of 0-8.67μgkg -1 and 15.75-95.75μgkg -1 for OPxEOs and NPxEOs (x=2-20), respectively. In conclusion, the newly developed UHPSFC-ESI-MS/MS method is rapid and versatile and could be extrapolated for qualitative and quantitative analysis of APxEOs in other leafy vegetables. Copyright © 2017 Elsevier B.V. All rights reserved.

21 CFR 172.834 - Ethoxylated mono- and diglycerides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... ethoxylated mono-and diglycerides (polyoxyethylene (20) mono- and diglycerides of fatty acids) (polyglycerate... labeling it shall be followed by either “polyoxyethylene (20) mono-and diglycerides of fatty acids” or... myristic acids; or (2) Direct esterification of glycerol with a mixture of primarily stearic, palmitic, and...

Regio- and Stereospecific Conversion of 4-Alkylphenols by the Covalent Flavoprotein Vanillyl-Alcohol Oxidase

PubMed Central

van den Heuvel, Robert H. H.; Fraaije, Marco W.; Laane, Colja; van Berkel, Willem J. H.

1998-01-01

The regio- and stereospecific conversion of prochiral 4-alkylphenols by the covalent flavoprotein vanillyl-alcohol oxidase was investigated. The enzyme was active, with 4-alkylphenols bearing aliphatic side chains of up to seven carbon atoms. Optimal catalytic efficiency occurred with 4-ethylphenol and 4-n-propylphenols. These short-chain 4-alkylphenols are stereoselectively hydroxylated to the corresponding (R)-1-(4′-hydroxyphenyl)alcohols (F. P. Drijfhout, M. W. Fraaije, H. Jongejan, W. J. H. van Berkel, and M. C. R. Franssen, Biotechnol. Bioeng. 59:171–177, 1998). (S)-1-(4′-Hydroxyphenyl)ethanol was found to be a far better substrate than (R)-1-(4′-hydroxyphenyl)ethanol, explaining why during the enzymatic conversion of 4-ethylphenol nearly no 4-hydroxyacetophenone is formed. Medium-chain 4-alkylphenols were exclusively converted by vanillyl-alcohol oxidase to the corresponding 1-(4′-hydroxyphenyl)alkenes. The relative cis-trans stereochemistry of these reactions was strongly dependent on the nature of the alkyl side chain. The enzymatic conversion of 4-sec-butylphenol resulted in two (4′-hydroxyphenyl)-sec-butene isomers with identical masses but different fragmentation patterns. We conclude that the water accessibility of the enzyme active site and the orientation of the hydrophobic alkyl side chain of the substrate are of major importance in determining the regiospecific and stereochemical outcome of vanillyl-alcohol oxidase-mediated conversions of 4-alkylphenols. PMID:9791114

Copper thiobis(alkylphenols) and antioxidant compositions thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braid, M.

1980-09-30

Novel copper thiobis(alkylphenol-phenolate) complexes are effective antioxidant additives for various organic media such as oils of lubricating viscosity and plastics. Additionally these novel copper organo-sulfur compounds are highly useful as energy quenchers and antisludging agents in a variety of organic substrates.

Effects of alkylphenols on CYP1A and CYP3A expression in first spawning Atlantic cod (Gadus morhua).

PubMed

Hasselberg, Linda; Meier, Sonnich; Svardal, Asbjørn; Hegelund, Tove; Celander, Malin C

2004-05-12

Alkylphenols are continuously released into the ocean as a result of offshore oil production. Alkylphenols, including 4-tert-butylphenol (C4), 4n-pentylphenol (C5), 4n-hexylphenol (C6), and 4n-heptylphenol (C7), up to 237 ppb concentrations, have been detected in produced water from oil platforms. Previous studies have shown that alkylphenols induce vitellogenesis in fish. Atlantic cod (Gadus morhua) of both sexes were force-fed with various doses ranging between 0.02 and 80 ppm of a mixture of alkylphenols (C4:C5:C6:C7 ratio 1:1:1:1) or 5 ppm 17 beta-estradiol. We investigated effects on hepatic CYP1A and CYP3A protein expression in protein blots, using antibodies against scup (Stenotomus chrysops) CYP1A1 and rainbow trout (Oncorhynchus mykiss) CYP3A. There was a sexually dimorphic expression of CYP1A and CYP3A protein levels, with females expressing higher levels than males. Treatment of male Atlantic cod with 17 beta-estradiol resulted in increased CYP1A and CYP3A protein levels. Exposure to alkylphenols resulted in a dose-dependent increase of CYP1A and CYP3A protein expression in males, but not in females. However, this increase of CYP1A protein levels was not reflected on the CYP1A-mediated ethoxyresorufin-O-deethylase (EROD) activity, implying that alkylphenols inhibited the CYP1A enzyme activity in vivo. In vitro inhibition studies with pooled liver microsomes from Atlantic cod confirmed that the alkylphenols mixture efficiently inhibited the CYP1A activity (IC50=10 microM), although the inhibitory effect of each individual alkylphenol varied. The IC50 values for each individual alkylphenol on the CYP1A activity were, in a descending order of magnitude: [C7>C6>C5>C4], ranging from 12 to 300 microM with decreased length of the 4-alkyl chain. The effect of alkylphenols on the CYP3A activity in vitro in liver microsomes also was investigated, using the fluorescent 7-benzyloxy-4-[trifluoromethyl]-coumarin (BFC) as a diagnostic CYP3A substrate. The alkylphenol

40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

The monitoring of pesticides and alkylphenols in selected rivers in the State of Selangor, Malaysia.

PubMed

Tan, B L L; Mustafa, A M

2004-01-01

Alkylphenols and most pesticides, especially organochlorine pesticides are endocrine-disrupting chemicals and they usually mimic the female hormone, estrogen. Using these chemicals in our environment would eventually lead us to consume them somehow in the food web. Several rivers in the State of Selangor, Malaysia were selected to monitor the level of alkylphenols and pesticides contamination for several months. The compounds were extracted from the water samples using liquid-liquid extraction method with dichloromethane and ethyl acetate as the extracting solvents. The alkylphenols and pesticides were analyzed by selected ion monitoring (SIM) mode using the quadrapole detector in Shimadzu QP-5000 gas chromatograph-mass spectrometer (GCMS). Recovery of most alkylphenols and pesticides were in the range of 50% to 120%. Trace amounts of the compounds were detected in the river water samples, mainly in the range of parts per trillion. This technique of monitoring the levels of endocrine-disruptors in river water is consistent and cost effective.

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge.

PubMed

Milinovic, Jelena; Vidal, Miquel; Lacorte, Silvia; Rigol, Anna

2014-02-01

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP1EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP1EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.

Effects of alkylphenols on bone metabolism in vivo and in vitro.

PubMed

Hagiwara, Hiromi; Sugizaki, Toshinori; Tsukamoto, Yu; Senoh, Emi; Goto, Tadashi; Ishihara, Yoko

2008-09-01

Alkylphenols are endocrine disruptors that show estrogen-like effects in various wildlife species. However, little information is available about the action of these chemicals on bone metabolism. We investigated the effects of alkylphenols, such as nonylphenol (NP) and octylphenol (OP), on the formation of bone using several culture systems for osteoclasts and osteoblasts, as well as in vivo experiments. NP and OP dose-dependently inhibited the formation of tartrate-resistant acid phosphatase-positive multinucleated cells (osteoclasts) in cocultures of mouse spleen cells or mouse bone marrow cells with ST2 cells. However, beta-estradiol at 10(-9)M to 10(-6)M did not affect this process. In contrast, neither compound affected the proliferation and differentiation of rat calvarial osteoblast-like cells (ROB cells). When NP or OP (0.1mg/kg body weight) was administered subcutaneously to pregnant mice at 10 days, 12 days and 14 days post-coitus, fetuses at 17.5 days post-coitus showed stimulation of sternebrae bone calcification. Our findings suggest that alkylphenols have critical effects on the formation of bone by non-estrogenic effects.

ALKYLPHENOL (APE) MONITORING AND ASSESSMENT OF REGION 5

EPA Science Inventory

Two draft reports have been prepared for publication - a USGS document titled "Alkylphenols and hormones in wastewater treatment plant influents, effluents, and receiving streams of the Great Lakes Region" and a journal article titled "Biological responses of male fatehead minno...

Endocrine disrupting alkylphenols: structural requirements for their adverse effects on Ca2+ pumps, Ca2+ homeostasis & Sertoli TM4 cell viability.

PubMed

Michelangeli, Francesco; Ogunbayo, Oluseye A; Wootton, Laura L; Lai, Pei F; Al-Mousa, Fawaz; Harris, Robert M; Waring, Rosemary H; Kirk, Christopher J

2008-11-25

Alkylphenols such as nonylphenol are pollutants that are widely dispersed within our environment. They bio-accumulate within man, with levels in the muM concentration range reported in human tissues. These chemicals act as endocrine disruptors, having xenoestrogenic activity. More recently alkylphenols have also been shown to affect Ca2+ signalling pathways. Here we show that alkylphenols are potent inhibitors of sarcoplasmic-endoplasmic reticulum Ca2+-ATPase (SERCA) activity. For linear chain alkylphenols the potency of inhibition is related to chain length, with the IC50 values for inhibition ranging from 8 microM for 4-n-nonylphenol (C9) to 1.3 mM for 4-n-propylphenol (C3). Branched chain alkylphenols generally had lower potencies than their linear chain counterparts, however, good correlations for all alkylphenols were observed between their Ca2+ pump inhibition and hydrophobicity, molecular volume and flexibility, indicating that these parameters are all important factors. Alkylphenols cause abnormal elevations of intracellular [Ca2+] within TM4 Sertoli cells (cells involved in sperm maturation) depolarise their mitochondria and induce cell death in these cells, in an alkyl chain size-dependent manner.

Treatment of solutions containing nonylphenol ethoxylate by photoelectrooxidation.

PubMed

da Silva, Salatiel Wohlmuth; Bordignon, Gustavo Lanferdini; Viegas, Cheila; Rodrigues, Marco Antônio Siqueira; Arenzon, Alexandre; Bernardes, Andréa Moura

2015-01-01

In this work the photoelectrooxidation (PEO) was applied in the treatment of a solution containing nonylphenol ethoxylate surfactant (NP4EO). The use of different lamps (125 and 250 W), current density (5 and 10 mA cm(-2)) and treatment time (0, 60, 120, 180 and 240 min) were investigated. The samples were characterized by UV/Vis, total organic carbon (TOC), gas chromatography associated to mass spectroscopy (GC/MS) and ecotoxicity. The reaction kinetics were calculated and the light flux and pH were measured. The results of analysis by UV/Vis show that there is degradation of nonylphenol ethoxylated in the treatment time of 240 min for all configurations, and the configurations that used a 250 W lamp and a current density of 10 mA cm(-2) obtained better results, with a reduction of 83% in TOC, indicating a high mineralization of the surfactant. It was further found in the GC/MS that the configurations that used the 125 W lamp promoted a smaller incident light flux on the solution, and, regardless of the applied current density, it was generated the reaction intermediate nonylphenol, more toxic than the parent compound. The opposite can be observed when a 250 W lamp was used, which produced a higher incident light flux. Based on the degradation products detected, a simplified mechanism for degradation of nonylphenol ethoxylate was proposed. Although a treatment time of 240 min with photoelectrooxidation with different configurations was not effective in the complete mineralization of the compound, a promising process was developed with the treatment using a lamp of 250 W and a current density of 10 mA cm(-2), which generated a solution with less toxicity than the original one. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anaerobic biodegradability of alkylphenols and fuel oxygenates in the presence of alternative electron acceptors.

PubMed

Puig-Grajales, L; Tan, N G; van der Zee, F; Razo-Flores, E; Field, J A

2000-11-01

Alkylphenols and fuel oxygenates are important environmental pollutants produced by the petrochemical industry. A batch biodegradability test was conducted with selected ortho-substituted alkylphenols (2-cresol, 2,6-dimethylphenol and 2-ethylphenol), fuel oxygenates (methyl tert-butyl ether, ethyl tert-butyl ether and tert-amylmethyl ether) and tert-butyl alcohol (TBA) as model compounds. The ortho-substituted alkylphenols were not biodegraded after 100 days of incubation under methanogenic, sulfate-, or nitrate-reducing conditions. However, biodegradation of 2-cresol and 2-ethylphenol (150 mg l(-1)) was observed in the presence of Mn (IV) as electron acceptor. The biodegradation of these two compounds took place in less than 15 days and more than 90% removal was observed for both compounds. Mineralization was indicated since no UV-absorbing metabolites accumulated after 23 days of incubation. These alkylphenols were also slowly chemically oxidized by Mn (IV). No biodegradation of fuel oxygenates or TBA (1 g l(-1)) was observed after 80 or more days of incubation under methanogenic, Fe (III)-, or Mn (IV)-reducing conditions, suggesting that these compounds are recalcitrant under anaerobic conditions. The fuel oxygenates caused no toxicity towards acetoclastic methanogens activity in anaerobic granular sludge.

Comparative toxicity of nonylphenol, nonylphenol-4-ethoxylate and nonylphenol-10-ethoxylate to wheat seedlings (Triticum aestivum L.).

PubMed

Zhang, Qingming; Wang, Feifei; Xue, Changhui; Wang, Caixia; Chi, Shengqi; Zhang, Jianfeng

2016-09-01

Nonylphenol polyethoxylates (NPEOs) are a group of surfactants that are widely used in industrial and household products and often detected in the environment. The metabolite of NPEOs, named nonylphenol (NP), has proven to be an endocrine disruptor, and its environmental behavior and eco-toxicity have been widely investigated in previous studies. However, to the best of our knowledge, insight into the toxicity differences of NP and NPEOs on important crops remains limited. Therefore, this study investigated the comparative toxicity of NP, nonylphenol-4-ethoxylate (NP4EO), and nonylphenol-10-ethoxylate (NP10EO) on wheat seedlings using hydroponic experiments. The results indicated that NP is most toxic to wheat followed by NP4EO, and NP10EO is the least toxic to wheat. The adverse effects of NP on wheat were observed for all the tested parameters including germination, shoot length, root length, chlorophyll, lipid peroxidation, and enzymatic activities. To gain insight into the molecular response, we analyzed the transcript abundance of SOD-Cu/Zn and CAT with NP, NP4EO, and NP10EO exposure using quantitative real-time PCR. The data revealed that both genes exhibited up- or down-regulated expression patterns that were consistent with the activities of the two enzymes. This result further conformed that NP is most toxic to wheat plants. Copyright © 2016 Elsevier Inc. All rights reserved.

Adsorption at air-water and oil-water interfaces and self-assembly in aqueous solution of ethoxylated polysorbate nonionic surfactants.

PubMed

Penfold, Jeffrey; Thomas, Robert K; Li, Peixun X; Petkov, Jordan T; Tucker, Ian; Webster, John R P; Terry, Ann E

2015-03-17

The Tween nonionic surfactants are ethoxylated sorbitan esters, which have 20 ethylene oxide groups attached to the sorbitan headgroup and a single alkyl chain, lauryl, palmityl, stearyl, or oleyl. They are an important class of surfactants that are extensively used in emulsion and foam stabilization and in applications associated with foods, cosmetics and pharmaceuticals. A range of ethoxylated polysorbate surfactants, with differing degrees of ethoxylation from 3 to 50 ethylene oxide groups, have been synthesized and characterized by neutron reflection, small-angle neutron scattering, and surface tension. In conjunction with different alkyl chain groups, this provides the opportunity to modify their surface properties, their self-assembly in solution, and their interaction with macromolecules, such as proteins. Adsorption at the air-water and oil-water interfaces and solution self-assembly of the range of ethoxylated polysorbate surfactants synthesized are presented and discussed.

Geosynthesis of organic compounds: I. Alkylphenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ioppolo-Armanios, M.; Alexander, R.; Kagi, R.I.

1995-07-01

Methylation, isopropylation, and sec-butylation are proposed as geosynthetic processes to account for the alkylphenol compositions of crude oils with phenol distributions dominated by ortho and para substituted compounds. Phenol distributions in eleven crude oils and four kerogen pyrolysates were analysed using GC-MS (gas chromatography-mass spectrometry). Ten of the crude oils show high relative abundances of ortho and para substituted phenol isomers and some were also enriched in C{sub 3}-C{sub 5} alkylphenols compared to the kerogen pyrolysates. Because the distributions of products obtained from the laboratory alkylation of cresols closely resemble those of phenols in these crude oils, we propose thatmore » similar alkylation processes occur in source rocks. Alkylation ratios reflecting the degree of methylation, isopropylation, and sec-butylation, which were based on the relative abundance of the dominant alkylation products compared to their likely precursor ortho-cresol, indicate that high levels of methylation occurred in crude oils over a wide range of maturities, whereas high levels of isopropylation and sec-butylation were observed only in mature samples. Dissolution of the phenols in crude oils by water contact was discounted as an explanation for the observed phenol distributions based on the relative distribution coefficients of phenols between a hydrocarbon phase and water.« less

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.

PubMed

Chen, Ling; Zhou, Hai-Yun; Deng, Qin-Ying

2007-06-01

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.

Production of ethoxylated fatty acids derived from Jatropha non-edible oil as a nonionic fat-liquoring agent.

PubMed

El-Shattory, Y; Abo-Elwafa, Ghada A; Aly, Saadia M; Nashy, El-Shahat H A

2012-01-01

Natural fatty derivatives (oleochemicals) have been used as intermediate materials in several industries replacing the harmful and expensive petrochemicals. Fatty ethoxylates are one of these natural fatty derivatives. In the present work Jatropha fatty acids were derived from the non edible Jatropha oil and used as the fat source precursor. The ethoxylation process was carried out on the derived fatty acids using a conventional cheap catalyst (K₂CO₃) in order to obtain economically and naturally valuable non-ionic surfactants. Ethoxylation reaction was proceeded using ethylene oxide gas in the presence of 1 or 2% K₂CO₃ catalyst at 120 and 145°C for 5, 8 and 12 hours. The prepared products were evaluated for their chemical and physical properties as well as its application as non- ionic fat-liquoring agents in leather industry. The obtained results showed that the number of ethylene oxide groups introduced in the fatty acids as well as their EO% increased as the temperature and time of the reaction increased. The highest ethoxylation number was obtained at 145°C for 8 hr. Also, the prepared ethoxylated products were found to be effective fat-liquors with high HLB values giving stable oil in water emulsions. The fat-liquored leather led to an improvement in its mechanical properties such as tensile strength and elongation at break. In addition, a significant enhancement in the texture of the treated leather by the prepared fat-liquors as indicated from the scanning electron microscope (SEM) images was observed.

Certification of reference materials for the determination of alkylphenols.

PubMed

Hanari, Nobuyasu; Ishikawa, Keiichiro; Shimizu, Yoshitaka; Otsuka, Satoko; Iwasawa, Ryoko; Fujiki, Naomi; Numata, Masahiko; Yarita, Takashi; Kato, Kenji

2015-04-01

Certified reference materials (CRMs) are playing an increasingly important role in national and international standardizing activities. In Japan, primary standard solutions for analyses of endocrine disrupters are supplied under the national standards dissemination system named the Japan Calibration Service System (JCSS). For the traceability on reference materials used for preparation of the primary standard solutions based on the JCSS, the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) has developed and certified high-purity reference materials of alkylphenols as NMIJ CRMs, such as 4-n-nonylphenol, 4-tert-octylphenol, 4-n-heptylphenol, 4-tert-butylphenol, and 2,4-dichlorophenol. Thereafter, it is essential to determine the alkylphenols by using these solutions based on the JCSS for environmental monitoring and risk assessments because analytical values obtained by using the solutions can ensure the reliability and traceability of the chemical analyses.

Equilibration of tert-alkylphenols (thermodynamic analysis of the alkylation of phenols using branched-chain olefins)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nesterova, T.N.; Malova, T.N.; Pil'shchikov, V.A.

1985-09-01

The authors describe the results of a study to evaluate the thermodynamic properties of t-Alk phi. These results, combined with earlier results, have enabled the authors to complete a thermodynamic analysis of the process for preparing tertiary alkylphenols which are widely used as additives in lubricating and fuel oils. Research was conducted over a fairly wide temperature range, in which the median temperature value corresponds to the upper temperature limit for a continuous process utilizing a type KU-2 ion-exchange resin catalyst; continuous operations are currently the most widely used method for industrial preparation of alkylphenols. Experimentally determined values of themore » equilibrium constants in a table indicate that they are influenced primarily by the nature of the reaction, and do not depend on the size of the tertiary alkyl substituents. Data in another table demonstrate that the thermodynamic properties of a given reaction are determined by the reaction type and are independent of the size of the tertiary alkylphenols. It was discovered that in order to increase the yield of the desired tert-alkylphenol product, the process should be carried out at the minimum possible temperature, using catalysts which are sufficiently active to guarantee thermodynamic control.« less

Binding of alkylphenols and alkylated non-phenolics to the rainbow trout (Oncorhynchus mykiss) plasma sex steroid-binding protein.

PubMed

Tollefsen, K-E

2007-09-01

Alkylphenols are well-known endocrine disrupters, mediating effects through the estrogen receptor (ER). Although the estrogenic properties of the alkylphenols are well documented, alternative mechanisms of action are poorly described. In the present work, the interaction of a range of alkyl-substituted phenols and alkyl-substituted non-phenolics with the rainbow trout (Oncorhynchus mykiss) sex steroid-binding protein (rtSBP) were determined by competitive ligand-binding studies. The role of alkyl chain length and branching, substituent position, number of alkylated groups, and the requirement of a phenolic ring structure were assessed. The results showed that the rtSBP binds to most chemical structures tested, although the highest affinity was obtained for mono-substituted alkylphenols with a chain length of four to eight methyl groups. Interestingly, rtSBP binding was also observed for non-phenolic compounds such as 4-t-butylcyclohexanol and 4-t-butylnitrobenzene suggesting that the rtSBP has a broad binding specificity for alkylphenols and alkylated non-phenolics.

Asphaltene aggregation and impact of alkylphenols.

PubMed

Goual, Lamia; Sedghi, Mohammad; Wang, Xiaoxiao; Zhu, Ziming

2014-05-20

The main objective of this study was to provide novel insights into the mechanism of asphaltene aggregation in toluene/heptane (Heptol) solutions and the effect of alkylphenols on asphaltene dispersion through the integration of advanced experimental and modeling methods. High-resolution transmission electron microscope (HRTEM) images revealed that the onset of asphaltene flocculation occurs near a toluene/heptane volume ratio of 70:30 and that flocculates are well below 1 μm in size. To assess the impact of alkylphenols on asphaltene aggregation, octylphenol (OP) and dodecylphenol (DP) were evaluated by impedance analysis based on their ability to delay the precipitation onset and to reduce the size of nonflocculated asphaltene aggregates in 80:20 toluene/heptane solutions. Although a longer dispersant chain length did not affect the precipitation onset, it reduced the size of the aggregates. Molecular dynamics simulations were then performed to understand the mechanism of interaction between a model asphaltene and OP in heptane. OP molecules saturated the H-bonding sites of asphaltenes and prevented them from interacting laterally between themselves. This explained why OP favored the formation of flocculates with filamentary rather than globular structures, which were clearly observed by HRTEM. Although OP proved to be an effective dispersant, its effectiveness was hindered by its self-association and the fact that it interacted at the periphery of asphaltenes, leaving their aromatic cores uncovered.

Ultra-high-pressure liquid chromatography-tandem mass spectrometry method for the determination of alkylphenols in soil.

PubMed

Wang, Jing; Pan, Hefang; Liu, Zhengzheng; Ge, Fei

2009-03-20

A novel method has been developed for the determination of alkylphenols in soil by ultra-high-pressure liquid chromatography employing small particle sizes, combined with tandem mass spectrometry. Soil samples were extracted with pressurized liquid extraction (PLE) and then cleaned with solid-phase extraction (SPE). The extracts were separated on C18 column (1.7 microm, 50 mm x 2.1mm) with a gradient elution and a mobile phase consisting of water and acetonitrile, and then detected by an electrospray ionization tandem mass spectrometry in negative ion mode with multiple reaction monitoring (MRM). Compared with traditional liquid chromatography, it took ultra-high-pressure liquid chromatography much less time to analyze alkylphenols. Additionally, the ultra-high-pressure liquid chromatography/tandem mass spectrometry method produces satisfactory reliability, sensitivity, and accuracy. The average recoveries of the three target analytes were 74.0-103.4%, with the RSD<15%. The calibration curves for alkylphenols were linear within the range of 0.01-0.4 microg/ml, with the correlation coefficients greater than 0.99. When 10 g soil sample was used for analysis, the limits of quantification (LOQs) of the three alkylphenols were all 1.0 microg/kg.

Selective oxidation of aliphatic C-H bonds in alkylphenols by a chemomimetic biocatalytic system.

PubMed

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Feng, Yingang; Liu, Shuang-Jiang; Li, Shengying

2017-06-27

Selective oxidation of aliphatic C-H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C-H bonds of p - and m -alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity.

Selective oxidation of aliphatic C–H bonds in alkylphenols by a chemomimetic biocatalytic system

PubMed Central

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Liu, Shuang-Jiang; Li, Shengying

2017-01-01

Selective oxidation of aliphatic C–H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum. The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C–H bonds of p- and m-alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity. PMID:28607077

Fenton Oxidation Kinetics and Intermediates of Nonylphenol Ethoxylates

PubMed Central

Cui, Kai; Yi, Hao; Zhou, Zi-jian; Zhuo, Qiong-fang; Bing, Yong-xin; Guo, Qing-wei; Xu, Zhen-cheng

2014-01-01

Abstract Removal of nonylphenol ethoxylates (NPEOs) in aqueous solution by Fenton oxidation process was studied in a laboratory-scale batch reactor. Operating parameters, including initial pH temperature, hydrogen peroxide, and ferrous ion dosage, were thoroughly investigated. Maximum NPEOs reduction of 84% was achieved within 6 min, under an initial pH of 3.0, 25°C, an H2O2 dosage of 9.74×10−3 M, and a molar ratio of [H2O2]/[Fe2+] of 3. A modified pseudo-first-order kinetic model was found to well represent experimental results. Correlations of reaction rate constants and operational parameters were established based on experimental data. Results indicated that the Fenton oxidation rate and removal efficiency were more dependent on the dosage of H2O2 than Fe2+, and the apparent activation energy (ΔE) was 17.5 kJ/mol. High-performance liquid chromatography and gas chromatograph mass spectrometer analytical results indicated degradation of NPEOs obtained within the first 2 min stepwise occurred by ethoxyl (EO) unit shortening. Long-chain NPEOs mixture demonstrated a higher degradation rate than shorter-chain ones. Nonylphenol (NP), short-chain NPEOs, and NP carboxyethoxylates were identified as the primary intermediates, which were mostly further degraded. PMID:24868141

Isolation of tert-alkylphenols from the products of alkylation of phenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nesterova, T.N.; Verevkin, S.P.; Rempel', R.D.

1987-08-10

The authors studied the conditions of isolation of tert-amyl-, hexyl-, heptyl-, octyl-, decyl-, and dodecylphenols, and tert-alkylcresols, alkylpyrocatechols, and alkylhydroquinones from alkylation products. The compounds were isolated in all cases from reaction mixtures obtained in presence of cation-exchange resins of the KU-2 type. A preliminary stage, flash evaporation of the reaction mass at 4-13 Pa for 5-15 min, is needed to prevent decomposition of tert-alkylphenols during their isolation from acid reaction mixtures by fractionation. Flash distillation of high-boiling tert-alkylphenols should be conducted in presence of a component lowering the boiling point of the mixture, added in 1:(0.5-1.0) weight ratio ofmore » original mixture to the component.« less

Risk assessment of nonylphenol and its ethoxylates in U.S. river water and sediment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weeks, J.A.; Adams, W.J.; Guiney, P.D.

1994-12-31

A comprehensive program addressing the risks of nonylphenol (NP) and its ethoxylates (NPE) in aquatic environments of the United States has been undertaken by the Alkyl Phenol Ethoxylates Panel of the Chemical Manufacturers Association cooperating with EPA. Several hundred million pounds of NPE surfactants are used in the US each year. Nonylphenol can be an intermediate product of degradation of nonylphenol ethoxylates. A survey of those river reaches most likely to contain NPE and NP residues was conducted based on a random sample of a subset of the EPA River Reach File defined by certain selection criteria. Applying enhanced analyticalmore » techniques, little or no NP and NPE were found in river water at most locations, while low levels were usually detected in sediment. Acute and chronic toxicity tests using a variety of organisms have also been completed. New results are presented for shrimp, fish, tadpoles, midges, and algae. The risk of NP to the aquatic environment is examined by comparison of observed levels with toxicity benchmarks, and by application of equilibrium partitioning theory to calculate sediment interstitial chemical concentrations.« less

Fluorotelomer ethoxylates: sources of highly fluorinated environmental contaminants part I: biotransformation.

PubMed

Frömel, Tobias; Knepper, Thomas P

2010-09-01

Polyethoxylated 2-perfluoroalkylethanols ('fluorotelomer ethoxylates', F-(CF(2)-CF(2)-)(x)-(CH(2)-CH(2)-O)(y)-H, FTEO) are an important class of non-ionic fluorinated surfactants, which have been disregarded as potential source of per- and polyfluorinated organic pollutants despite their high production and application amounts. A commercial mixture of FTEO with a perfluoroalkyl chain length between 6 and 10 carbon atoms and an ethoxymer distribution between 0 and 13 was subjected to a biodegradation test. Monitoring of the aerobic biotransformation process by HPLC-ESI-MS/MS showed that FTEO are rapidly transformed with a half-life of approximately 1d. Structural elucidation of the biotransformation products with the help of hybrid quadrupole--linear ion trap tandem mass spectrometry revealed oxidation to the respective carboxylic acid followed by sequential shortening of ethoxylate units which led to FTEO carboxylates (FTEOC). The conversion rate of FTEOC was found to diminish with decreasing number of ethoxylate units and virtually ceased for compounds with seven intact ethoxy units. These short-chain FTEOC were not further degraded within 48d. Nonetheless, perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) were detected, whose formation is ascribed to degradation of residual fluorotelomer alcohols present in the commercial product. This article represents the first of two parts of a series concerning FTEO. Whilst this part is clearly focused on results of a biodegradation study of FTEO, part two will pinpoint analytical aspects, synthesis of biotransformation products and first evidence of environmental presence of the biotransformation products. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Treatability of nonylphenol ethoxylate surfactants in on-site wastewater disposal systems.

PubMed

Huntsman, Brent E; Staples, Charles A; Naylor, Carter G; Williams, Jim-Bob

2006-11-01

The fate of nine-mole nonylphenol ethoxylate (NPE9) discharged to an on-site wastewater disposal (septic) system was the focus of a 2-year investigation. Known amounts of NPE9-based detergent were metered daily into the plumbing at a single-family household. The ethoxylate-containing wastewater was discharged to the highly anoxic environment of a 4500-L septic tank before distribution to the oxic subsurface via 100 m of leach line. After 180 days of injecting detergent to the septic system, periodic soil pore water and/or groundwater samples were collected and analyzed for nonylphenol ethoxylates (NPEs), nonylphenol ether carboxylates, and nonylphenol. The NPE9 and degradation intermediates that were measured were reduced by 99.99% on a molar basis. An 18% reduction in molar concentration within the septic tank was observed. This was followed by a further 96.7% reduction of molar concentration within the leach lines. As the pore water migrated through the vadose zone, an additional 99.69% reduction in molar concentration was measured between the bottom of the leach lines (leach line effluent) and the lowest vadose zone monitoring location. The results obtained from these analyses indicate that degradation of the surfactant occurs within the anoxic portion of the disposal system with continued rapid biodegradation in the oxic unsaturated zone. Only trace amounts of degradation residuals were detected in soil pore water. The concentration and distribution of various degradation intermediates with respect to location, time, and ambient physical conditions were evaluated. Rapid and systematic degradation of NPE in on-site wastewater disposal systems was documented.

Occurrence of alkylphenols and bisphenol A in wild mussel samples from the Spanish Atlantic coast and Bay of Biscay.

PubMed

Salgueiro-González, N; Turnes-Carou, I; Viñas, L; Besada, V; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2016-05-15

Wild mussels (Mytilus galloprovincialis) were selected as bioindicators of chemical pollution to evaluate the occurrence and spatial distribution of five endocrine disrupting compounds in the Spanish Atlantic coast and Bay of Biscay. A total of 24 samples were collected in May, 2011 and analysed by selective pressurized liquid extraction followed by liquid chromatography tandem mass spectrometry determination. Branched alkylphenols (4-tert-octylphenol and nonylphenol) were determined in more than 90% of the analysed samples whereas the presence of linear alkylphenols (4-n-octylphenol and 4-n-nonylphenol) was scarcely detected (<12% of the samples). Wastewater treatment plants discharges and nautical, fishing and shipping activities were considered the primary sources of contamination by alkylphenols. Bisphenol A was found in 16% of the analysed samples associated to punctual industrial discharges. A total endocrine disrupting compound (alkylphenols and bisphenol A) average concentration of 604ngg(-1) dw was calculated and nonylphenol was the main contributor in almost all sampling points. Copyright © 2016 Elsevier Ltd. All rights reserved.

Asymmetric Oxidation of o-Alkylphenols with Chiral 2-(o-Iodoxyphenyl)-Oxazolines

PubMed Central

Boppisetti, Jagadish K.; Birman, Vladimir B.

2009-01-01

A new class of chiral iodine (V) derivatives has been prepared. These compounds have been found to transform ortho-alkylphenols into ortho-quinol Diels-Alder dimers with significant levels of asymmetric induction. PMID:19231848

Estrogenicity of alkylphenols and alkylated non-phenolics in a rainbow trout (Oncorhynchus mykiss) primary hepatocyte culture.

PubMed

Tollefsen, K-E; Eikvar, Sissel; Finne, Eivind Farmen; Fogelberg, Oscar; Gregersen, Inger Katharina

2008-10-01

Alkylphenols act as estrogen mimics by binding to and transactivating estrogen receptors (ERs) in fish. In the present study, activation of ER-mediated production of the estrogenic biomarker vitellogenin (vtg) in a primary culture of rainbow trout (Oncorhynchus mykiss) hepatocytes was used to construct a structure-activity relationship for this ubiquitous group of aquatic pollutants. The role of alkyl chain length and branching, substituent position, number of alkylated groups, and the requirement of a phenolic ring structure was assessed. The results showed that most alkylphenols were estrogenic, although with 3-300 thousand times lower affinity than the endogenous estrogen 17beta-estradiol. Mono-substituted tertiary alkylphenols with moderate (C4-C5) and long alkyl chain length (C8-C9) in the para position exhibited the highest estrogenic potency. Substitution with multiple alkyl groups, presence of substituents in the ortho- and meta-position and lack of a hydroxyl group on the benzene ring reduced the estrogenic activity, although several estrogenic alkylated non-phenolics were identified. Co-exposures with the natural estrogen 17beta-estradiol led to identification of additional estrogenic compounds as well as some anti-estrogens. A combination of low affinity for the ER and cytotoxicity was identified as factors rendering some of the alkylphenols non-estrogenic in the bioassay when tested alone.

Aquatic toxicity of four alkylphenols (3-tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, and 4-isopropylphenol) and their binary mixtures to microbes, invertebrates, and fish.

PubMed

Choi, Kyungho; Sweet, Leonard I; Meier, Peter G; Kim, Pan-Gyi

2004-02-01

The acute and chronic toxicity of four simple alkylphenols with butyl and propyl substitutions was evaluated with aquatic microbes, invertebrates, and fish. These alkylphenols-3-tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, and 4-isopropylphenol-have been detected in various environmental media, but their impact on aquatic fauna has seldom been evaluated. Relative susceptibility to each phenolic varied by test species. The marine bacterium Vibrio fischeri was the most susceptible to the alkylphenols, up to 3 orders of magnitude more sensitive than species of higher trophic levels. For 4-isopropylphenol, the 5-min Microtox EC(50) value was 0.01 mg/L, whereas the EC(50) for Ceriodaphnia after a 48-h exposure was 10.1 mg/L. Notable differences in sensitivity to the alkylphenols was also observed with the Microtox assay: 4-isopropylphenol was > 200 times more toxic to V. fischeri than was 2-isopropylphenol (EC(50) = 2.72 mg/L). For V. fischeri, the mixture toxicity of the alkylphenols was additive in nature and was predicted by a concentration addition model. The energy of the lowest unoccupied molecular orbital (ELUMO) explained the observed toxicity of the individual alkylphenols to V. fischeri (r(2) = 0.92, p < 0.05). These results suggest that the mode of action of polar narcotic alkylphenols to V. fischeri is different than that of other test organisms, possibly because of the differences in the cell structure of the prokaryotic V. fischeri. Copyright 2004 Wiley Periodicals, Inc. Environ Toxicol 19: 45-50, 2004.

RELATIVE BINDING AFFINITY OF ALKYLPHENOLS TO RAINBOW TROUT ESTROGEN RECEPTOR

EPA Science Inventory

RELATIVE BINDING AFFINITY OF ALKYLPHENOLS TO RAINBOW TROUT ESTROGEN RECEPTOR. T R Henry1, J S Denny2 and P K Schmieder2. USEPA, ORD, NHEERL, 1Experimental Toxicology Division and 2Mid-Continent Ecology Division, Duluth, MN, USA.
The USEPA has been mandated to screen industria...

Nonylphenol ethoxylates and other additives in aircraft deicers, antiicers, and waters receiving airport runoff.

PubMed

Corsi, Steven R; Zitomer, Daniel H; Field, Jennifer A; Cancilla, Devon A

2003-09-15

Samples of nine different formulations of aircraft deicer and antiicer fluids (ADAF) were screened for the presence of selected surfactants. Nonylphenol ethoxylates (NPnEO) were identified in three ADAF formulations, octylphenol ethoxylates were identified in two formulations, and six formulations contained alcohol ethoxylates. A preliminary field study was conducted at General Mitchell International Airport, Milwaukee, WI, to quantify NPnEO (n = 1-15) and one of its byproducts, nonylphenol (NP), in airport runoff. Samples were collected from two airport outfalls, from the receiving stream, and from an upstream reference site during intensive ADAF application events. NPnEO was measured at concentrations up to 1190microg/L in airport outfall samples, up to 77 ug/L in samples from the receiving stream and less than 5.0 microg/L from the upstream reference. Concentrations of glycol and other ADAF-related constituents, including NPnEO, were reduced by approximately 1 order of magnitude between the outfall sites and the receiving stream site; however, concentrations of NP in the receiving stream remained similar to those from the outfalls (< 0.04 microg/L at the upstream reference, 0.98 and 7.67 microg/L at outfalls, and 3.89 microg/L in the receiving stream). The field data suggest that NP is generated through degradation of NPnEO from airport runoff.

Nonylphenol ethoxylates and other additives in aircraft deicers, antiicers, and waters receiving airport runoff

USGS Publications Warehouse

Corsi, Steven R.; Zitomer, Daniel H.; Field, Jennifer A.; Cancilla, Devon A.

2003-01-01

Samples of nine different formulations of aircraft deicer and antiicer fluids (ADAF) were screened for the presence of selected surfactants. Nonylphenol ethoxylates (NPnEO) were identified in three ADAF formulations, octylphenol ethoxylates were identified in two formulations, and six formulations contained alcohol ethoxylates. A preliminary field study was conducted at General Mitchell International Airport, Milwaukee, WI, to quantify NPnEO (n = 1-15) and one of its byproducts, nonylphenol (NP), in airport runoff. Samples were collected from two airport outfalls, from the receiving stream, and from an upstream reference site during intensive ADAF application events. NPnEO was measured at concentrations up to 1190microg/L in airport outfall samples, up to 77 ug/L in samples from the receiving stream and less than 5.0 microg/L from the upstream reference. Concentrations of glycol and other ADAF-related constituents, including NPnEO, were reduced by approximately 1 order of magnitude between the outfall sites and the receiving stream site; however, concentrations of NP in the receiving stream remained similar to those from the outfalls (< 0.04 microg/L at the upstream reference, 0.98 and 7.67 microg/L at outfalls, and 3.89 microg/L in the receiving stream). The field data suggest that NP is generated through degradation of NPnEO from airport runoff.

SEPARATION OF T-MAZ ETHOXYLATED SORBITAN FATTY ACID ESTERS BY SUPERCRITICAL FLUID CHROMATOGRAPHY

EPA Science Inventory

The application of supercritical fluid chromatography (SFC) to the analysis of T-MAZ ethoxylated sorbitan fatty acid esters is described. FC separation methods utilize a density programming technique and a 50 um I.D. capillary column. his work demonstrates that capillary column S...

SEPARATION OF T-MAZ ETHOXYLATED SORBITAN FATTY ACID ESTERS BY REVERSE PHASE CHROMATOGRAPHY

EPA Science Inventory

The method for determination of T-MAZ ethoxylated sorbitan fatty acid esters is described. This work demonstrates that with a less retentive C8 alkyl bonded phase packing, reverse phase chromatography can be used to analyze nonionic polymer mixtures with a molecular weight range ...

Low-Dose Alkylphenol Exposure Promotes Mammary Epithelium Alterations and Transgenerational Developmental Defects, But Does Not Enhance Tumorigenic Behavior of Breast Cancer Cells

PubMed Central

Chamard-Jovenin, Clémence; Thiebaut, Charlène; Chesnel, Amand; Bresso, Emmanuel; Morel, Chloé; Smail-Tabbone, Malika; Devignes, Marie-Dominique; Boukhobza, Taha; Dumond, Hélène

2017-01-01

Fetal and neonatal exposure to long-chain alkylphenols has been suspected to promote breast developmental disorders and consequently to increase breast cancer risk. However, disease predisposition from developmental exposures remains unclear. In this work, human MCF-10A mammary epithelial cells were exposed in vitro to a low dose of a realistic (4-nonylphenol + 4-tert-octylphenol) mixture. Transcriptome and cell-phenotype analyses combined to functional and signaling network modeling indicated that long-chain alkylphenols triggered enhanced proliferation, migration ability, and apoptosis resistance and shed light on the underlying molecular mechanisms which involved the human estrogen receptor alpha 36 (ERα36) variant. A male mouse-inherited transgenerational model of exposure to three environmentally relevant doses of the alkylphenol mix was set up in order to determine whether and how it would impact on mammary gland architecture. Mammary glands from F3 progeny obtained after intrabuccal chronic exposure of C57BL/6J P0 pregnant mice followed by F1–F3 male inheritance displayed an altered histology which correlated with the phenotypes observed in vitro in human mammary epithelial cells. Since cellular phenotypes are similar in vivo and in vitro and involve the unique ERα36 human variant, such consequences of alkylphenol exposure could be extrapolated from mouse model to human. However, transient alkylphenol treatments combined to ERα36 overexpression in mammary epithelial cells were not sufficient to trigger tumorigenesis in xenografted Nude mice. Therefore, it remains to be determined if low-dose alkylphenol transgenerational exposure and subsequent abnormal mammary gland development could account for an increased breast cancer susceptibility. PMID:29109696

Draft Genome Sequence of Sphingobium fuliginis OMI, a Bacterium That Degrades Alkylphenols and Bisphenols

PubMed Central

Ogata, Yuka; Yahara, Tatsuya; Yokoyama, Takashi; Ishizawa, Hidehiro; Takada, Kazuki; Inoue, Daisuke; Sei, Kazunari

2017-01-01

ABSTRACT Sphingobium fuliginis OMI is a bacterium that can degrade a variety of recalcitrant alkylphenols and bisphenols. This study reports the draft genome sequence of S. fuliginis OMI. PMID:29167253

Utilisation of an enzyme-linked immunosorbent assay (ELISA) for determination of alkylphenols in various environmental matrices. Comparison with LC-MS/MS method.

PubMed

Pasquet, Camille; Vulliet, Emmanuelle

2011-10-15

Among the wide range of substances discharged continuously in the environment, alkylphenols became a major focus of environmental research in the last decades, as it was found that they possess endocrine disrupting properties. Knowledge about the occurrence and levels of alkylphenols in environment is critical for the risk assessment of these compounds on both ecosystem and human health. However, the analysis of traces of alkylphenols in environmental matrices is a very difficult task, and the suitable methods involve generally an extraction followed by an extensive sample clean-up before detection, steps often time-consuming and costly. In order to reduce the analysis time, obtain a high throughput of analysis and thus improve work efficiency, the objective of the present study is to investigate the use of immunochemical technique (ELISA) for the determination of nonylphenol and octylphenol in soils and various kinds of water. To our knowledge, this is the first time that the determination of alkylphenols in soil using immunoassay technique is described. A methodology is developed, based on the combination of a single preparation step and the use of a simply ELISA kit. The performances of the method are compared with LC-MS/MS, considered as reference. The developed procedure offers the sensitivity and selectivity necessary for the detection of the target alkylphenols in the ng/g or ng/L range, and is successfully applied to the analysis of several samples. Results indicate that alkylphenols are quantified with concentrations in the same order than LC-MS/MS, meaning that ELISA may be useful not only in screening the samples and get a positive/negative response, but also it allows a good approximation of the concentrations. Copyright © 2011 Elsevier B.V. All rights reserved.

[Kinetics of alkylphenols degradation in aqueous phase with excilamp irradiation].

PubMed

Liu, Yu-Hai; Ye, Zhao-Lian; Wen, Ying-Pin; Bi, Cheng-Lu

2014-06-01

The 206 nm irradiation from excilamp was able to directly photo-degrade 4-nonylphenol (4-NP) and 4-octylphenol (4-OP), but it could not oxidize them completely into CO2. Under the same irradiation condition, the removal efficiency of 4-OP was higher than that of 4-NP. Pseudo-first order kinetic model and modified kinetic model were used to fit the kinetics of photo-degradation process, and the direct photolysis rate constants under 206 nm UV irradiation were obtained. The experimental results demonstrated that the photolysis rate constant was higher at lower initial concentration of alkylphenols. Two kinetic models were appropriate for the direct photolysis of alkylphenols at low concentration, but the modified model did not fit for high concentrations. Degradation rate can be obviously enhanced when adding H2O2 into the reaction, but the TOC removal was distinct only when the dosage of H2O2 was high. At last, we concluded that the direct photolysis rate constant k(d) was 0.032 8 min(-1) and the reaction rate constant k(pH) between 4-OP and H2O2 was 17.4520 L x (mol x min)(-1).

78 FR 25388 - Significant New Use Rule on Ethoxylated, Propoxylated Diamine Diaryl Substituted Phenylmethane...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-01

...). ACTION: Final rule. SUMMARY: EPA is finalizing a significant new use rule (SNUR) under the Toxic Substances Control Act (TSCA) for the chemical substance identified generically as ethoxylated, propoxylated... manufacture, import, or process this chemical substance for an activity that is designated as a significant...

The alkylphenols 4-nonylphenol, 4-tert-octylphenol and 4-tert-butylphenol aggravate atopic dermatitis-like skin lesions in NC/Nga mice.

PubMed

Sadakane, Kaori; Ichinose, Takamichi; Takano, Hirohisa; Yanagisawa, Rie; Koike, Eiko; Inoue, Ken-ichiro

2014-08-01

Phthalate esters in plastics act as adjuvants for immunoglobulin production, which aggravates allergic disease. However, the effects of alkylphenols (used as plasticizers and surfactants) on atopic dermatitis have not been studied in detail. Therefore, the goal of the present study was to investigate the effects of the alkylphenols 4-nonylphenol (NP), 4-tert-octylphenol (OP) and 4-tert-butylphenol (BP) in a murine model of atopic dermatitis. NC/Nga mice were intraperitoneally administered NP, OP or BP and were subcutaneously injected with mite allergen in one ear to induce atopic dermatitis-like skin lesions (ADSLs). The condition of the skin was observed, and the levels of immunoglobulin in serum and inflammatory cytokines in lesions were determined. NP exacerbated mite allergen-induced ADSLs according to dose. OP and BP also significantly exacerbated skin lesions but not as a function of dose. Alkylphenols tended to increase the levels of IgE and antigen-specific IgG1 in serum. Further, the treatment of the alkylphenols increased the expression in lesions of inflammatory cytokines, interleukin-4 and monocyte chemotactic protein-3. Thymic stromal lymphopoietin levels increased according to ADSL severity. In contrast, the levels of the T-helper 1 cytokines (interleukin-18 and interferon-gamma) decreased. NP, OP or BP may enhance T-helper 2-type immune responses in NC/Nga mice, which aggravates mite allergen-induced ADSLs. Therefore, the uptake of very low levels of alkylphenols may contribute to the increase in the incidence of atopic dermatitis. Copyright © 2013 John Wiley & Sons, Ltd.

Draft Genome Sequence of Sphingobium fuliginis OMI, a Bacterium That Degrades Alkylphenols and Bisphenols.

PubMed

Kuroda, Masashi; Ogata, Yuka; Yahara, Tatsuya; Yokoyama, Takashi; Ishizawa, Hidehiro; Takada, Kazuki; Inoue, Daisuke; Sei, Kazunari; Ike, Michihiko

2017-11-22

Sphingobium fuliginis OMI is a bacterium that can degrade a variety of recalcitrant alkylphenols and bisphenols. This study reports the draft genome sequence of S. fuliginis OMI. Copyright © 2017 Kuroda et al.

Extractive recovery of phenol and p-alkylphenols from aqueous solutions with hydrophobic ketones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korenman, Ya.I.; Ermolaeva, T.N.; Podolina, E.A.

1994-03-10

Aliphatic and cyclic hydrophobic ketones were used for extractive recovery of phenol and p-alkylphenols from aqueous solutions, giving a 95-98% extraction of toxicants under the recommended conditions. The extracting agents were cyclohexanone, methylcyclohexanone, butyl methyl ketone, and isobutyl methyl ketone.

40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols and...

Survey of phthalates, alkylphenols, bisphenol A and herbicides in Spanish source waters intended for bottling.

PubMed

Bono-Blay, Francisco; Guart, Albert; de la Fuente, Boris; Pedemonte, Marta; Pastor, Maria Cinta; Borrell, Antonio; Lacorte, Silvia

2012-09-01

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination. Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed. Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77-124 %) and limits of quantification were between 0.0004 and 0.029 μg/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018 μg/L for octylphenol to 0.970 μg/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115 μg/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds. Target compounds were detected in a very low concentration and only in very few samples. This indicates the good

Persistence of nonylphenol ethoxylate surfactants and their primary degradation products in sediments from near a municipal outfall in the Strait of Georgia, British Columbia, Canada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shang, D.Y.; Macdonald, R.W.; Ikonomou, M.G.

1999-05-01

Marine sediment cores and surface grabs were collected from the Strait of Georgia, British Columbia, Canada, near the Iona municipal outfall and were analyzed for nonylphenol (NP) and its ethoxylate compounds (NPnEOs). The authors used normal-phase liquid chromatography with electrospray mass spectrometric detection to determine concentrations of ethoxylates from n = 1 to n = 19. Over half the NPnEO inventory in marine sediments resides in ethoxylates of chain length greater than n = 2, suggesting that analyses limited to short-chain ethoxylates (n = 2) are under-reporting total NPnEO by a factor of 2. The NPnEO vertical profiles and oligomermore » distributions in dated sediment cores suggest that little degradation occurs once these compounds enter the sediments: the half-life for these compounds is estimated to be greater than 60 yr. The lack of change in NPnEO oligomer distribution with age suggests that degradation by chain shortening does not occur significantly. A rough inventory shows that over 30 t of NPnEO resides in Fraser River Delta sediments near the Iona municipal outfall and that the entire Strait of Georgia sediments contain over 170 t of NPnEO.« less

Thermo-responsive polymer tethered metal-organic framework core-shell magnetic microspheres for magnetic solid-phase extraction of alkylphenols from environmental water samples.

PubMed

Jia, Yuqian; Su, Hao; Wong, Y-L Elaine; Chen, Xiangfeng; Dominic Chan, T-W

2016-07-22

In this work, the thermo-responsive polymer PNIPAM tethered to Fe3O4@SiO2@MOF core-shell magnetic microspheres was first synthesized by a surface-selective post-synthetic strategy and underwent highly efficient magnetic solid-phase extraction (MSPE) of alkylphenols from aqueous samples. Alkylphenols, including 4-tert-octylphenol (OP) and 4-n-nonylphenol (NP), were selected as target compounds. The sample quantification was carried out using LC-MS/MS in multiple reaction monitor (MRM) mode. Under optimal working conditions, the developed method showed good linearity in the range of 5-1000ngL(-1), a low limit of detection (1.5ngL(-1)), and good repeatability (relative standard deviation, <8%, n=5) for NP and OP. Owning to the hydrophilic/hydrophobic switchable properties of the nanocomposite, high recoveries (78.7-104.3%) of alkylphenols were obtained under different extraction conditions. The levels of OP and NP in environmental samples collected from local river, lake and pond waters were analyzed using the developed method. It was believed that the synthesized material with the thermo-responsive coating, large surface areas and magnetic properties should have great potential in the extraction and removal of alkylphenols from environmental samples. Copyright © 2016 Elsevier B.V. All rights reserved.

An Alkylphenol Mix Promotes Seminoma Derived Cell Proliferation through an ERalpha36-Mediated Mechanism

PubMed Central

Ajj, Hussein; Chesnel, Amand; Pinel, Sophie; Plenat, François; Flament, Stephane; Dumond, Helene

2013-01-01

Long chain alkylphenols are man-made compounds still present in industrial and agricultural processes. Their main use is domestic and they are widespread in household products, cleansers and cosmetics, leading to a global environmental and human contamination. These molecules are known to exert estrogen-like activities through binding to classical estrogen receptors. In vitro, they can also interact with the G-protein coupled estrogen receptor. Testicular germ cell tumor etiology and progression are proposed to be stimulated by lifelong estrogeno-mimetic exposure. We studied the transduction signaling pathways through which an alkyphenol mixture triggers testicular cancer cell proliferation in vitro and in vivo. Proliferation assays were monitored after exposure to a realistic mixture of 4-tert-octylphenol and 4-nonylphenol of either TCam-2 seminoma derived cells, NT2/D1 embryonal carcinoma cells or testis tumor in xenografted nude mice. Specific pharmacological inhibitors and gene-silencing strategies were used in TCam-2 cells in order to demonstrate that the alkylphenol mix triggers CREB-phosphorylation through a rapid, ERα36-PI3kinase non genomic pathway. Microarray analysis of the mixture target genes revealed that this pathway can modulate the expression of the DNA-methyltransferase-3 (Dnmt3) gene family which is involved in DNA methylation control. Our results highlight a key role for ERα36 in alkylphenol non genomic signaling in testicular germ cell tumors. Hence, ERα36-dependent control of the epigenetic status opens the way for the understanding of the link between endocrine disruptor exposure and the burden of hormone sensitive cancers. PMID:23626723

Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil.

PubMed

Cao, Zhengwen; Engelhardt, Jan; Dierks, Michael; Clough, Matthew T; Wang, Guang-Hui; Heracleous, Eleni; Lappas, Angelos; Rinaldi, Roberto; Schüth, Ferdi

2017-02-20

A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC x /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Enrichment by Conventional and Polymerizable Sulfated Nonylphenol Ethoxylate Emulsifiers in Water-Based Pressure-Sensitive Adhesive

Treesearch

Jilin Zhang; Yuxi Zhao; Matthew R. Dubay; Steven J. Severtson; Larry E. Gwin; Carl J. Houtman

2013-01-01

Comparisons of properties are made for pressure-sensitive adhesives (PSAs) generated via emulsion polymerization using both conventional and reactive emulsifiers. The emulsifiers are ammonium salts of sulfated nonylphenol ethoxylates with similar chemical structures and hydrophilic−lipophilic balances. The polymerizable surfactant possesses a reactive double...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

40 CFR 721.9280 - Reaction product of ethoxylated fatty acid oils and a phenolic pentaerythritol tetraester.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of ethoxylated fatty... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9280 Reaction product of... new uses subject to reporting. (1) The chemical substance identified generically as a reaction product...

ENVIRONMENTAL ESTROGENIC EFFECTS OF ALKYLPHENOL ETHOXYLATES. (R828676C002)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Toxicity of nonylphenol and nonylphenol ethoxylates to Ceriodaphnia

DOE Office of Scientific and Technical Information (OSTI.GOV)

England, D.; Bucksath, J.; Naylor, C.G.

1995-12-31

The 7-day survival and reproduction toxicity test on Ceriodaphnia dubia was performed using Good Laboratory Practices procedures. The definitive GLP tests were preceded by range-finding tests with only nominal concentrations and by analytical method validation. Substances used were industrial-grade nonylphenol (CAS No. 84852-15-3) and its 1.5-mole ethoxylate (CAS No. 9016-45-9). Analysis was done by solvent extraction and HPLC. All work was done in glassware to minimize loss of test substances to surface adsorption. The NOEC values for NP and NPE{sub 1.5} were, respectively, 89 and 285/{micro}g/L. LC50 values (96 hour) were 276 and 1016/{micro}g/L, respectively. These results demonstrate that Ceriodaphniamore » are much less sensitive to these chemicals than are other aquatic organisms.« less

Improvement in fermentation characteristics of degermed ground corn by lipid supplementation.

PubMed

Murthy, Ganti S; Singh, Vijay; Johnston, David B; Rausch, Kent D; Tumbleson, M E

2006-08-01

With rapid growth of fuel ethanol industry, and concomitant increase in distillers dried grains with solubles (DDGS), new corn fractionation technologies that reduce DDGS volume and produce higher value coproducts in dry grind ethanol process have been developed. One of the technologies, a dry degerm, defiber (3D) process (similar to conventional corn dry milling) was used to separate germ and pericarp fiber prior to the endosperm fraction fermentation. Recovery of germ and pericarp fiber in the 3D process results in removal of lipids from the fermentation medium. Biosynthesis of lipids, which is important for cell growth and viability, cannot proceed in strictly anaerobic fermentations. The effects of ten different lipid supplements on improving fermentation rates and ethanol yields were studied and compared to the conventional dry grind process. Endosperm fraction (from the 3D process) was mixed with water and liquefied by enzymatic hydrolysis and was fermented using simultaneous saccharification and fermentation. The highest ethanol concentration (13.7% v/v) was achieved with conventional dry grind process. Control treatment (endosperm fraction from 3D process without lipid supplementation) produced the lowest ethanol concentration (11.2% v/v). Three lipid treatments (fatty acid ester, alkylphenol, and ethoxylated sorbitan ester 1836) were most effective in improving final ethanol concentrations. Fatty acid ester treatment produced the highest final ethanol concentration (12.3% v/v) among all lipid supplementation treatments. Mean final ethanol concentrations of alkylphenol and ethoxylated sorbitan ester 1836 supplemented samples were 12.3 and 12.0% v/v, respectively.

Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis.

PubMed

Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q

2017-03-01

The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin. Copyright © 2016. Published by Elsevier Ltd.

The effect of oil-water-rock partitioning on the occurrence of alkylphenols in petroleum systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, P.; Larter, S.; Jones, M.

1997-05-01

Low molecular weight (C{sub 0}-C{sub 3}) alkylphenols are ubiquitous constituents of crude oils and formation waters of petroleum systems, and they represent legislatively monitored pollutants in produced oils and waters from offshore petroleum facilities. Their origin and the controls on their abundance are uncertain. Analysis of forty-four oils from various petroleum provinces, together with laboratory partitioning experiments, has provided further information on these controls. Although phenols are clearly partitioned between oil and water in petroleum systems, the consistency of most nondegraded petroleum phenol distributions (despite the apparent decrease of phenol concentrations in petroleums with increasing secondary migration distance) requires phenolmore » partitioning between petroleum, water, and solid phases-chiefly kerogen in the carrier bed. The retention of significant phenol concentrations in petroleums that have migrated tens of kilometres does indicate that petroleum typically only equilibrates with minor volumes of rock and associated waters. Laboratory experiments indicate that oils which have migrated approximately 25 km in the North Sea Tampen Spur through Jurassic sandstones may have equilibrated with less than 20 vol of rock and water, and possibly much less than 1 vol, depending on the sorbing phases within the rock (i.e., mineral or organic matter) and the wetting phase (oil or water). We conclude, supporting the hypothesis of Ioppolo-Armanios et al. (1995), that although ortho-substituted isomers dominate the phenol distributions of many petroleums, this reflects catalytic alkylation/isomerisation of unknown alkylphenol precursors in source rocks, rather than selective removal of meta- and para-substituted alkylphenol isomers from petroleum by water washing. 35 refs., 7 figs., 2 tabs.« less

Phthalates and alkylphenols in industrial and domestic effluents: case of Paris conurbation (France).

PubMed

Bergé, A; Gasperi, J; Rocher, V; Gras, L; Coursimault, A; Moilleron, R

2014-08-01

Phthalates and alkylphenols are toxics classified as endocrine disrupting compounds (EDCs). They are of particular concern due to their ubiquity and generally higher levels found in the environment comparatively to other EDCs. Industrial and domestic discharges might affect the quality of receiving waters by discharging organic matter and contaminants through treated waters and combined sewer overflows. Historically, industrial discharges are often considered as the principal vector of pollution in urban areas. If this observation was true in the past for some contaminants, no current data are today available to compare the quality of industrial and domestic discharges as regards EDCs. In this context, a total of 45 domestic samples as well as 101 industrial samples were collected from different sites, including 14 residential and 33 industrial facilities. This study focuses more specifically on 4 phthalates and 2 alkylphenols, among the most commonly studied congeners. A particular attention was also given to routine wastewater quality parameters. For most substances, wastewaters from the different sites were heavily contaminated; they display concentrations up to 1200 μg/l for di-(2-ethylhexyl) phthalate and between 10 and 100 μg/l for diethyl phthalate and nonylphenol. Overall, for the majority of compounds, the industrial contribution to the flux of contaminant reaching the wastewater treatment plants ranges between 1 and 3%. The data generated during this work constitutes one of the first studies conducted in Europe on industrial fluxes for a variety of sectors of activity. The study of the wastewater contribution was used to better predict the industrial and domestic contributions at the scale of a huge conurbation heavily urbanized but with a weak industrial cover, illustrated by Paris. Our results indicate that specific investigations on domestic discharges are necessary in order to reduce the release of phthalates and alkylphenols in the sewer systems

Oxidative degradation of alkylphenols by horseradish peroxidase.

PubMed

Sakuyama, Hisae; Endo, Yasushi; Fujimoto, Kenshiro; Hatana, Yasuhiko

2003-01-01

Alkylphenols such as bisphenol A (2,2-bis(4-hydroxyphenyl)propane; BPA), p-nonylphenol (p-NP), and p-octylphenol (p-OP) that are known as endocrine disrupters were oxidized by horseradish (Armoracia rusticana) peroxidase (HRP) with H2O2. The optimal pHs for BPA, p-NP, and p-OP were 8.0, 7.0, and 5.0, respectively. The optimal temperature for BPA was 20 degrees C. Although BPA was rapidly degraded by HRP, its degradation depended on the concentration of HRP. Most of the oxidation products of BPA were polymers, although some 4-isopropenylphenol was produced. When male Japanese medaka (Oryzias latipes) were exposed to BPA, vitellogenin in the blood increased. However, no increased vitellogenin was observed in medaka exposed to HRP-oxidized BPA. The enzymatic oxidation of BPA using HRP was able to eliminate its estrogen-like activity.

Partitioning of polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachates and stormwater.

PubMed

Kalmykova, Yuliya; Björklund, Karin; Strömvall, Ann-Margret; Blom, Lena

2013-03-01

Partitioning of organic pollutants is essential to their fate, mobility and removal from water and soil. To study the partitioning behavior of selected alkylphenols, bisphenol A, phthalates and polycyclic aromatic hydrocarbons (PAHs), a method for separating the truly dissolved and colloidal phase of organic pollutants was developed, verified and applied to samples of landfill leachate and stormwater from urban areas and waste-sorting sites. Alkylphenols, bisphenol A, phthalates and PAHs were detected in all the untreated samples (total concentrations), most of the filtered samples and frequently in the colloid-bound phase. Concentrations of alkylphenols and PAHs in urban stormwater were one order of magnitude lower than in the landfill leachates and stormwater from waste-sorting sites. The difference between total, dissolved and colloid-bound concentrations in the water samples was not statistically significant for any phenols or phthalates, but for three of the PAHs; naphthalene (mostly dissolved), phenanthrene and fluoranthene (mostly particulate). These results indicate that in landfill leachates and stormwaters, organic pollutants are predominantly attached to colloids and/or truly dissolved in contrast to their expected strong sorption to particulate matter. Occurrence and concentrations of pollutants in dissolved and colloid-bound phases correlated negatively with the K(OW). However, even highly hydrophobic compounds were frequently detected in filtered samples, i.e. the dissolved phases, and it is suggested that the organic content in the colloids decreases the compounds' partition to particles. The results confirm that the K(OW) values of specific organic pollutants well describe the compounds partition-binding process to dissolved organic carbon (DOC) colloids. Our findings call for a re-assessment of the organic pollutants' mobility and associated risks. This knowledge can also serve as a base for selecting efficient treatment methods for stormwater and

Catabolism of 4-alkylphenols by Acinetobacter sp. OP5: genetic organization of the oph gene cluster and characterization of alkylcatechol 2, 3-dioxygenase.

PubMed

Tuan, Nguyen Ngoc; Lin, Yi-Wen; Huang, Shir-Ly

2013-03-01

In this study, a specific PCR primer set was successfully designed for alkylcatechol 2, 3-dioxygenase genes and applied to detect the presence of this biomarker in 4-t-octylphenol-degrading Acinetobacter sp. strain OP5. A gene cluster (ophRBA1A2A3A4A5A6CEH) encoding multicomponent phenol hydroxylase and alkylcatechol 2, 3-dioxygenase was then cloned from this strain and showed the highest homology to those involved in the published medium-chain alkylphenol gene clusters. The pure enzyme of recombinant cell harboring ophB showed meta-cleavage activities for 4-methylcatechol (1,435%), 4-ethylcatechol (982%), catechol (100%), 4-t-butylcatechol (16.6%), and 4-t-octylcatechol (3.2%). The results suggest that the developed molecular technique is useful and easy in detection of medium/long-chain alkylphenol degradation gene cluster. In addition, it also provides a better understanding of the distribution of biodegradative genes and pathway for estrogenic-active long-chain alkylphenols in bacteria. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ultra-trace analysis of hormones, pharmaceutical substances, alkylphenols and phthalates in two French natural mineral waters.

PubMed

Dévier, Marie-Hélène; Le Menach, Karyn; Viglino, Liza; Di Gioia, Lodovico; Lachassagne, Patrick; Budzinski, Hélène

2013-01-15

The aim of this work was to investigate the potential presence of a broad range of organic compounds, such as hormones, alkylphenols, bisphenol A and phthalates, as well as pharmaceutical substances in two brands of bottled natural mineral waters (Evian and Volvic, Danone). The phthalates were determined by solid-phase microextraction coupled to gas chromatography-mass spectrometry (SPME-GC-MS) and the other compounds by liquid chromatography-tandem mass spectrometry (LC-MS/MS) or gas chromatography-mass spectrometry (GC-MS) after solid-phase extraction. The potential migration of alkylphenols, bisphenol A and phthalates from polyethylene terephthalate (PET) bottles was also investigated under standardized test conditions. Evian and Volvic natural mineral waters contain none of the around 120 targeted organic compounds. Traces of 3 pharmaceuticals (ketoprofen, salicylic acid, and caffeine), 3 alkylphenols (4-nonylphenol, 4-t-octylphenol, and 4-nonylphenol diethoxylate), and some phthalates including di(2-ethylhexyl)phthalate (DEHP) were detected in the samples, but they were also present in the procedural blanks at similar levels. The additional test procedures demonstrated that the few detected compounds originated from the background laboratory contamination. Analytical procedures have been designed both in the bottling factory and in the laboratory in order to investigate the sources of DEHP and to minimize to the maximum this unavoidable laboratory contamination. It was evidenced that no migration of the targeted compounds from bottles occurred under the test conditions. The results obtained in this study underline the complexity of reaching a reliable measure to qualify the contamination of a sample at ultra-trace level, in the field of very pure matrices. The analytical procedures involving glassware, equipment, hoods, and rooms specifically dedicated to trace analysis allowed us to reach reliable procedural limits of quantification at the ng/L level, by

Concentration of organic contaminants in fish and their biological effects in a wastewater-dominated urban stream

USGS Publications Warehouse

Lozano, Nuria; Rice, Clifford P.; Pagano, James; Zintek, Larry; Barber, Larry B.; Murphy, Elizabeth W.; Nettesheim, Todd G.; Minarik, Thomas A.; Schoenfuss, Heiko L.

2012-01-01

Data are presented on the concentrations of alkylphenol and alkylphenol ethoxylates (APEs) and persistent organic compounds in largemouth bass collected from a waste-water dominated stream in downtown Chicago. The fish residue concentrations of APEs are compared to concentrations of the APEs in the water that were collected at weekly intervals over two months bracketing the fall (2006) and a spring (2007) fish collection. The concentrations of APEs were significantly higher in the spring-collected fish (5.42 μg/g) versus the fall (0.99 μg/g) tand these differences were shared by differences in the water concentrations (spring — 11.47 versus fall — 3.44 μg/L). The differences in water concentration were negatively correlated with water temperatures observed over the two sampling times. Fish residue concentrations of persistent organic compounds (PCBs, PBDEs, toxaphene, and many legacy pesticides including the DDT family) did not vary from fall to spring. Some of these residue concentrations were comparable to the highest NPE (nonylphenol ethoxylate) homologue concentrations, e.g. NP1EO was 3.5 μg/g in the bass for the spring, the PBDE-congener 47 and p,p′-DDE averaged 1.0 μg/g and 0.5 μg/g, respectively, over both seasons. All the other persistent single-analyte concentrations were lower. Biological endpoints for endocrine effects measured in the same fish showed that there was an apparent positive correlation for physiological effects based on increased vitellogenin levels in males versus concentration of NPEs; however there were no observable histological differences in fall versus spring fish samples.

Detergent-dispersant additives based on high-molecular-weight alkylphenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulieva, K.N.; Namazova, I.I.; Ismailova, N.D.

1988-09-01

This article describes the synthesis and investigation of Mannich bases produced for alkylphenols, obtained in turn from ethylene oligomers. These oligomers are the still bottoms from distillation products of high-temperature oligomerization of ethylene in the presence of triethylaluminum. Two narrow cuts obtained from the distillation of oligomer fraction were used to study the influence of ethylene oligomer molecular weight on the properties of the additives. The additives were blended in DS-11 oil to evaluate their detergency-dispersancy and other properties. Comparison blends were made with succinimide additives based on the same ethylene oligomers. The Mannich bases give improvements in the oxidationmore » resistance, anticorrosion properties, and detergency-dispersancy of the DS-11 diesel oil.« less

Preparation of C₁₈-functionalized magnetic polydopamine microspheres for the enrichment and analysis of alkylphenols in water samples.

PubMed

Wang, Xianying; Deng, Chunhui

2016-02-01

In this work, C18-functionalized magnetic polydopamine microspheres (Fe3O4@PDA@C18) were successfully synthesized and applied to the analysis of alkylphenols in water samples. The magnetic Fe3O4 particles coated with hydrophilic surface were synthesized via a solvothermal reaction and the self-polymerization of dopamine. And then the C18 groups were fabricated by a silylanization method. Benefit from the merits of Fe3O4 particles, polydopamine coating and C18 groups, the Fe3O4@PDA@C18 material possessed several properties of super magnetic responsiviness, good water dispersibility, π-electron system and hydrophobic C18 groups. Thus, the materials had great potential to be developed as the adsorbent for the magnetic solid-phase extraction (MSPE) technique. Here, we selected three kinds of alkylphenols (4-tert-octylphenol, 4-n-nonylphenol, 4-n-octylphenol) to be the target analyst for evaluating the performance of the prepared material. In this study, various extraction parameters were investigated and optimized, such as pH values of water sample solution, amount of adsorbents, adsorption and desorption time, the species of desorption solution. Meanwhile, the method validations were studied, including linearity, limit of detection and method precision. From the results, Fe3O4@PDA@C18 composites were successfully applied as the adsorbents for the extraction of alkylphenols in water samples. The proposed material provided an approach for a simple, rapid magnetic solid-phase extraction for hydrophobic compounds in environmental samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of hydraulic fracturing flowback and produced waters using accurate mass: identification of ethoxylated surfactants.

PubMed

Thurman, E Michael; Ferrer, Imma; Blotevogel, Jens; Borch, Thomas

2014-10-07

Two series of ethylene oxide (EO) surfactants, polyethylene glycols (PEGs from EO3 to EO33) and linear alkyl ethoxylates (LAEs C-9 to C-15 with EO3-EO28), were identified in hydraulic fracturing flowback and produced water using a new application of the Kendrick mass defect and liquid chromatography/quadrupole-time-of-flight mass spectrometry. The Kendrick mass defect differentiates the proton, ammonium, and sodium adducts in both singly and doubly charged forms. A structural model of adduct formation is presented, and binding constants are calculated, which is based on a spherical cagelike conformation, where the central cation (NH4(+) or Na(+)) is coordinated with ether oxygens. A major purpose of the study was the identification of the ethylene oxide (EO) surfactants and the construction of a database with accurate masses and retention times in order to unravel the mass spectral complexity of surfactant mixtures used in hydraulic fracturing fluids. For example, over 500 accurate mass assignments are made in a few seconds of computer time, which then is used as a fingerprint chromatogram of the water samples. This technique is applied to a series of flowback and produced water samples to illustrate the usefulness of ethoxylate "fingerprinting", in a first application to monitor water quality that results from fluids used in hydraulic fracturing.

Alkylphenol Xenoestrogens with Varying Carbon Chain Lengths Differentially and Potently Activate Signaling and Functional Responses in GH3/B6/F10 Somatomammotropes

PubMed Central

Kochukov, Mikhail Y.; Jeng, Yow-Jiun; Watson, Cheryl S.

2009-01-01

Background Alkylphenols varying in their side-chain lengths [ethyl-, propyl-, octyl-, and nonylphenol (EP, PP, OP, and NP, respectively)] and bisphenol A (BPA) represent a large group of structurally related xenoestrogens that have endocrine-disruptive effects. Their rapid nongenomic effects that depend on structure for cell signaling and resulting functions are unknown. Objectives We compared nongenomic estrogenic activities of alkylphenols with BPA and 17β-estradiol (E2) in membrane estrogen receptor-α–enriched GH3/B6/F10 pituitary tumor cells. These actions included calcium (Ca) signaling, prolactin (PRL) release, extracellular-regulated kinase (ERK) phosphorylation, and cell proliferation. Methods We imaged Ca using fura-2, measured PRL release via radioimmunoassay, detected ERK phosphorylation by fixed cell immunoassay, and estimated cell number using the crystal violet assay. Results All compounds caused increases in Ca oscillation frequency and intracellular Ca volume at 100 fM to 1 nM concentrations, although long-chain alkylphenols were most effective. All estrogens caused rapid PRL release at concentrations as low as 1 fM to 10 pM; the potency of EP, PP, and NP exceeded that of E2. All compounds at 1 nM produced similar increases in ERK phosphorylation, causing rapid peaks at 2.5–5 min, followed by inactivation and additional 60-min peaks (except for BPA). Dose–response patterns of ERK activation at 5 min were similar for E2, BPA, and PP, whereas EP caused larger effects. Only E2 and NP increased cell number. Some rapid estrogenic responses showed correlations with the hydrophobicity of estrogenic molecules; the more hydrophobic OP and NP were superior at Ca and cell proliferation responses, whereas the less hydrophobic EP and PP were better at ERK activations. Conclusions Alkylphenols are potent estrogens in evoking these nongenomic responses contributing to complex functions; their hydrophobicity can largely predict these behaviors. PMID

Draft Genome Sequence of Pseudomonas nitroreducens Strain TX1, Which Degrades Nonionic Surfactants and Estrogen-Like Alkylphenols.

PubMed

Huang, Shir-Ly; Chen, Hsin; Hu, Anyi; Tuan, Nguyen Ngoc; Yu, Chang-Ping

2014-01-30

Pseudomonas nitroreducens TX1 ATCC PTA-6168 was isolated from rice field drainage in Taiwan. The bacterium is of special interest because of its capability to use nonionic surfactants (alkylphenol polyethoxylates) and estrogen-like compounds (4-t-octylphenol and 4-nonylphenol) as a sole carbon source. This is the first report on the genome sequence of P. nitroreducens.

Trends in analytical methodologies for the determination of alkylphenols and bisphenol A in water samples.

PubMed

Salgueiro-González, N; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2017-04-15

In the last decade, the impact of alkylphenols and bisphenol A in the aquatic environment has been widely evaluated because of their high use in industrial and household applications as well as their toxicological effects. These compounds are well-known endocrine disrupting compounds (EDCs) which can affect the hormonal system of humans and wildlife, even at low concentrations. Due to the fact that these pollutants enter into the environment through waters, and it is the most affected compartment, analytical methods which allow the determination of these compounds in aqueous samples at low levels are mandatory. In this review, an overview of the most significant advances in the analytical methodologies for the determination of alkylphenols and bisphenol A in waters is considered (from 2002 to the present). Sample handling and instrumental detection strategies are critically discussed, including analytical parameters related to quality assurance and quality control (QA/QC). Special attention is paid to miniaturized sample preparation methodologies and approaches proposed to reduce time- and reagents consumption according to Green Chemistry principles, which have increased in the last five years. Finally, relevant applications of these methods to the analysis of water samples are examined, being wastewater and surface water the most investigated. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of alkylphenols and alkylphenol mono- and diethoxylates in environmental samples by high-performance liquid chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahel, M.; Giger, W.

1985-07-01

A routine method is described for the quantitative determination of 4-nonylphenol (NP) and 4-nonylphenol mono-(NP1EO) and diethoxylate (NP2EO) in samples from wastewater and sludge treatment and from the aquatic environment. An exhaustive steam-distillation/solvent-extraction procedure was employed to enrich the analytes from aqueous and solid samples. Quantitative determinations were performed by normal-phase high-performance liquid chromatography (HP-LC) using aminosilica columns. Relative standard deviations were 3.0-4.4% in a river water containing 3.9 ..mu..g/L NP, 23.4 ..mu..g/L NP1EO, and 9.4 ..mu..g/L NP2EO. A digested sewage sludge with 1.6 g of NP/kg of dry matter was analyzed with a relative standard deviation of 3.7%. Recoveriesmore » were higher than 80%, and the estimated detection limit in water samples was 0.5 ..mu..g/L. Reversed-phase HPLC on octylsilica provided complementary qualitative data, particularly on homologous alkylphenolic compounds. Good agreement was found between quantitative determinations by HPLC and by high-resolution gas chromatography with flame ionization detection and directly coupled mass spectrometry. Municipal wastewater effluents, sewage sludges, and natural waters were analyzed to demonstrate the method's broad applicability. 19 references, 4 tables, 4 figures.« less

A Novel Bifunctional Alkylphenol Anesthetic Allows Characterization of γ-Aminobutyric Acid, Type A (GABAA), Receptor Subunit Binding Selectivity in Synaptosomes.

PubMed

Woll, Kellie A; Murlidaran, Sruthi; Pinch, Benika J; Hénin, Jérôme; Wang, Xiaoshi; Salari, Reza; Covarrubias, Manuel; Dailey, William P; Brannigan, Grace; Garcia, Benjamin A; Eckenhoff, Roderic G

2016-09-23

Propofol, an intravenous anesthetic, is a positive modulator of the GABAA receptor, but the mechanistic details, including the relevant binding sites and alternative targets, remain disputed. Here we undertook an in-depth study of alkylphenol-based anesthetic binding to synaptic membranes. We designed, synthesized, and characterized a chemically active alkylphenol anesthetic (2-((prop-2-yn-1-yloxy)methyl)-5-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenol, AziPm-click (1)), for affinity-based protein profiling (ABPP) of propofol-binding proteins in their native state within mouse synaptosomes. The ABPP strategy captured ∼4% of the synaptosomal proteome, including the unbiased capture of five α or β GABAA receptor subunits. Lack of γ2 subunit capture was not due to low abundance. Consistent with this, independent molecular dynamics simulations with alchemical free energy perturbation calculations predicted selective propofol binding to interfacial sites, with higher affinities for α/β than γ-containing interfaces. The simulations indicated hydrogen bonding is a key component leading to propofol-selective binding within GABAA receptor subunit interfaces, with stable hydrogen bonds observed between propofol and α/β cavity residues but not γ cavity residues. We confirmed this by introducing a hydrogen bond-null propofol analogue as a protecting ligand for targeted-ABPP and observed a lack of GABAA receptor subunit protection. This investigation demonstrates striking interfacial GABAA receptor subunit selectivity in the native milieu, suggesting that asymmetric occupancy of heteropentameric ion channels by alkylphenol-based anesthetics is sufficient to induce modulation of activity. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

A Novel Bifunctional Alkylphenol Anesthetic Allows Characterization of γ-Aminobutyric Acid, Type A (GABAA), Receptor Subunit Binding Selectivity in Synaptosomes*

PubMed Central

Woll, Kellie A.; Murlidaran, Sruthi; Pinch, Benika J.; Hénin, Jérôme; Wang, Xiaoshi; Salari, Reza; Covarrubias, Manuel; Dailey, William P.; Brannigan, Grace; Garcia, Benjamin A.; Eckenhoff, Roderic G.

2016-01-01

Propofol, an intravenous anesthetic, is a positive modulator of the GABAA receptor, but the mechanistic details, including the relevant binding sites and alternative targets, remain disputed. Here we undertook an in-depth study of alkylphenol-based anesthetic binding to synaptic membranes. We designed, synthesized, and characterized a chemically active alkylphenol anesthetic (2-((prop-2-yn-1-yloxy)methyl)-5-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenol, AziPm-click (1)), for affinity-based protein profiling (ABPP) of propofol-binding proteins in their native state within mouse synaptosomes. The ABPP strategy captured ∼4% of the synaptosomal proteome, including the unbiased capture of five α or β GABAA receptor subunits. Lack of γ2 subunit capture was not due to low abundance. Consistent with this, independent molecular dynamics simulations with alchemical free energy perturbation calculations predicted selective propofol binding to interfacial sites, with higher affinities for α/β than γ-containing interfaces. The simulations indicated hydrogen bonding is a key component leading to propofol-selective binding within GABAA receptor subunit interfaces, with stable hydrogen bonds observed between propofol and α/β cavity residues but not γ cavity residues. We confirmed this by introducing a hydrogen bond-null propofol analogue as a protecting ligand for targeted-ABPP and observed a lack of GABAA receptor subunit protection. This investigation demonstrates striking interfacial GABAA receptor subunit selectivity in the native milieu, suggesting that asymmetric occupancy of heteropentameric ion channels by alkylphenol-based anesthetics is sufficient to induce modulation of activity. PMID:27462076

[Determination of alkylphenol and alkylphenolpolyethoxylates in brine by solid phase extraction and high performance liquid chromatography-mass spectrometry].

PubMed

Wang, Jincheng; Xiong, Li; Zhang, Haijun; Chen, Jiping

2011-12-01

A simple method based on solid phase extraction (SPE) coupled with high performance liquid chromatography-mass spectrometry (HPLC-MS) was developed for the determination of octylphenol (OP), nonylphenol (NP), octylphenol ethoxylates (OPEOs) and nonylphenol ethoxylates (NPEOs) in brine. The extraction and cleanup of brine samples were performed on C18 solid-phase extraction cartridges. The complete separation among OP, NP, OPEOs and NPEOs was achieved on a Hypersil GOLD analytical column with methanol-water as the mobile phase. The determination was achieved using HPLC-MS with electrospray ionization (ESI) in selected ion monitoring mode. The results showed that the average recoveries of target compounds were 59.6% - 104.4% and the corresponding relative standard deviations (RSDs, n = 3) were 1.0% - 13.5%. The instrumental limits of detection for the compounds were 0.08 - 3 microg/L. This method was applied to the analysis of the samples of seawater near Dalian coast. The results showed that both NP and NPEOs were detected in all samples and their concentrations in seaport and oil port were much higher than those in other sampling sites.

Draft Genome Sequence of Pseudomonas nitroreducens Strain TX1, Which Degrades Nonionic Surfactants and Estrogen-Like Alkylphenols

PubMed Central

Chen, Hsin; Hu, Anyi; Tuan, Nguyen Ngoc

2014-01-01

Pseudomonas nitroreducens TX1 ATCC PTA-6168 was isolated from rice field drainage in Taiwan. The bacterium is of special interest because of its capability to use nonionic surfactants (alkylphenol polyethoxylates) and estrogen-like compounds (4-t-octylphenol and 4-nonylphenol) as a sole carbon source. This is the first report on the genome sequence of P. nitroreducens. PMID:24482523

Biomagnification profiles of polycyclic aromatic hydrocarbons, alkylphenols and polychlorinated biphenyls in Tokyo Bay elucidated by delta13C and delta15N isotope ratios as guides to trophic web structure.

PubMed

Takeuchi, Ichiro; Miyoshi, Noriko; Mizukawa, Kaoruko; Takada, Hideshige; Ikemoto, Tokutaka; Omori, Koji; Tsuchiya, Kotaro

2009-05-01

Biomagnification profiles of polycyclic aromatic hydrocarbons (PAHs), alkylphenols, and polychlorinated biphenyls (PCBs) from the innermost part of Tokyo Bay, Japan were analyzed using stable carbon (delta(13)C) and nitrogen (delta(15)N) isotope ratios as guides to trophic web structure. delta(15)N analysis indicated that all species of mollusks tested were primary consumers, while decapods and fish were secondary consumers. Higher concentrations of PCBs occurred in decapods and fish than in mollusks. In contrast, concentrations of PAHs and alkylphenols were lower in decapods and fish than in mollusks. Unlike PCBs, whose concentrations largely increased with increasing delta(15)N (i.e. increasing trophic level), all PAHs and alkylphenols analyzed followed a reverse trend. Molecular weights of PAHs are lower than those of PCBs, therefore low membrane permeability caused by large molecular size is an unlikely factor in the "biodilution" of PAHs. Organisms at higher trophic levels may rapidly metabolize PAHs or they may assimilate less of them.

Synthesis of m-Alkylphenols via a Ruthenium-Catalyzed C-H Bond Functionalization of Phenol Derivatives.

PubMed

Li, Gang; Gao, Panpan; Lv, Xulu; Qu, Chen; Yan, Qingkai; Wang, Ya; Yang, Suling; Wang, Junjie

2017-05-19

The first example of the synthesis of m-alkylphenols via a ruthenium-catalyzed C Ar -H bond functionalization of phenol derivatives with sec/tert-alkyl bromides is reported. Mechanistic studies indicated that the m-C Ar -H bond alkylation may involve a radical process and that a six-membered ruthenacycle complex was the active catalyst. Moreover, this approach can provide an expedited strategy for the atom-/step-economical synthesis of many noteworthy pharmaceuticals and other functional molecules.

Carbon nanotube modified glassy carbon electrode for electrochemical oxidation of alkylphenol ethoxylate.

PubMed

Patiño, Yolanda; Díaz, Eva; Lobo-Castañón, María Jesús; Ordóñez, Salvador

2018-06-01

Electrochemical oxidation of an emerging pollutant, 2-(4-methylphenoxy)ethanol (MPET), from water has been studied by cyclic voltammetry (CV). Multiwall carbon nanotubes glassy carbon electrodes (MWCNT-GCE) were used as working electrode due to their extraordinary properties. The oxidation process is irreversible, since no reduction peaks were observed in the reverse scan. The electrocatalytic effect of MWCNT was confirmed as the oxidation peak intensity increases in comparison to bare-GCE. The effect of functional groups on MWCNT was also studied by MWCNT functionalized with NH 2 (MWCNT-NH 2 ) and COOH (MWCNT-COOH) groups. The oxidation peak current decreases in the following order: MWCNT > MWCNT-NH 2 > MWCNT-COOH. Taking into account the normalized peak current, MWCNT-NH 2 exhibits the best results due to its strong interaction with MPET. Under optimal conditions (pH = 5.0 and volume of MWCNT = 10 μL), degradation was studied for MWCNT-GCE and MWCNT-NH 2 -GCE. A complete MPET removal was observed using MWCNT-GCE after four CV cycles, for a volume/area (V/A) ratio equal to 19. In the case of MWCNT-NH 2 -GCE, the maximum MPET removal was close to 90% for V/A = 37, higher than that obtained for MWCNT-GCE at the same conditions (≈80%). In both cases, no organic by-products were detected.

Application of liquid-liquid-liquid microextraction and high-performance liquid chromatography for the determination of alkylphenols and bisphenol-A in water.

PubMed

Lin, Che-Yi; Fuh, Ming-Ren; Huang, Shang-Da

2011-02-01

A method termed liquid-liquid-liquid microextraction (LLLME) was utilized to extract 4-t-butylphenol, 4-t-octylphenol, 4-n-nonylphenol, and bisphenol-A from water. The extracted target analytes were separated and quantified by high-performance liquid chromatography using a fluorescence detector. In LLLME, the donor phase (i.e. water sample) was made weakly acidic by adding monobasic potassium phosphate (KH(2) PO(4)); the organic phase adopted was 4-chlorotoluene; the acceptor phase (i.e. enriched extract) was 0.2 M tetraethylammonium hydroxide dissolved in ethylene glycol. This study solves a problem associated with the surface activity of long-chain alkylphenolate ions, permitting LLLME to extract long-chain alkylphenols. Experimental conditions such as acceptor phase composition, organic phase identity, acceptor phase volume, sample agitation, extraction time, and salt addition were optimized. The relative standard deviation (RSD, 2.0-5.8%), coefficient of determination (r(2) 0.9977-0.9999), and detection limit (0.017-0.0048 ng/mL) of the proposed method were achieved under the selected optimized conditions. The method was successfully applied to analyses of lake and tap water samples, and the relative recoveries of target analytes from the spiked lake and tap water samples were 92.8-106.3 and 93.6-105.6%, respectively. The results obtained with the proposed method confirm this microextraction technique to be reliable for the monitoring of alkylphenols and bisphenol-A in water samples. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of alkylphenols in water samples using liquid chromatography-tandem mass spectrometry after pre-column derivatization with dansyl chloride.

PubMed

Pernica, Marek; Poloucká, Petra; Seifertová, Marta; Šimek, Zdeněk

2015-10-23

The present study describes an effect of reaction condition of pre-column derivatization of alkylphenols (APs): bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), and isomers of 4-nonylphenol (iso-NP) with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride, DNSC) on their LC-ESI-MS/MS determination in water samples. Chemical derivatization improves the sensitivity and selectivity of LC-MS/MS analysis. In principle, alkylphenols can be analyzed by LC-MS/MS without derivatization. However, pre-column derivatization of APs increases the sensitivity up to 1000 times in comparison with the analysis of underivatized alkylphenols. Reaction conditions affecting formation of the DNSC-derivatives, such as various solvent, reaction temperature, reaction time, DNSC concentration and pH values were tested. The most suitable conditions, in terms of achieving a high sensitivity, resulting from this study are: acetonitrile as reaction solvent, 60 min as reaction time, 60 °C as reaction temperature, pH values 10.5, 0.5 mg mL(-1) as DNSC concentration. Calibration curves are linear at least in the range of 1-1000 ng mL(-1), limits of detection (LOD) and limits of quantification (LOQ) ranging from 0.02 to 0.25 pg/injection and from 0.08 to 0.83 pg/injection, respectively. The improved procedure was successfully applied for the analysis of APs and BPA in real water samples. The median concentration of BPA and iso-NP obtained in bottled waters was 4.7 ng L(-1) and 33.5 ng L(-1), respectively. The median concentration of 4-t-OP was 1.3 ng L(-1.) Copyright © 2015 Elsevier B.V. All rights reserved.

Determination and occurrence of phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs in an industrial sewage grid discharging to a Municipal Wastewater Treatment Plant.

PubMed

Sánchez-Avila, Juan; Bonet, Jordi; Velasco, Gemma; Lacorte, Silvia

2009-06-15

Industrial and urban discharges release organic contaminants which might affect the quality of receiving waters if not properly eliminated in Wastewater Treatment Plants (WWTP). This study is aimed to evaluate the source, transport and fate of contaminants of industrial origin in a sewage grid discharging to a WWTP and finally to the sea. The sampling network covered an industrial and urban area and wastewaters, influents and effluents of a WWTP were analyzed using a newly developed multiresidual method to capture a wide range contaminants (phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs). Alkylphenols and phthalates followed by PAHs were the main compounds detected at levels between 0.01 to 698 microg l(-1) in the sewage pipelines. At the WWTP influent they were detected at concentrations up to 345 microg l(-1). The contaminant load was eliminated in a 64-92% during the primary and secondary treatment of the plant. However, alkylphenols, phthalates bisphenol A and traces of PAHs were discharged with the effluent, producing a total net input of 825 g d(-1) to the sea. The study of wastewaters herein proposed can be used to better predict the loads into WWTP to improve treatment conditions according to specific sewage inputs and to assess the risks associated with the continuous discharge of contaminants to receiving plants.

The endocrine disrupting alkylphenols and 4,4'-DDT interfere with estrogen conversion and clearance by mouse liver cytosol.

PubMed

El-Hefnawy, Talal; Hernandez, Claudia; Stabile, Laura P

2017-09-01

Endocrine disrupting chemicals (EDCs) are ubiquitous compounds known for negative impacts on reproductive functions and for increasing cancer risk. EDCs are believed to cause the harmful effects in part through their inappropriate low-affinity binding to steroid receptors and other possible non-receptor mediated paradigms, however there is a need to further elucidate other mechanisms involving the direct and indirect impact of EDCs on reproductive functions. We examined the metabolism of 17β-estradiol (E2) and estrone (E1) by cell-free hepatic cytosol in the presence of alkylphenols (nonylphenol/NP and 4-tert-octylphenol/tOP), Dichlorodiphenyltrichloroethane (4,4'-DDT) and other EDCs. Tandem liquid chromatography mass spectrometry was utilized to quantitatively assess the impact of each EDC on estrogen clearance, inter-conversions and downstream metabolism by mouse liver cytosol. The results revealed that NP and tOP (0.1-3μg/mL) significantly reduced the hepatic cytosol clearance and biotransformation of estrogens with inclination for accumulating E2, the stronger estrogen form, than E1. Alkylphenols also caused up to a 34-fold increase in the E2/E1 ratio possibly by suppressing the hepatic E2→E1 conversion by 17β-hydroxysteroid dehydrogenase (17βHSD) types 2, 4 while displaying a weaker inhibition of E1→E2 conversion by type 1, 17βHSD. On the other hand, the pesticide 4,4'-DDT was a weaker inhibitor of clearance of estrogens by the cytosol preparations when compared to alkylphenols, whereas chemicals such as phthalates and atrazine were ineffective. Our data suggest that exposure to NP, tOP and DDT can indirectly increase the estrogenic load by suppressing the hepatic clearance of estrogens and by elevating the E2/1 ratio and could therefore increase the risk of reproductive lesions. Copyright © 2017 Society for Biology of Reproduction & the Institute of Animal Reproduction and Food Research of Polish Academy of Sciences in Olsztyn. Published by Elsevier

Determination of alkylphenols and 17beta-estradiol in fish homogenate. Extraction and clean-up strategies.

PubMed

Navarro, P; Bustamante, J; Vallejo, A; Prieto, A; Usobiaga, A; Arrasate, S; Anakabe, E; Puy-Azurmendi, E; Zuloaga, O

2010-09-17

The determination of target analytes such as nonyl- and octylphenols and 17beta-estradiol in fish homogenate require of solid-liquid extraction step. In this work microwave-assisted extraction (MAE) and focused-ultrasound liquid extraction (FUSLE) were studied as two different alternatives for extraction of the target compounds in zebrafish (Danio rerio) homogenate. In this work solid phase extraction (SPE) using 5-g and 10-g Florisil cartridges and gel permeation chromatography (GPC) were studied for the clean-up of the MAE and FUSLE extracts due to the non-selective extraction step. Although good recoveries were obtained both for SPE (106% and 126% range) and GPC (79% and 100% range) clean-up procedures, cleaner chromatograms were obtained after SPE and finally 5-g Florisil cartridges were tested since no improvement was observed when 10-g Florisil cartridges were used. Under optimized clean-up conditions, MAE and FUSLE provided comparable results for 4nOP and NP, while more accurate results were obtained for 4tOP and E2 after FUSLE. Finally, the method was applied to the determination of alkylphenols and 17beta-estradiol in zebrafish homogenate that had been exposed to known concentrations of the target analytes. In the case of alkylphenols two different isomers of nonyl- and octylphenol (4-(3',6'-dimethyl-3'-hepthyl)phenol, 363-NP, and 4-(3'-methyl-3'-hepthyl)phenol, 33-OP) were studied. 2010 Elsevier B.V. All rights reserved.

[Determination of bisphenol A, tetrabromobisphenol A and alkylphenols in water samples of sewage treatment plant using liquid chromatography-tandem mass spectrometry].

PubMed

Ding, Jie; Zhang, Shenghu; Liu, Jining; Zhou, Linjun; Chen, Guosong; Shi, Lili

2014-05-01

Bisphenol A, tetrabromobisphenol A and alkylphenols have received much attention in recent years because of their endocrine disrupting effects to aquatic ecosystem. The fate of these compounds in sewage treatment plant which is important to deal with this kind of compounds has significance on the study of exposure levels of the target compounds in the environment, and the development of analytical method is the basis on the above study. An analytical method based on liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) with negative ionization mode has been developed for measuring bisphenol A, tetrabromobisphenol A and six alkylphenols in raw and treated sewage samples. The target compounds were separated on a ZORBAX Eclipse Plus C18 column (150 mm x 2.1 mm, 3.5 microm) with mobile phases of acetonitril and 0.02% (v/v) ammonia. Analyte confirmations were performed under multiple reaction monitoring (MRM) mode and the eight compounds were separated within 11 min. The calibration curves were linear in the range of 1 - 100 microg/L (R2 > or = 0.998). The quantification limits of the eight compounds were 2.0 - 20 ng/L. The recovery experiments were performed with samples spiked at the levels of 0.2, 2 and 20 microg/L, and the recoveries for the target compounds were in the range of 64.3%-118.0%, 65.9% - 100.5% and 70.3%-102.7% (RSD < 7.1%, n = 3), respectively. Based on the analytical method, the raw and treated sewage samples from an industrial park of Jiangsu Province were analyzed. Five compounds were detected in the water outlet in the range of 11.9-3 015.3 ng/L. It shows that the method is simple, selective, sensitive and can be used to analyze the water samples of sewage treatment plant containing alkylphenols.

Determination of alkylphenols in eluates from pyrolysis solid residues using dispersive liquid-liquid microextraction.

PubMed

Bernardo, M; Gonçalves, M; Lapa, N; Mendes, B

2010-05-01

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was applied for the determination of 11 alkylphenols in eluates of chars produced in the co-pyrolysis of different wastes. The optimized DLLME procedure, 4 mL of sample solution, 15 microL of trichloroethylene as extraction solvent, 1 mL of acetone as dispersion solvent and addition of 15% (w/v) of NaCl, was validated. Under the optimum conditions, the enrichment factors were in the range of 82-180. Calibration curves were constructed for each analyte in pure water in the concentration range of 0.5-8 microg/L with correlation coefficients higher than 0.999. The limits of detection were between 0.07 and 0.17 microg/L. The repeatability of the method was evaluated using water samples fortified with the analyte mixture at two concentration levels: the relative standard deviation (RSD) values were between 3.7% and 8.0% for a concentration of 0.5 microg/L, and between 4.2% and 6.4% for a concentration of 3 microg/L. The recoveries of the analytes evaluated by fortification of real eluate samples were in the range of 67.9-97.9% for eluate 1 (obtained from a decontaminated char) and in the range of 61.9-101.4% for eluate 2 (obtained from the untreated char). o-Methylphenol presented low recoveries for both eluates showing a possible matrix effect. The results obtained show that this method is adequate for the determination of alkylphenols in environmental aqueous samples and presents itself as a fast and inexpensive technique, using minor amounts of organic solvents. Copyright (c) 2010. Published by Elsevier Ltd.

Determination of sex hormones and nonylphenol ethoxylates in the aqueous matrixes of two pilot-scale municipal wastewater treatment plants.

PubMed

Esperanza, Mar; Suidan, Makram T; Nishimura, Fumitake; Wang, Zhong-Min; Sorial, George A; Zaffiro, Alan; McCauley, Paul; Brenner, Richard; Sayles, Gregory

2004-06-01

Two analytical methods were developed and refined for the detection and quantitation of two groups of endocrine-disrupting chemicals (EDCs) in the liquid matrixes of two pilot-scale municipal wastewater treatment plants. The targeted compounds are seven sex hormones (estradiol, ethinylestradiol, estrone, estriol, testosterone, progesterone, and androstenedione), a group of nonionic surfactants (nonylphenol polyethoxylates), and their biodegradation byproducts nonylphenol and nonylphenol ethoxylates with one, two, and three ethoxylates. Solid phase extraction using C-18 for steroids and graphitized carbon black for the surfactants were used for extraction. HPLC-DAD and GC/MS were used for quantification. Each of the two 20 L/h pilot-scale plants consists of a primary settling tank followed by a three-stage aeration tank and final clarification. The primary and the waste-activated sludge are digested anaerobically in one plant and aerobically in the other. The pilot plants are fed with a complex synthetic wastewater spiked with the EDCs. Once steady state was reached, liquid samples were collected from four sampling points to obtain the profile for all EDCs along the treatment system. Complete removal from the aqueous phase was obtained for testosterone, androstenedione, and progesterone. Removals for nonylphenol polyethoxylates, estradiol, estrone, and ethinylestradiol from the aqueous phase exceeded 96%, 94%, 52%, and 50%, respectively. Levels of E3 in the liquid phase were low, and no clear conclusions could be drawn concerning its removal.

Water-based gas purge microsyringe extraction coupled with liquid chromatography for determination of alkylphenols from sea food Laminaria japonica Aresh.

PubMed

Yang, Cui; Zhao, Jinhua; Wang, Juan; Yu, Hongling; Piao, Xiangfan; Li, Donghao

2013-07-26

A novel organic solvent-free mode of gas purge microsyringe extraction, termed water-based gas purge microsyringe extraction, was developed. This technique can directly extract target compounds in wet samples without any drying process. Parameters affecting the extraction efficiency were investigated. Under optimal extraction conditions, the recoveries of alkylphenols were between 87.6 and 105.8%, and reproducibility was between 5.2 and 12.1%. The technique was also used to determine six kinds of alkylphenols (APs) from samples of Laminaria japonica Aresh. The OP and NP were detected in all the samples, and concentrations ranged from 26.0 to 54.5ngg(-1) and 45.0-180.4ngg(-1), respectively. The 4-n-butylphenol was detected in only one sample and its concentration was very low. Other APs were not detected in L. japonica Aresh samples. The experimental results demonstrated that the technique is fast, simple, non-polluting, allows for quantitative extraction, and a drying process was not required for wet samples. Since only aqueous solution and a conventional microsyringe were used, this technique proved affordable, efficient, and convenient for the extraction of volatile and semivolatile ionizable compounds. Copyright © 2013 Elsevier B.V. All rights reserved.

A Multi-tracer Approach to Determining the Fate of Wastewater in Groundwater

NASA Astrophysics Data System (ADS)

Moran, J. E.; Beller, H. R.; Leif, R.; Singleton, M. J.

2006-12-01

In California, demand for limited fresh water supplies for use as drinking water has increased, and recycled water is increasingly used for irrigation or for groundwater recharge. In this study, analysis of multiple tracers, including general minerals, stable isotopes of the water molecule (for source water identification and evidence for evaporation) and of nitrate (wastewater denitrification indicators), and tritium-helium groundwater age, allow identification and quantification of the fraction of water produced at a well that originated as applied wastewater effluent. Wastewater target compounds include metabolites of alkylphenol ethoxylate nonionic surfactants, pharmaceuticals such as ibuprofen and carbamazepine, personal care products such as triclosan and polycyclic musk fragrance compounds, the insect repellent DEET, and caffeine. In spite of a high fraction (up to 70 percent) of wastewater recharge produced at monitoring wells from two sites (in Livermore, CA and Gilroy, CA), the only detections greater than 50 ng/L were of alkylphenol carboxylic acids and the anti-seizure pharmaceuticals carbamazepine and primadone. However, even these compounds occurred at concentrations in groundwater that were significantly lower than concentrations observed in treated wastewater effluent. This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract No. W-7405-ENG-48.

Alkylphenols and alkylphenol ethoxylates, PBDEs, PCBs and chlorinated pesticides in largemouth bass from North Shore Channel of the Chicago River, Illinois

USDA-ARS?s Scientific Manuscript database

Fall 2006 and Spring 2007 samples of fish, water and effluent (Chicago Northside Water Reclamation Plant) were collected and analyzed for several persistent and semi-persistent chemicals that are believed to be significantly loading into the North Branch of the Chicago River from the Northside Water...

Pressurized hot water extraction followed by miniaturized membrane assisted solvent extraction for the green analysis of alkylphenols in sediments.

PubMed

Salgueiro-González, N; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2015-02-27

A novel and Green analytical methodology for the determination of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol) in sediments was developed and validated. The method was based on pressurized hot water extraction (PHWE) followed by miniaturized membrane assisted solvent extraction (MASE) and liquid chromatography-electrospray ionization tandem mass spectrometry detection (LC-ESI-MS/MS). The extraction conditions were optimized by a Plackett-Burman design in order to minimize the number of assays according to Green principles. Matrix effect was studied and compensated using deuterated labeled standards as surrogate standards for the quantitation of the target compounds. The analytical features of the method were satisfactory: relative recoveries varied between 92 and 103% and repeatability and intermediate precision were <9% for all compounds. Quantitation limits of the method (MQL) ranged from 0.061 (4-n-nonylphenol) to 1.7ngg(-1) dry weight (nonylphenol). Sensitivity, selectivity, automaticity and fastness are the main advantages of the exposed methodology. Reagent consumption, analysis time and waste generation were minimized. The "greenness" of the proposed method was evaluated using an analytical Eco-Scale approach and satisfactory results were obtained. The applicability of the proposed method was demonstrated analysing sediment samples of Galicia coast (NW of Spain) and the ubiquity of alkylphenols in the environment was demonstrated. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

Nakai, Satoshi; Okuda, Tetsuji; Nishijima, Wataru; Okada, Mitsumasa

2015-10-01

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 14 d of biodegradation, whereas intermediate ozonation at the 9th day of biodegradation improved subsequent DOC removal during 14 d 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Experimental Studies on the Hydrotreatment of Kraft Lignin to Aromatics and Alkylphenolics Using Economically Viable Fe-Based Catalysts

PubMed Central

2017-01-01

Limonite, a low-cost iron ore, was investigated as a potential hydrotreatment catalyst for kraft lignin without the use of an external solvent (batch reactor, initial H2 pressure of 100 bar, 4 h). The best results were obtained at 450 °C resulting in 34 wt % of liquefied kraft lignin (lignin oil) on lignin intake. The composition of the lignin oil was determined in detail (elemental composition, GC-MS, GC×GC-FID, and GPC). The total GC-detectable monomeric species amounts up to 31 wt % on lignin intake, indicating that 92 wt % of the products in the lignin oil are volatile and thus of low molecular weight. The lignin oil was rich in low-molecular-weight alkylphenolics (17 wt % on lignin) and aromatics (8 wt % on lignin). Performance of the limonite catalyst was compared to other Fe-based catalysts (goethite and iron disulfide) and limonite was shown to give the highest yields of alkylphenolics and aromatics. The limonite catalyst before and after reaction was characterized using XRD, TEM, and nitrogen physisorption to determine changes in structure during reaction. Catalyst recycling tests were performed and show that the catalyst is active after reuse, despite the fact that the morphology changed and that the surface area of the catalyst particles was decreased. Our results clearly reveal that cheap limonite catalysts have the potential to be used for the depolymerization/hydrodeoxygenation of kraft lignin for the production of valuable biobased phenolics and aromatics. PMID:28413733

Determination of nonylphenol and nonylphenol ethoxylates in wastewater using MEKC.

PubMed

Núñez, Laura; Wiedmer, Susanne K; Parshintsev, Jevgeni; Hartonen, Kari; Riekkola, Marja-Liisa; Tadeo, José L; Turiel, Esther

2009-06-01

Nonylphenol ethoxylates (NPEO(x)) are surfactants which are used worldwide and can be transformed in the environment by microorganisms to form nonylphenol (NP). Analysis of these compounds was carried out with micellar electrokinetic capillary chromatography (MEKC). Different parameters such as background electrolyte (BGE) solution, pH, type of surfactant, and sample stacking were optimized. The use of CHES (20 mM, pH 9.1) in combination with 50 mM sodium cholate as a surfactant as BGE solution, together with sample stacking using 50 mM NaCl in the sample and an injection time of 20 s, provided the best separation of the compounds studied. The method was applied to the determination of target analytes in two types of sludge water coming from two steps of a wastewater treatment plant. Liquid-liquid extraction was carried out using toluene as solvent, resulting in recoveries around 100% for all studied analytes. The presence of NPEO(x) was observed in the first step of the sludge water treatment, based on migration time and UV spectra. Identification was confirmed using tandem MS. LOQs of the studied compounds were in the range of 12.7 to 30.8 ng/mL, which is satisfactory for the analysis of real wastewater samples.

Utilization of Triton X-100 and polyethylene glycols during surfactant-mediated biodegradation of diesel fuel.

PubMed

Wyrwas, Bogdan; Chrzanowski, Łukasz; Ławniczak, Łukasz; Szulc, Alicja; Cyplik, Paweł; Białas, Wojciech; Szymański, Andrzej; Hołderna-Odachowska, Aleksandra

2011-12-15

The hypothesis regarding preferential biodegradation of surfactants applied for enhancement of microbial hydrocarbons degradation was studied. At first the microbial degradation of sole Triton X-100 by soil isolated hydrocarbon degrading bacterial consortium was confirmed under both full and limited aeration with nitrate as an electron acceptor. Triton X-100 (600 mg/l) was utilized twice as fast for aerobic conditions (t(1/2)=10.3h), compared to anaerobic conditions (t(1/2)=21.8h). HPLC/ESI-MS analysis revealed the preferential biodegradation trends in both components classes of commercial Triton X-100 (alkylphenol ethoxylates) as well as polyethylene glycols. The obtained results suggest that the observed changes in the degree of ethoxylation for polyethylene glycol homologues occurred as a consequence of the 'central fission' mechanism during Triton X-100 biodegradation. Subsequent experiments with Triton X-100 at approx. CMC concentration (150 mg/l) and diesel oil supported our initial hypothesis that the surfactant would become the preferred carbon source even for hydrocarbon degrading bacteria. Regardless of aeration regimes Triton X-100 was utilized within 48-72 h. Efficiency of diesel oil degradation was decreased in the presence of surfactant for aerobic conditions by approx. 25% reaching 60 instead of 80% noted for experiments without surfactant. No surfactant influence was observed for anaerobic conditions. Copyright © 2011 Elsevier B.V. All rights reserved.

Factors determining accumulation of bisphenol A and alkylphenols at a low trophic level as exemplified by mussels Mytilus trossulus.

PubMed

Staniszewska, Marta; Graca, Bożena; Sokołowski, Adam; Nehring, Iga; Wasik, Andrzej; Jendzul, Anna

2017-01-01

The aim of the study was to investigate abiotic and biotic factors influencing the accumulation of endocrine disrupting compounds (EDCs) such as bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in mussels Mytilus trossulus from the Gulf of Gdansk (Southern Baltic). The key abiotic factor influencing BPA, OP and NP accumulation in mussels is their hydrophilicity/lipophilicity, which affects their main assimilation routes - by digestive tract for the more lipophilic OP and NP, and additionally by the gills for the less lipophilic BPA. As a result, high condition index (i.e. higher soft tissue weight) is more often correlated with high concentrations of OP and NP in mussels than with BPA. Furthermore, alkylphenols have 6-8 times greater accumulative potential than BPA. Concentration of the studied compounds was lower in females than in males following spawning, and the effect lasted longer for BPA than for alkylphenols. The influence of season and hydrological conditions on BPA, OP, NP in the mussel was more pronounced than the proximity of external sources of these compounds. An increase in water temperature in summer probably stimulated the solubility of BPA, the least lipophilic of the studied compounds, and led to increased assimilation of this compound from water (through gills). On the other hand, high OP and NP concentrations in mussels occurred in spring, which was caused by increased surface run-off and sediments resuspension. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ground-state IVR of jet-cooled p-alkylphenols and p-alkylanilines studied by stimulated emission ion dip and stimulated Raman-UV optical double-resonance spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ebata, T.; Ito, M.

1992-04-16

This paper reports the intramolecular vibrational redistribution (IVR) of the jet-cooled p-alkylphenols and p-alkylanilines in S{sub 0} state by using stimulated emission ion dip and stimulated raman-UV optical double-resonance spectroscopy. The IVR rate constants of several vibrational levels localized in the benzene ring are estimated. 31 refs., 12 figs., 4 tabs.

Separation of alkylphenols by normal-phase and reversed-phase high-performance liquid chromatography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schabron, J.F.; Hurtubise, R.J.; Silver, H.F.

1978-11-01

Empirical correlation factors were developed which relate log k' values for alkylphenols, the naphthols, and two phenylphenols to structural features. Both normal-phase and reversed-phase chromatographic systems were studied. The stationary phases employed in the normal-phase work were ..mu..-Bondapak CN, ..mu..-Bondapak NH/sub 2/, and ..mu..-Porasil. The structural features which affect retention in the normal-phase chromatographic systems are the number of ortho substituents, the number of aliphatic carbons, and the number of aromatic rings. The stationary phases employed in the reversed-phase work were ..mu..-Bondapak C/sub 18/ and ..mu..-Bondapak CN. The structural features which affect retention in the reversed-phase chromatographic systems are themore » number of aliphatic carbons and the number of aromatic double bonds. On ..mu..-Bondapak C/sub 18/, the presence or absence of a nonaromatic ring is of added importance.« less

Degradation of alkylphenols by white rot fungus Irpex lacteus and its manganese peroxidase.

PubMed

Moon, Dong-Soo; Song, Hong-Gyu

2012-10-01

Alkylphenols are common endocrine disrupters that are produced from the degradation of widely used surfactants. Since they cause various harmful effects on aquatic life and in humans, they should be removed from the environments being contaminated. White rot fungus Irpex lacteus can completely degrade 100 mg/L of octylphenol, nonylphenol, and phenylphenol during 1 day of incubation in the complex YMG medium, which was the highest degrading capability among nine strains of white rot fungi tested. In the N-limited Kirk's basal salts medium, I. lacteus could degrade almost 100 % of 100 mg/L octylphenol and nonylphenol in 1 h, and exhibited a high activity of manganese peroxidase (MnP; 1,790 U/L). MnP of I. lacteus was purified by ion exchange chromatography, and this degraded 99 % of 50 mg/L octylphenol and removed 80 % of estrogenic activity in 2 hours. In addition, the purified MnP (10 U/mL) degraded over 90 % of 50 mg/L nonylphenol in 1 h.

Anti-scratching behavioral effect of the essential oil and phytol isolated from Artemisia princeps Pamp. in mice.

PubMed

Ryu, Kwon-Ryeol; Choi, Jong-Youl; Chung, Suna; Kim, Dong-Hyun

2011-01-01

The anti-scratching behavioral effect of the essential oil and phytol isolated from Artemisia princeps Pamp. (AP, family Asteraceae), which is widely used in traditional medicine for inflammatory diseases, was investigated IN VIVO. Treatment of mice with AP essential oil (APEO) and phytol inhibited histamine- and compound 48/80-induced scratching behaviors. The anti-scratching behavioral effects of APEO and phytol are in proportion to their vascular permeability-inhibitory effects. These agents also inhibited the level of allergic cytokines, IL-4, and TNF- α, and the activation of transcription factors, NF- κB and c-jun (AP-1), in histamine-treated skin tissues. Based on these results, APEO and phytol may improve scratching behavior in skin by inhibiting the expression of allergic cytokines via the regulation of NF- κB and AP-1 activation. © Georg Thieme Verlag KG Stuttgart · New York.

Endocrine disrupting alkylphenolic chemicals and other contaminants in wastewater treatment plant effluents, urban streams, and fish in the Great Lakes and Upper Mississippi River Regions

USGS Publications Warehouse

Barber, Larry B.; Loyo-Rosales, Jorge E.; Rice, Clifford P.; Minarik, Thomas A.; Oskouie, Ali K.

2015-01-01

Urban streams are an integral part of the municipal water cycle and provide a point of discharge for wastewater treatment plant (WWTP) effluents, allowing additional attenuation through dilution and transformation processes, as well as a conduit for transporting contaminants to downstream water supplies. Domestic and commercial activities dispose of wastes down-the-drain, resulting in wastewater containing complex chemical mixtures that are only partially removed during treatment. A key issue associated with WWTP effluent discharge into streams is the potential to cause endocrine disruption in fish. This study provides a long-term (1999-2009) evaluation of the occurrence of alkylphenolic endocrine disrupting chemicals (EDCs) and other contaminants discharged from WWTPs into streams in the Great Lakes and Upper Mississippi River Regions (Indiana, Illinois, Michigan, Minnesota, and Ohio). The Greater Metropolitan Chicago Area Waterways, Illinois, were evaluated to determine contaminant concentrations in the major WWTP effluents and receiving streams, and assess the behavior of EDCs from their sources within the sewer collection system, through the major treatment unit processes at a WWTP, to their persistence and transport in the receiving stream. Water samples were analyzed for alkylphenolic EDCs and other contaminants, including 4-nonylphenol (NP), 4-nonylphenolpolyethoxylates (NPEO), 4-nonylphenolethoxycarboxylic acids (NPEC), 4-tert-octylphenol (OP), 4-tert-octylphenolpolyethoxylates (OPEO), bisphenol A, triclosan, ethylenediaminetetraacetic acid (EDTA), and trace elements. All of the compounds were detected in all of the WWTP effluents, with EDTA and NPEC having the greatest concentrations. The compounds also were detected in the WWTP effluent dominated rivers. Multiple fish species were collected from river and lake sites and analyzed for NP, NPEO, NPEC, OP, and OPEO. Whole-body fish tissue analysis indicated widespread occurrence of alkylphenolic compounds

Synthesis and surface activity properties of alkylphenol polyoxyethylene nonionic trimeric surfactants

NASA Astrophysics Data System (ADS)

Yang, Fang; Li, Gang; Qi, Jian; Zhang, Song-Mei; Liu, Rong

2010-10-01

A series of trimeric n-alkylphenol polyoxyethylene surfactants (TAP) were successfully synthesized and the molecular structure were confirmed by NMR, FTIR spectrum and elemental analysis. Using the same synthesis route, the trimeric nonylphenol polyoxyethylene surfactant (TNP) was synthesized using industrial product nonylphenol and paraformaldehyde, and its molecular structure was characterized by 1HNMR, FTIR spectrum and elemental analysis. The optimal reaction conditions were established. The surface activity properties of TAP and TNP (such as the critical micelle concentration (cmc), the values of surface tension at the cmc ( γcmc), the maximum surface excess concentration ( Γcmc), and the minimum surface area per surfactant molecule ( Acmc)), were determined by means of Wilhelmy plate method and steady-state fluorescence probe method, respectively. The experimental results show that the lengths of the hydrophilic group oxyethylene (EO) chains and hydrophobic group methylene chains have an influence on the cmc, γcmc, Γcmc, and Acmc of series of surfactants. Furthermore, TAP are arranged to staggered three-dimensional array mode at the air-water interface, which has exhibited better surface properties, such as low cmc values, strong adsorption affinities and wet abilities.

Sequential ASE extraction of alkylphenols from sediments: Occurrence and environmental implications.

PubMed

Gong, Jian; Xu, Lei; Yang, Yu; Chen, Di-Yun; Ran, Yong

2011-08-30

The occurrence of alkylphenols (APs) including nonylphenol (NP) and octylphenol (OP) in the riverine sediments from the Pearl River Delta (PRD), South China was investigated and compared by Soxhlet extraction (S-APs) with dichloromethane and by sequential accelerated solvent extraction (ASE) (A-APs) with 1:6 toluene/methanol, respectively. Concentrations of OP and NP range from <1 to 463ng/g dw and 31-21,885ng/g dw, respectively, demonstrating that the contamination level of APs in the PRD is one of the highest in the world. Moreover, the A-APs contents are highly significantly related to and on average 1.5 times the S-APs contents. For sequential two ASE extractions, APs in the first extract accounts for 82.2-99.2% of their total contents in the sequential two extractions. The correlation analysis shows that S-APs and A-APs are both significantly associated with the contents of total organic carbon (TOC), suggesting that the variable extraction efficiency of these two methods is related to the presence of condensed organic matter in the sediments. Copyright © 2011 Elsevier B.V. All rights reserved.

Nonylphenol: Properties, legislation, toxicity and determination.

PubMed

Araujo, Frederico G DE; Bauerfeldt, Glauco F; Cid, Yara Peluso

2017-08-07

This paper aims to gather and discuss important information about nonylphenol, such as physical chemistry properties, toxicity and analytical methods in various matrices. As a degradation product of ethoxylated alkylphenols, nonylphenol presents a higher degree of reactivity than its precursor. Due to its harmful effects on the environment, use and production of nonylphenol has been banned in European Union countries, alongside their precursors. The guide on quality of drinking water (USEPA) recommends a maximum concentration of 28 µg L-1 for fresh water. In Brazil, there is no clear legislation containing values ​​of maximum concentration of nonylphenol. Due to this lack of regulation, a continuous monitoring is necessary of this pollutant in environmental samples. This paper aims to encourage further studies on nonylphenol, seen as a critical environmental pollutant. For proper monitoring is necessary to have reliable analytical methods and easy to perform in routine analysis.

Determination of nonylphenol and short-chained nonylphenol ethoxylates in drain water from an agricultural area.

PubMed

Zgoła-Grześkowiak, Agnieszka; Grześkowiak, Tomasz; Rydlichowski, Robert; Łukaszewski, Zenon

2009-04-01

Water samples from agricultural drains were tested for the presence of nonylphenol and nonylphenol mono- and diethoxylates. The analytes belong to biodegradation products of long-chained nonylphenol ethoxylates, which are used as additives in pesticide formulations. Quantification of these analytes was performed by HPLC with fluorescence detection after isolation by using multi-capillary polytetrafluoroethylene (PTFE) trap extraction. This newly developed technique allowed obtaining about 90% recovery of these analytes in synthetic samples and several percent lower recovery in real samples. Also, no additional sample cleaning was needed before chromatographic analysis. The limit of quantitation for all the analytes was 0.1 microg L(-1). The nonylphenol, nonylphenol mono- and diethoxylates were detected at the concentrations ranging from 0.5 to 6.0 microg L(-1), from 0.2 to 0.7 microg L(-1) and from below 0.02 to 0.4 microg L(-1), respectively. Concentrations of nonylphenol and its derivatives were higher in samples taken in spring than in summer.

Degradation of the commercial surfactant nonylphenol ethoxylate by advanced oxidation processes.

PubMed

da Silva, Salatiel Wohlmuth; Klauck, Cláudia Regina; Siqueira, Marco Antônio; Bernardes, Andréa Moura

2015-01-23

Four different oxidation process, namely direct photolysis (DP) and three advanced oxidation processes (heterogeneous photocatalysis - HP, eletrochemical oxidation - EO and photo-assisted electrochemical oxidation - PEO) were applied in the treatment of wastewater containing nonylphenol ethoxylate (NPnEO). The objective of this work was to determine which treatment would be the best option in terms of degradation of NPnEO without the subsequent generation of toxic compounds. In order to investigate the degradation of the surfactant, the processes were compared in terms of UV/Vis spectrum, mineralization (total organic carbon), reaction kinetics, energy efficiency and phytotoxicity. A solution containing NPnEO was prepared as a surrogate of the degreasing wastewater, was used in the processes. The results showed that the photo-assisted processes degrade the surfactant, producing biodegradable intermediates in the reaction. On the other hand, the electrochemical process influences the mineralization of the surfactant. The process of PEO carried out with a 250W lamp and a current density of 10mA/cm(2) showed the best results in terms of degradation, mineralization, reaction kinetics and energy consumption, in addition to not presenting phytotoxicity. Based on this information, this process can be a viable alternative for treating wastewater containing NPnEO, avoiding the contamination of water resources. Copyright © 2014 Elsevier B.V. All rights reserved.

Polybrominated diphenyl ethers (PBDEs) in fish tissue may be an indicator of plastic contamination in marine habitats.

PubMed

Rochman, Chelsea M; Lewison, Rebecca L; Eriksen, Marcus; Allen, Harry; Cook, Anna-Marie; Teh, Swee J

2014-04-01

The accumulation of plastic debris in pelagic habitats of the subtropical gyres is a global phenomenon of growing concern, particularly with regard to wildlife. When animals ingest plastic debris that is associated with chemical contaminants, they are at risk of bioaccumulating hazardous pollutants. We examined the relationship between the bioaccumulation of hazardous chemicals in myctophid fish associated with plastic debris and plastic contamination in remote and previously unmonitored pelagic habitats in the South Atlantic Ocean. Using a published model, we defined three sampling zones where accumulated densities of plastic debris were predicted to differ. Contrary to model predictions, we found variable levels of plastic debris density across all stations within the sampling zones. Mesopelagic lanternfishes, sampled from each station and analyzed for bisphenol A (BPA), alkylphenols, alkylphenol ethoxylates, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), exhibited variability in contaminant levels, but this variability was not related to plastic debris density for most of the targeted compounds with the exception of PBDEs. We found that myctophid sampled at stations with greater plastic densities did have significantly larger concentrations of BDE#s 183 -209 in their tissues suggesting that higher brominated congeners of PBDEs, added to plastics as flame-retardants, are indicative of plastic contamination in the marine environment. Our results provide data on a previously unsampled pelagic gyre and highlight the challenges associated with characterizing plastic debris accumulation and associated risks to wildlife. Copyright © 2014 Elsevier B.V. All rights reserved.

Reproductive Alterations in Chronically Exposed Female Mice to Environmentally Relevant Doses of a Mixture of Phthalates and Alkylphenols.

PubMed

Patiño-García, Daniel; Cruz-Fernandes, Leonor; Buñay, Julio; Palomino, Jaime; Moreno, Ricardo D

2018-02-01

Endocrine-disrupting chemicals (EDCs) are exogenous compounds that modify hormone biosynthesis, causing adverse effects to human health. Among them, phthalates and alkylphenols are important due to their wide use in plastics, detergents, personal care products, cosmetics, and food packaging. However, their conjoint effects over reproductive female health have not been addressed. The aim of this work was to test the effect of chronically exposed female mice to a mixture of three phthalates [bis (2-ethylhexyl), dibutyl, and benzyl butyl] and two alkylphenols (4-nonylphenol and 4-tert-octylphenol) from conception to adulthood at environmentally relevant doses. These EDCs were administered in two doses: one below the minimal risk dose to cause adverse effects on human development and reproduction [1 mg/kg body weight (BW)/d of the total mixture] and the other one based on the reference value close to occupational exposure in humans (10 mg/kg BW/d of the total mixture). Our results show that both doses had similar effects regarding the uterus and ovary relative weight, estrous cyclicity, serum levels of progesterone and 17β-estradiol, and expression of key elements in the steroidogenesis pathway (acute steroidogenic regulatory protein and CYP19A1). However, only the 1-mg/kg BW/d dose delayed the onset of puberty and the transition from preantral to antral follicles, whereas the 10-mg/kg BW/d dose decreased the number of antral follicles and gonadotropin receptor expression. In addition, we observed changes in several fertility parameters in exposed females and in their progeny (F2 generation). In conclusion, our results indicate that chronic exposure to a complex EDC mixture, at environmentally relevant doses, modifies reproductive parameters in female mice. Copyright © 2018 Endocrine Society.

Two-dimensional chromatography of complex polymers, 8. Separation of fatty alcohol ethoxylates simultaneously by end group and chain length.

PubMed

Raust, Jacques-Antoine; Bruell, Adele; Sinha, Pritish; Hiller, Wolf; Pasch, Harald

2010-09-01

A comprehensive two-dimensional liquid chromatography system was developed to precisely describe the molecular heterogeneity of fatty alcohol ethoxylates. The end-group functionality was analyzed by gradient HPLC while ethylene oxide oligomer distributions were characterized by liquid adsorption chromatography. A baseline separation of all functionality fractions irrespective of the ethylene oxide oligomer chain length was achieved on nonpolar X-Terra(®) C(18) with a methanol-water gradient, whereas an isocratic flow of isopropanol-water on a polar Chromolith(®) Si column gave a separation according to the oligomer chain length without interference of the end-group distribution. The combination of these two methods to conduct online two-dimensional liquid chromatography experiments resulted in a comprehensive two-dimensional picture on the molecular heterogeneity of the sample.

Comparative evaluation of some methods of investigations of the composition of hydroxyethylated alkylphenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fabrichnaya, A.L.; Rubanov, V.E.; Tavrin, A.E.

1987-11-10

Hydroxyethylated alkylphenols (HEAP/sub n/), which are nonionogenic surfactants, are used in the petroleum industry for increasing the extraction of oil. An attempt was made in this study to use methods of column fractionation, turbidimetric titration (TT), and gel permeation chromatography (GPC) for determining the molecular inhomogeneity of HEAP/sub n/ (n = 10) characterized by the molecular-weight distribution (MWD). The study of the MWD of HEAP by different methods showed that as a function of the problems actually posed, all of the methods can be used for this purpose. For operational control of the molecular and structural inhomogeneities in the preparationmore » of HEAP, it is desirable to use such methods as GPC and TT. The preference which should be given to GPC due to its rapidity and the volume of the information obtained is neutralized by the difficulty in procuring the instruments. For this reason, the availability and simplicity of the apparatus used is a favorable circumstance for the use of TT.« less

Pseudomonas japonica sp. nov., a novel species that assimilates straight chain alkylphenols.

PubMed

Pungrasmi, Wiboonluk; Lee, Haeng-Seog; Yokota, Akira; Ohta, Akinori

2008-02-01

A bacterial strain, WL(T), which was isolated from an activated sludge, was able to degrade alkylphenols. 16S rDNA sequence analysis indicated that strain WL(T) belonged to the genus Pseudomonas (sensu stricto) and formed a monophyletic clade with the type strain of Pseudomonas graminis and other members in the Pseudomonas putida subcluster with sequence similarity values higher than 97%. Genomic relatedness based on DNA-DNA hybridization of strain WL(T) to these strains is 2-41%. Strain WL(T) contained ubiquinone-9 as the main respiratory quinone, and the G+C content of DNA was 66 mol%. The organism contained hexadecanoic acid (16:0), hexadecenoic acid (16:1) and octadecenoic acid (18:1) as major cellular fatty acids. The hydroxy fatty acids detected were 3-hydroxydecanoic acid (3-OH 10:0), 3-hydroxydodecanoic acid (3-OH 12:0) and 2-hydroxydodecanoic acid (2-OH 12:0). These results, as well as physiological and biochemical characteristics clearly indicate that the strain WL(T) represents a new Pseudomonas species, for which the name Pseudomonas japonica is proposed. The type strain is strain WL(T) (=IAM 15071T=TISTR 1526T).

Evaluation of two pilot scale membrane bioreactors for the elimination of selected surfactants from municipal wastewaters

NASA Astrophysics Data System (ADS)

González, Susana; Petrovic, Mira; Barceló, Damiá

2008-07-01

SummaryThe removal of selected surfactants, linear alkylbenzene sulfonates (LAS), coconut diethanol amides (CDEA) and alkylphenol ethoxylates and their degradation products were investigated using a two membrane bioreactor (MBR) with hollow fiber and plate and frame membranes. The two pilot plants MBR run in parallel to a full-scale conventional activated sludge (CAS) treatment. A total of eight influent samples with the corresponding effluent samples were analysed by solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS-MS). The results indicate that both MBR have a better effluent quality in terms of chemical and biological oxygen demand (COD and BOD), NH4+ , concentration and total suspended solids (TSS). MBR showed a better similar performance in the overall elimination of the total nonylphenolic compounds, achieving a 75% of elimination or a 65% (the same elimination reached by CAS). LAS and CDEA showed similar elimination in the three systems investigated and no significant differences were observed.

Toxicity and kinetic parameters of the aerobic biodegradation of the phenol and alkylphenols by a mixed culture.

PubMed

Acuña-Argüelles, M E; Olguin-Lora, P; Razo-Flores, E

2003-04-01

A mixed culture aerobically metabolized phenol, cresol isomers (o-,m-,p-), 2-ethylphenol and xylenol isomers (2,5-DMP and 3,4-DMP) as the sole carbon and energy source. This culture had a high tolerance towards phenol with values of maximum degradation rate (Vmax) of 47 microM phenol mg-1 protein h-1 and inhibition substrate constant (Ki) of 10 mM. These kinetic parameters were considerably diminished and the toxicity increased with the alkylphenols. For example with 2,5-xylenol, Vmax and Ki values of 0.8 microM 2,5-xylenol mg-1 protein h-1 and 1.3 mM, respectively, were obtained. The cresols were 5-fold more toxic than phenol, whereas 2-ethylphenol and 3,4-xylenol were 11-fold more toxic, and 2,5-xylenol was 34-fold more toxic than phenol.

Separation and characterization of polycyclic aromatic hydrocarbons and alkylphenols in coal derived solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hurtubise, R.J.; Allen, T.W.; Hussain, A.

1981-03-29

Dry-column chromatography with an aluminum oxide stationary phase and a n-hexane-ether (19:1) mobile phase was used to separate polycyclic aromatic hydrocarbons (PAH) by ring size. Prior to the dry-column chromatography step, the coal derived solvents were added to an acid treated silica gel column and eluted with chloroform. This step removed pyridine-type nitrogen heterocycles. After separation of the individual ring fractions, the fractions were further separated by either thin layer chromatography (TLC) or high performance liquid chromatography (HPLC). If TLC was used, then after separation fluorescence profiles of each PAH ring fraction distributed on 30%-acetylated cellulose chromatoplates were obtained withmore » a spectrodensitometer. Measurement of fluorescence peak heights gave an approximate measure of the amount of the 3-, 4-, 5-, and 6- ring PAH. For HPLC separation, the 3- and 4- ring PAH fractions obtained from the dry-column chromatography step were separated with a ..mu..-Bondapak C/sub 18/ column and methanol:water (65:35) mobile phase. The HPLC separated PAH were characterized by chromatographic correlation factors and corrected fluorescence excitation spectra. Alkylphenols were identified in coal recycle solvent sample following separation by HPLC.« less

Determination of parabens and endocrine-disrupting alkylphenols in soil by gas chromatography-mass spectrometry following matrix solid-phase dispersion or in-column microwave-assisted extraction: a comparative study.

PubMed

Pérez, R A; Albero, B; Miguel, E; Sánchez-Brunete, C

2012-03-01

Two rapid methods were evaluated for the simultaneous extraction of seven parabens and two alkylphenols from soil based on matrix solid-phase dispersion (MSPD) and microwave-assisted extraction (MAE). Soil extracts were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide and analyzed by gas chromatography with mass spectrometry. Extraction and clean-up of samples were carried out by both methods in a single step. A glass sample holder, inside the microwave cell, was used in MAE to allow the simultaneous extraction and clean-up of samples and shorten the MAE procedure. The detection limits achieved by MSPD were lower than those obtained by MAE because the presence of matrix interferences increased with this extraction method. The extraction yields obtained by MSPD and MAE for three different types of soils were compared. Both procedures showed good recoveries and sensitivity for the determination of parabens and alkylphenols in two of the soils assayed, however, only MSPD yielded good recoveries with the other soil. Finally, MSPD was applied to the analysis of soils collected in different sites of Spain. In most of the samples analyzed, methylparaben and butylparaben were detected at levels ranging from 1.21 to 8.04 ng g(-1) dry weight and 0.48 to 1.02 ng g(-1) dry weight, respectively.

Isopycnic Phases and Structures in H2O/CO2/Ethoxylated Alcohol Surfactant Mixtures

NASA Technical Reports Server (NTRS)

Paulaitis, Michael E.; Zielinski, Richard G.; Kaler, Eric W.

1996-01-01

Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(i)E(j)) surfactants can form three coexisting liquid phases at conditions where two of the phases have the same density (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing the surfactants C8E5, C10E6, and C12E6, but not for those mixtures containing either C4E1 or CgE3. Pressure-temperature (PT) projections for this isopycnic three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. As a preliminary to measuring the microstructure in isopycnic three component mixtures, phase behavior and small angle neutron scattering (SANS) experiments were performed on mixtures of D2O/CO2/ n-hexaethyleneglycol monododecyl ether (C12E6) as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%). Parameters extracted from model fits of the SANS spectra indicate that, while micellar structure remains essentially unchanged, critical concentration fluctuations increase as the phase boundary and plait point are approached.

Artemisia princeps Pamp. Essential oil and its constituents eucalyptol and α-terpineol ameliorate bacterial vaginosis and vulvovaginal candidiasis in mice by inhibiting bacterial growth and NF-κB activation.

PubMed

Trinh, Hien-Trung; Lee, In-Ah; Hyun, Yang-Jin; Kim, Dong-Hyun

2011-12-01

To investigate the inhibitory effects of Artemisia princeps Pamp. (family Asteraceae) essential oil (APEO) and its main constituents against bacterial vaginosis and vulvovaginal candidiasis, their antimicrobial activities against Gardnerella vaginalis and Candida albicans in vitro and their anti-inflammatory effects against G. vaginalis-induced vaginosis and vulvovaginal candidiasis were examined in mice. APEO and its constituents eucalyptol and α-terpineol were found to inhibit microbe growths. α-Terpineol most potently inhibited the growths of G. vaginalis and C. albicans with MIC values of 0.06 and 0.125 % (v/v), respectively. The antimicrobial activity of α-terpineol was found to be comparable to that of clotrimazole. Intravaginal treatment with APEO, eucalyptol, or α-terpineol significantly decreased viable G. vaginalis and C. albicans numbers in the vaginal cavity and myeloperoxidase activity in mouse vaginal tissues compared with controls. These agents also inhibited the expressions of proinflammatory cytokines (IL-1 β, IL-6, TNF- α), COX-2, iNOS, and the activation of NF- κB and increased expression of the anti-inflammatory cytokine IL-10. In addition, they inhibited the expressions of proinflammatory cytokines and the activation of NF- κB in lipopolysaccharide-stimulated peritoneal macrophages, and α-terpineol most potently inhibited the expressions of proinflammatory cytokines and NF- κB activation. Based on these findings, APEO and its constituents, particularly α-terpineol, ameliorate bacterial vaginosis and vulvovaginal candidiasis by inhibiting the growths of vaginal pathogens and the activation of NF- κB. © Georg Thieme Verlag KG Stuttgart · New York.

Alkylphenol metabolites in fish bile as biomarkers of exposure to offshore oil industry produced water in feral fish.

PubMed

Beyer, Jonny; Sundt, Rolf C; Sanni, Steinar; Sydnes, Magne O; Jonsson, Grete

2011-01-01

The measurement of low-concentration alkylphenol (AP) exposure in fish is relevant in connection with monitoring and risk assessment of offshore oil industry produced water (PW) discharges. Detection of AP markers in fish bile offers significantly greater sensitivity than detection of AP in tissues such as liver. Recent studies revealed that gas chromatography-mass spectrometry in electron ionization mode (GC-EI-MS) enabled a selective and sensitive analytical detection of PW AP in mixtures with unknown composition. A procedure consisting of enzymatic deconjugation of metabolites in fish bile followed by derivatization with bis(trimethylsilyl)trifluoroacetamide and then separation and quantification of derivatized AP using GC-EI-MS is presented. The use of this procedure as a possible recommended approach for assessment and biomonitoring of AP contamination in fish populations living down-current from offshore oil production fields is presented.

Environmental risk assessment of alkylphenols from offshore produced water on fish reproduction.

PubMed

Beyer, Jonny; Myhre, Lars Petter; Sundt, Rolf C; Meier, Sonnich; Tollefsen, Knut-Erik; Vabø, Rune; Klungsøyr, Jarle; Sanni, Steinar

2012-04-01

Concern has been raised over whether environmental release of alkylphenols (AP) in produced water (PW) discharges from the offshore oil industry could impose a risk to the reproduction of fish stocks in the North Sea. An environmental risk assessment (ERA) was performed to determine if environmental exposure to PW APs in North Sea fish populations is likely to be high enough to give effects on reproduction endpoints. The DREAM (Dose related Risk and Effect Assessment Model) software was used in the study and the inputs to the ERA model included PW discharge data, fate information of PW plumes, fish distribution information, as well as uptake and elimination information of PW APs. Toxicodynamic data from effect studies with Atlantic cod (Gadus morhua) exposed to APs were used to establish a conservative environmental risk threshold value for AP concentration in seawater. By using the DREAM software to 1) identify the areas of highest potential risk and 2) integrate fish movement and uptake/elimination rates of APs for the chosen areas we found that the environmental exposure of fish to APs from PW is most likely too low to affect reproduction in wild populations of fish in the North Sea. The implications related to risk management of offshore PW and uncertainties in the risk assessment performed are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

Fate and occurrence of alkylphenolic compounds in sewage sludges determined by liquid chromatography tandem mass spectrometry.

PubMed

Koh, Y K K; Chiu, T Y; Paterakis, N; Boobis, A; Scrimshawe, M D; Lester, J N; Cartmell, E

2009-12-01

An analytical method has been developed and applied to determine the concentrations of the nonionic alkylphenol polyethoxylate surfactants and their metabolites, alkylphenoxy carboxylates and alkyphenols, in sewage sludges. The compounds were extracted with methanol/acetone (1:1 v/v) from sludge, and concentrated extracts were cleaned by silica solid-phase extraction prior to determination by liquid chromatography tandem mass spectrometry. The recoveries, determined by spiking sewage sludge at two concentrations, ranged from 51% to 89% with method detection limits from 6 microg kg(-1) to 60 microg kg(-1). The methodology was subsequently applied to sludge samples obtained from a carbonaceous activated sludge plant, a nitrifying/denitrifying activated sludge plant and a nitrifying/ denitrifying activated sludge plant with phosphorus removal. Concentrations of nonylphenolic compounds were two to three times higher than their octyl analogues. Long-chain nonylphenol polyethoxylates (NP3-12EO) ranged from 16 microg kg(-1) to 11754 microg kg(-1). The estrogenic metabolite nonylphenol was present at concentrations ranging from 33 microg kg(-1) to 6696 microg kg(-1).

Mechanism-based inactivation of dopamine beta-hydroxylase by p-cresol and related alkylphenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goodhart, P.J.; DeWolf, W.E. Jr.; Kruse, L.I.

1987-05-05

The mechanism-based inhibition of dopamine beta-hydroxylase by p-cresol (4-methylphenol) and other simple structural analogues of dopamine, which lack a basic side-chain nitrogen, is reported. p-Cresol binds DBH by a mechanism that is kinetically indistinguishable from normal dopamine substrate binding. Under conditions (pH 6.6) of random oxygen and phenethylamine substrate addition p-cresol adds randomly, whereas at pH 4.5 or in the presence of fumarate activator addition of p-cresol precedes oxygen binding as is observed with phenethylamine substrate. p-Cresol is shown to be a rapid (kinact = 2.0 min-1, pH 5.0) mechanism-based inactivator of DBH. This inactivation exhibits pseudo-first-order kinetics, is irreversible,more » is prevented by tyramine substrate or competitive inhibitor, and is dependent upon oxygen and ascorbic acid cosubstrates. Inhibition occurs with partial covalent incorporation of p-cresol into DBH. A plot of -log kinact vs. pH shows maximal inactivation occurs at pH 5.0 with dependence upon enzymatic groups with apparent pK values of 4.51 +/- 0.06 and 5.12 +/- 0.06. p-Cresol and related alkylphenols, unlike other mechanism-based inhibitors of DBH, lack a latent electrophile. These inhibitors are postulated to covalently modify DBH by a direct insertion of an aberrant substrate-derived benzylic radical into an active site residue.« less

Phase Separation Kinetics in Isopycnic Mixtures of H2O/CO2/Ethoxylated Alcohol Surfactants

NASA Technical Reports Server (NTRS)

Lesemann, Markus; Paulaitis, Michael E.; Kaler, Eric W.

1999-01-01

Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(sub i)E(sub j)) surfactants form three coexisting liquid phases at conditions where two of the phases have equal densities (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing C8E5, C10E6, and C12E6 surfactants, but not for those mixtures containing either C4E1 or C8E3 surfactants. Pressure-temperature (PT) projections for this three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. Measurements of the microstructure in H2O/CO2/C12E6 mixtures as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%) have also been carried out to show that while micellar structure remains essentially un-changed, critical concentration fluctuations increase as the phase boundary and plait point are approached. In this report, we present our first measurements of the kinetics of isopycnic phase separation for ternary mixtures of H2O/CO2/C8E5.

Alkylphenols, Other Endocrine-Active Chemicals, and Fish Responses in Three Streams in Minnesota - Study Design and Data, February-September 2007

USGS Publications Warehouse

Lee, Kathy E.; Schoenfuss, Heiko L.; Jahns, Nathan D.; Brown, Greg K.; Barber, Larry B.

2008-01-01

This report presents the study design and environmental data for an integrated chemical and biological study of three streams (South Fork Crow River, Redwood River, and Grindstone River) that receive wastewater in Minnesota. The objective of the study was to identify distribution patterns of endocrine-active chemicals and other organic chemicals indicative of wastewater, and to identify fish responses in the same streams. Endocrine-active chemicals are a class of chemicals that interfere with the natural regulation of endocrine systems, and an understanding of their distribution in aquatic systems is important so that aquatic organism exposure can be evaluated. This study was a cooperative effort of the U.S. Geological Survey (USGS), the Minnesota Pollution Control Agency, and St. Cloud State University (St. Cloud, Minn.). The USGS collected and analyzed water and quality-assurance samples and measured streamflow during six sampling events in each of three streams. Water samples were collected upstream from and at two successive points downstream from wastewater-treatment plant (WWTP) effluent discharge and from treated effluent from February through September 2007. Bed-sediment samples were collected during one sampling period at each of the stream locations. Water and bed-sediment samples were analyzed for endocrine-active chemicals including alkylphenols, alkylphenol polyethoxylates, and nonylphenol ethoxycarboxlylates (NPECs). Water samples also were analyzed for major ions, nutrients, and organic carbon. In addition, as part of an intensive time-series investigation, the USGS staff collected daily water samples for 8 weeks from the Redwood River near Marshall, Minn., for analyses of total alkylphenols and atrazine. St. Cloud State University staff collected and analyzed fish to determine male fish responses at all water sampling sites and at an additional site near the discharge of wastewater-treatment plant effluent to these streams. Male fish responses

Reconstruction of the pollution history of alkylphenols (4-tert-octylphenol, 4-nonylphenol) in the Baltic Sea.

PubMed

Graca, Bożena; Staniszewska, Marta; Zakrzewska, Danuta; Zalewska, Tamara

2016-06-01

This paper reports the reconstruction of the pollution history of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in the Baltic Sea. Alkylphenols are endocrine-disrupting compound and therefore toxic to aquatic organisms. Sediment cores were collected from regions with relatively stable sedimentation conditions. The cores were dated by the (210)Pb method. The OP and NP were determined using HPLC-FL. The highest inventory of these compounds was observed in the Gotland Deep (610 μg m(2) of NP and 47 μg m(2) of OP) and the lowest-on the slope of the Gdansk Deep (24 μg m(2) of NP and 16 μg m(2) of OP). Such spatial distribution was probably, among other factors, the result of the uplift of the sea floor. The pollution trends of OP and NP in sediments coincided with the following: (1) the beginnings of eutrophication (1960s/1970s of the twentieth century) and (2) strong increase in the areal extent and volume of hypoxia and anoxia in the Baltic (present century).

Solid phase extraction with high polarity Carb/PSA as composite fillers prior to UPLC-MS/MS to determine six bisphenols and alkylphenols in trace level hotpot seasoning.

PubMed

Dong, Hao; Zeng, Xiaofang; Bai, Weidong

2018-08-30

The present study reports an ultra high-performance liquid chromatography tandem mass spectrometry method for the simultaneous determination of six bisphenols (bisphenol A, bisphenol B and bisphenol F) and alkylphenols (4-nonylphenol, 4-n-nonylphenol and octylphenol) in hotpot seasoning. Samples were dispersed in n-hexane after addition of internal standards bisphenol A-d 4 and 4-n-nonylphenol-d 4 . Sample solutions were then centrifuged, and the supernatants purified using solid phase extraction with high polarity Carb/PSA composite fillers. Six target analytes were separated on a Waters ACQUITY BEH C18 column by gradient elution with methanol and 0.05% ammonium hydroxide in water as the mobile phase, and determined under multiple reactions monitoring mode. The limits of detection and quantitation, matrix effect, recovery and precision of the method were investigated. Results were linear in the concentration range 0.1-250 µg/L for all compounds of interest, with R 2  > 0.9950. Limits of detection were in the range 0.1-0.4 μg/kg, and limits of quantitation were between 0.5 μg/kg and 1.0 μg/kg. The mean recoveries for negative samples at three spiked concentrations were in the range 87.9%-102.4%, and the intra-day precision and inter-day precision were in the ranges 2.1-8.2% and 4.8-11.2%, respectively. This method is accurate and sensitive, and had good clean-up characteristics, which might apply to screening and quantitation of target bisphenols and alkylphenols in hotpot seasoning. Copyright © 2018 Elsevier Ltd. All rights reserved.

CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes.

PubMed

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E; Yadav, Jagjit S

2013-04-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills).

CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes

PubMed Central

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.

2013-01-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

A laboratory study of the biodegradation of an alcohol ethoxylate surfactant by native soil microbes

NASA Astrophysics Data System (ADS)

Ang, Carolina C.; Abdul, Abdul S.

1992-09-01

Laboratory experiments were conducted to study the biodegradation of a nonionic alcohol ethoxylate surfactant by native microbes from a contaminated site. Three sets of experiments consisting of 13 microcosms were carried out to evaluate the rate of biodegradation and the effect of nutrients and supplementary oxygen on the degradation process. The results from these active microcosms were compared with those for controlled microcosms in which a biocide was added to inhibit biological activities. In the presence of ground water and sterilized soil, surfactant solutions with initial concentrations of 1000, 650, 250, and 180 mgl -1 were reduced to less than 5 mgl -1 in 36 days, 20 days, 17 days, and 17 days, respectively. The biodegradation rate in microcosms with added nutrients was more than twice the rate in the reactor without nutrients. The results from experiments in which various nitrogen and phosphorus nutrients were added showed that a ratio of 10 carbon:2 nitrogen:1 phosphorus was the optimum for the biodegradation of surfactant under the microcosm conditions. The addition of 5 mgl -1 of oxygen in the form of hydrogen peroxide increased the degradation rate of surfactant by 30%. The study showed that microbes indigenous to the soil and ground water at a contaminated site rapidly degrade the low levels of the surfactant that may remain at the site after soil washing, and that the degradation rate can be increased by the addition of nutrients and oxygen.

The First Normal Stress Difference in Waterborne Paints Thickened by Hydrophobically Ethoxylated Urethane (HEUR) Rheology Modifier: A Simplified Phase Diagram

NASA Astrophysics Data System (ADS)

Chatterjee, Tirtha; van Dyk, Antony; Ginzburg, Valeriy; Nakatani, Alan

Since their invention in the 1970s, hydrophobically ethoxylated urethane (HEUR) associative thickeners are widely used to modify the rheology of waterborne paints. While their flow curves (viscosity vs. shear rate) and microstructure have been studied extensively in recent years, there is surprisingly little information on the paint normal stress under application conditions. However, understanding of normal stress behavior is critical for many applications such as brush drag and spatter. In this work we will demonstrate that in HEUR-based paints the first normal stress difference (N1) is controlled by two factors: (a) adsorption of HEUR molecules on latex particles and (b) ability of non-adsorbed HEUR to form transient bridges between particles with HEUR shells. By controlling these two effects, one can design a paint formulation with targeted N1 behavior (positive or negative N1 under high shear). Finally, a simplified phase diagram will be presented connecting formulation composition-microstructure- and N1 behavior. The results would serve as guidelines to formulate paints to meet the specific customer needs.

Simultaneous determination of phthalates, their metabolites, alkylphenols and bisphenol A using GC-MS in urine of men with fertility problems.

PubMed

Kranvogl, Roman; Knez, Jure; Miuc, Alen; Vončina, Ernest; Vončina, Darinka Brodnjak; Vlaisavljević, Veljko

2014-01-01

A GC-MS method was successfully applied to measure simultaneously the concentrations of endocrine disrupting compounds (5 dialkyl phthalates, 9 phthalate monoesters, 3 alkylphenols and bisphenol A) in 136 male urine samples. In the present study the method was validated and concentrations of EDCs were determined. The results were compared with results from other studies. Correlations between endocrine disrupting compounds and also correlations of endocrine disrupting compounds with two semen quality parameters are presented and evaluated. Significant positive correlations were found between almost all the endocrine disrupting compounds. The parameter sum of DEHP (SUM DEHP) was positively correlated to all the endocrine disrupting compounds but negatively to two semen quality parameters. Negative correlations between the endocrine disrupting compounds and the semen quality parameters could indicate that endocrine disrupting compounds could cause reproductive problems by decreasing the semen count and quality. This research will have helped to evaluate human exposure to endocrine disrupting compounds.

Polar herbicides, pharmaceutical products, perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and nonylphenol and its carboxylates and ethoxylates in surface and tap waters around Lake Maggiore in Northern Italy.

PubMed

Loos, Robert; Wollgast, Jan; Huber, Tania; Hanke, Georg

2007-02-01

A survey of contamination of surface and drinking waters around Lake Maggiore in Northern Italy with polar anthropogenic environmental pollutants has been conducted. The target analytes were polar herbicides, pharmaceuticals (including antibiotics), steroid estrogens, perfluorooctanesulfonate (PFOS), perfluoroalkyl carboxylates (including perfluorooctanoate PFOA), nonylphenol and its carboxylates and ethoxylates (NPEO surfactants), and triclosan, a bactericide used in personal-care products. Analysis of water samples was performed by solid-phase extraction (SPE) then liquid chromatography-triple-quadrupole (tandem) mass spectrometry (LC-MS-MS). By extraction of 1-L water samples and concentration of the extract to 100 microL, method detection limits (MDLs) as low as 0.05-0.1 ng L(-1) were achieved for most compounds. Lake-water samples from seven different locations in the Southern part of Lake Maggiore and eleven samples from different tributary rivers and creeks were investigated. Rain water was also analyzed to investigate atmospheric input of the contaminants. Compounds regularly detected at very low concentrations in the lake water included: caffeine (max. concentration 124 ng L(-1)), the herbicides terbutylazine (7 ng L(-1)), atrazine (5 ng L(-1)), simazine (16 ng L(-1)), diuron (11 ng L(-1)), and atrazine-desethyl (11 ng L(-1)), the pharmaceuticals carbamazepine (9 ng L(-1)), sulfamethoxazole (10 ng L(-1)), gemfibrozil (1.7 ng L(-1)), and benzafibrate (1.2 ng L(-1)), the surfactant metabolite nonylphenol (15 ng L(-1)), its carboxylates (NPE(1)C 120 ng L(-1), NPE(2)C 7 ng L(-1), NPE(3)C 15 ng L(-1)) and ethoxylates (NPE( n )Os, n = 3-17; 300 ng L(-1)), perfluorinated surfactants (PFOS 9 ng L(-1), PFOA 3 ng L(-1)), and estrone (0.4 ng L(-1)). Levels of these compounds in drinking water produced from Lake Maggiore were almost identical with those found in the lake itself, revealing the poor performance of sand filtration and chlorination applied by the local

Alkylphenols, polycyclic aromatic hydrocarbons, and organochlorines in sediment from Lake Shihwa, Korea: Instrumental and bioanalytical characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khim, J.S.; Villeneuve, D.L.; Kannan, K.

1999-11-01

Lake Shihwa is an artificial lake, located on the west coast of Korea, that has experienced environmental deterioration since 1994, when it was formed by construction of a sea dike. This study used instrumental analysis and in vitro bioassays to characterize organic contaminants in sediment collected from 11 stations on Lake Shihwa. Alkylphenol (AP) concentrations in Lake Shihwa sediment ranged from 20.2 to 1,820 ng/g nonylphenol and from 4.69 to 50.5 ng/g octylphenol, on a dry weight basis. Maximum concentrations of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides, and polychlorinated biphenyls (PCBs) were 30.8, 2.26, and 12.3 ng/g (dry weight), respectively.more » Significant estrogenic activity was associated with fractions containing APs. Mass-balance analysis suggested that reported concentrations of APs account for less than 20% of the estrogenic activity observed. No significant dioxin like activity was associated with fractions containing classic aryl hydrocarbon receptor agonists, such as PCBs, but the mid-polarity fractions containing PAHs and most polar fractions yielded significant dioxin like activity. Overall, most of the in vitro bioassay responses appear to have been caused by unidentified and/or undetectable compounds associated with Lake Shihwa sediment.« less

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants.

PubMed

Zhang, Cuifeng; Xu, Tingting; Bao, Zhongbin; Chen, Lijun

2017-01-01

The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer.

Determination of alkylphenol and alkylphenolethoxylates in biota by liquid chromatography with detection by tandem mass spectrometry and fluorescence spectroscopy

USGS Publications Warehouse

Schmitz-Afonso, I.; Loyo-Rosales, J.E.; de la Paz Aviles, M.; Rattner, B.A.; Rice, C.P.

2003-01-01

A quantitative method for the simultaneous determination of octylphenol, nonylphenol and the corresponding ethoxylates (1 to 5) in biota is presented. Extraction methods were developed for egg and fish matrices based on accelerated solvent extraction followed by a solid-phase extraction cleanup, using octadecylsilica or aminopropyl cartridges. Identification and quantitation were accomplished by liquid chromatography-electrospray tandem mass spectrometry (LC-MS-MS) and compared to the traditional liquid chromatography with fluorescence spectroscopy detection. LC-MS-MS provides high sensitivity and specificity required for these complex matrices and an accurate quantitation with the use of 13C-labeled internal standards. Quantitation limits by LC-MS-MS ranged from 4 to 12 ng/g in eggs, and from 6 to 22 ng/g in fish samples. These methods were successfully applied to osprey eggs from the Chesapeake Bay and fish from the Great Lakes area. Total levels found in osprey egg samples were up to 18 ng/g wet mass and as high as 8.2 ug/g wet mass in the fish samples.

Alkylphenols in surface sediments of the Yellow Sea and East China Sea inner shelf: occurrence, distribution and fate.

PubMed

Duan, Xiao-yong; Li, Yan-xia; Li, Xian-guo; Zhang, Da-hai; Gao, Yi

2014-07-01

Alkylphenols (APs) have been found as ubiquitous environmental pollutants with reproductive and developmental toxicity. In this study, APs in surface sediments of the Yellow Sea (YS) and East China Sea (ECS) inner shelf were analyzed to assess influences of riverine and atmospheric inputs of pollutants on the marine environment. NP concentrations ranged from 349.5 to 1642.8 ng/g (average 890.1 ng/g) in the YS sediments and from 31.3 to 1423.7 ng/g (average 750.1 ng/g) in the ECS inner shelf sediments. NP distribution pattern was mainly controlled by the sedimentary environment. OP concentration was 0.8-9.3 ng/g (average 4.7 ng/g) in the YS sediments and 0.7-11.1 ng/g (average 5.1 ng/g) in the ECS sediments. Assessment of the influence of distances from land on OP concentrations provided evidence for the predominance of coastal riverine and/or atmospheric inputs rather than long-range transport. And the biological pump may play an important role for sequestration of OP in the nearshore area. Copyright © 2013 Elsevier Ltd. All rights reserved.

Low Work Function 2.81 eV Rb2CO3-Doped Polyethylenimine Ethoxylated for Inverted Organic Light-Emitting Diodes.

PubMed

Kim, Jeonggi; Kim, Hyo-Min; Jang, Jin

2018-06-06

We report a low work function (2.81 eV), Rb 2 CO 3 -doped polyethyleneimine ethoxylated (PEIE) which is used for highly efficient and long-lifetime, inverted organic light-emitting diodes (OLEDs). Doping Rb 2 CO 3 into PEIE decreases the work function of Li-doped ZnO (LZO) by 1.0 eV and thus significantly improves electron injection ability into the emission layer (EML). The inverted OLED with PEIE:Rb 2 CO 3 interfacial layer (IL) exhibits higher efficiency and longer operation lifetime than those of the device with a PEIE IL. It is found also that Mg-doped ZnO (MZO) can be used instead of LZO as electron transporting layer. Rb 2 CO 3 shows a low work function of 2.81 eV. The OLED with MZO/PEIE:Rb 2 CO 3 exhibits low operating voltage of 5.0 V at 1000 cd m -2 and low efficiency roll-off of 11.8% at high luminance of 10 000 cd m -2 . The results are due to the suppressed exciton quenching at the MZO/organic EML interface.

Analytical methods for the quantification of bisphenol A, alkylphenols, phthalate esters, and perfluoronated chemicals in biological samples.

PubMed

Nakazawa, Hiroyuki; Iwasaki, Yusuke; Ito, Rie

2014-01-01

Our modern society has created a large number of chemicals that are used for the production of everyday commodities including toys, food packaging, cosmetic products, and building materials. We enjoy a comfortable and convenient lifestyle with access to these items. In addition, in specialized areas, such as experimental science and various medical fields, laboratory equipment and devices that are manufactured using a wide range of chemical substances are also extensively employed. The association between human exposure to trace hazardous chemicals and an increased incidence of endocrine disease has been recognized. However, the evaluation of human exposure to such endocrine disrupting chemicals is therefore imperative, and the determination of exposure levels requires the analysis of human biological materials, such as blood and urine. To obtain as much information as possible from limited sample sizes, highly sensitive and reliable analytical methods are also required for exposure assessments. The present review focuses on effective analytical methods for the quantification of bisphenol A (BPA), alkylphenols (APs), phthalate esters (PEs), and perfluoronated chemicals (PFCs), which are chemicals used in the production of everyday commodities. Using data obtained from liquid chromatography/mass spectrometry (LC/MS) and LC/MS/MS analyses, assessments of the risks to humans were also presented based on the estimated levels of exposure to PFCs.

The effect of the UV photon flux on the photoelectrocatalytic degradation of endocrine-disrupting alkylphenolic chemicals.

PubMed

da Silva, Salatiel Wohlmuth; Viegas, Cheila; Ferreira, Jane Zoppas; Rodrigues, Marco Antônio Siqueira; Bernardes, Andréa Moura

2016-10-01

The photoelectrocatalytic (PEC) degradation of 4-nonylphenol ethoxylate (NP4EO) using a low, moderate, or high UV photon flux in different treatment times was investigated. The byproducts were verified using gas chromatography with flame ionization detection (GC-FID) and gas chromatography with quadrupole mass analyzer (GC-qMS). The GC results showed that the use of a low (2.89 μmol m(-2)s(-1)) or a high (36.16 μmol m(-2)s(-1)) UV photon flux reaching the anode surface was associated to the production of alcohols and the toxic byproduct nonylphenol (NP), leading to the same degradation pathway. Meanwhile, the use of a moderate UV photon flux (14.19 μmol m(-2)s(-1)) reaching the anode surface did not produce alcohols or the NP toxic byproduct. This study demonstrates that different UV photon fluxes will have an influence in the degradation of NP4EO with or without generation of toxic byproducts. Furthermore, it is concluded that, after the determination of the UV photon flux able to degrade NP4EO without NP formation, the treatment time is essential in removal of NP4EO, since increasing the treatment time of 4 to 10 h, when using the PEC best conditions (moderate UV photon flux), implies in a higher treatment efficiency.

Alkyl polyglucoside vs. ethoxylated surfactant-based microemulsions as vehicles for two poorly water-soluble drugs: physicochemical characterization and in vivo skin performance.

PubMed

Pajić, Nataša Z Bubić; Todosijević, Marija N; Vuleta, Gordana M; Cekić, Nebojša D; Dobričić, Vladimir D; Vučen, Sonja R; Čalija, Bojan R; Lukić, Milica Ž; Ilić, Tanja M; Savić, Snežana D

2017-12-20

Two types of biocompatible surfactants were evaluated for their capability to formulate skin-friendly/non-irritant microemulsions as vehicles for two poorly water-soluble model drugs differing in properties and concentrations: alkyl polyglucosides (decyl glucoside and caprylyl/capryl glucoside) and ethoxylated surfactants (glycereth-7-caprylate/ caprate and polysorbate 80). Phase behavior, structural inversion and microemulsion solubilization potential for sertaconazole nitrate and adapalene were found to be highly dependent on the surfactants structure and HLB value. Performed characterization (polarized light microscopy, pH, electrical conductivity, rheological, FTIR and DSC measurements) indicated a formulation containing glycereth- 7-caprylate/caprate as suitable for incorporation of both drugs, whereas alkyl polyglucoside-based systems did not exhibit satisfying solubilization capacity for sertaconazole nitrate. Further, monitored parameters were strongly affected by sertaconazole nitrate incorporation, while they remained almost unchanged in adapalene-loaded vehicles. In addition, results of the in vivo skin performance study supported acceptable tolerability for all investigated formulations, suggesting selected microemulsions as promising carriers worth exploring further for effective skin delivery of model drugs.

Potential endocrine disrupting organic chemicals in treated municipal wastewater and river water

USGS Publications Warehouse

Barber, L.B.; Brown, G.K.; Zaugg, S.D.

2000-01-01

Select endocrine disrupting organic chemicals were measured in treated wastewater from Chicago, IL, Minneapolis/St. Paul, MN, Detroit, MI, and Milwaukee, WI, and in the Des Plaines, Illinois, and Minnesota Rivers during the fall of 1997 and the spring of 1998. Emphasis was given to alkylphenolpolyethoxylate (APEO) derived compounds, although 17-??-estradiol, bisphenol A, caffeine, total organic carbon, ethylenediaminetetraacetic acid (EDTA), and other compounds also were measured. Contaminants were isolated by continuous liquid-liquid extraction (CLLE) with methylene chloride and analyzed by gas chromatography/mass spectrometry in full scan and selected ion monitoring modes. The extracts were derivatized to form the methyl esters of alkylphenolethoxycarboxylates (APEC), and EDTA was isolated by evaporation and derivatized to form the tetrapropyl ester. The mass spectra of nonylphenol (NP) and octylphenol (OP) compounds are complex and show variations among the different ethoxylate and carboxylate homologs, reflecting variations in the ethylene oxide chain length. Recoveries for target compounds and surrogate standards ranged from 20-130%, with relative standard deviations of 9.9-53%. Detection limits for the various compounds ranged from 0.06-0.35 ??g/L. Analysis of the wastewater effluents detected a number of compounds including NP, NPEO, OP, OPEO, NPEC, caffeine, and EDTA at concentrations ranging from <1-439 ??g/L, with EDTA and NPEC being most abundant. There was variability in compound distributions and concentrations between the various sewage treatment plants, indicating differences in treatment type and influent composition. Several wastewater-derived compounds were detected in the river samples, with EDTA and NPEC persisting for considerable distance downstream from wastewater discharges, and NP and NPEO being attenuated more rapidly.

Ethoxylated adjuvants of glyphosate-based herbicides are active principles of human cell toxicity.

PubMed

Mesnage, R; Bernay, B; Séralini, G-E

2013-11-16

Pesticides are always used in formulations as mixtures of an active principle with adjuvants. Glyphosate, the active ingredient of the major pesticide in the world, is an herbicide supposed to be specific on plant metabolism. Its adjuvants are generally considered as inert diluents. Since side effects for all these compounds have been claimed, we studied potential active principles for toxicity on human cells for 9 glyphosate-based formulations. For this we detailed their compositions and toxicities, and as controls we used a major adjuvant (the polyethoxylated tallowamine POE-15), glyphosate alone, and a total formulation without glyphosate. This was performed after 24h exposures on hepatic (HepG2), embryonic (HEK293) and placental (JEG3) cell lines. We measured mitochondrial activities, membrane degradations, and caspases 3/7 activities. The compositions in adjuvants were analyzed by mass spectrometry. Here we demonstrate that all formulations are more toxic than glyphosate, and we separated experimentally three groups of formulations differentially toxic according to their concentrations in ethoxylated adjuvants. Among them, POE-15 clearly appears to be the most toxic principle against human cells, even if others are not excluded. It begins to be active with negative dose-dependent effects on cellular respiration and membrane integrity between 1 and 3ppm, at environmental/occupational doses. We demonstrate in addition that POE-15 induces necrosis when its first micellization process occurs, by contrast to glyphosate which is known to promote endocrine disrupting effects after entering cells. Altogether, these results challenge the establishment of guidance values such as the acceptable daily intake of glyphosate, when these are mostly based on a long term in vivo test of glyphosate alone. Since pesticides are always used with adjuvants that could change their toxicity, the necessity to assess their whole formulations as mixtures becomes obvious. This challenges

Methods for degrading lignocellulosic materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlasenko, Elena; Cherry, Joel; Xu, Feng

2008-04-08

The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolyticmore » enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermentating microoganisms; and (c) recovering the organic substance from the fermentation.« less

Methods for degrading lignocellulosic materials

DOEpatents

Vlasenko, Elena [Davis, CA; Cherry, Joel [Davis, CA; Xu, Feng [Davis, CA

2008-04-08

The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermentating microoganisms; and (c) recovering the organic substance from the fermentation.

Methods for degrading lignocellulosic materials

DOEpatents

Vlasenko, Elena [Davis, CA; Cherry, Joel [Davis, CA; Xu, Feng [Davis, CA

2011-05-17

The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermenting microorganisms; and (c) recovering the organic substance from the fermentation.

Removal of alkylphenols and polybromodiphenylethers by a biofiltration treatment plant during dry and wet-weather periods.

PubMed

Gilbert, S; Gasperi, J; Rocher, V; Lorgeoux, C; Chebbo, G

2012-01-01

This paper investigates the occurrence of alkylphenols (APs) and polybromodiphenylethers (PBDEs) in raw wastewater during dry and wet-weather periods, and their removal by physico-chemical lamellar settling and biofiltration techniques. Due to in-sewer deposit erosion and, to a lesser extent, to external inputs, raw effluents exhibit from 1.5 to 5 times higher AP and PBDE concentrations during wet periods compared with dry ones. The lamellar settler obtains high removal of APs and PBDEs under both dry and wet-weather flows (>53% for Σ(6)AP and >89% for Σ(4)PBDE), confirming the insensitivity of this technique to varying influent conditions. Indeed, despite the higher pollutant concentrations observed in raw effluents under wet-weather flows, adjusting the addition of coagulant-flocculent allows for efficient removal. By combining physical and biological processes, the biofiltration unit treats nutrient pollution, as well as Σ(6)AP and Σ(4)PBDE contamination (58 ± 5% and 75 ± 6% respectively). Although the operating conditions of the biofiltration unit are modified during wet periods, the performance in nutrient pollution, APs and light PBDE congeners remains high. Nevertheless, lower efficiency has been noted in nitrogen pollution, i.e. no denitrification occurs, and BDE-209 (not removed during wet-weather periods). In conclusion, this study demonstrates that the combination of both techniques treats AP and PBDE pollution efficiently during dry periods, but that they are also suitable for stormwater treatment.

Bisphenol A and Related Alkylphenols Exert Nongenomic Estrogenic Actions Through a G Protein-Coupled Estrogen Receptor 1 (Gper)/Epidermal Growth Factor Receptor (Egfr) Pathway to Inhibit Meiotic Maturation of Zebrafish Oocytes.

PubMed

Fitzgerald, Amanda C; Peyton, Candace; Dong, Jing; Thomas, Peter

2015-12-01

Xenobiotic estrogens, such as bisphenol A (BPA), disrupt a wide variety of genomic estrogen actions, but their nongenomic estrogen actions remain poorly understood. We investigated nongenomic estrogenic effects of low concentrations of BPA and three related alkylphenols on the inhibition of zebrafish oocye maturation (OM) mediated through a G protein-coupled estrogen receptor 1 (Gper)-dependent epidermal growth factor receptor (Egfr) pathway. BPA (10-100 nM) treatment for 3 h mimicked the effects of estradiol-17beta (E2) and EGF, decreasing spontaneous maturation of defolliculated zebrafish oocytes, an effect not blocked by coincubation with actinomycin D, but blocked by coincubation with a Gper antibody. BPA displayed relatively high binding affinity (15.8% that of E2) for recombinant zebrafish Gper. The inhibitory effects of BPA were attenuated by inhibition of upstream regulators of Egfr, intracellular tyrosine kinase (Src) with PP2, and matrix metalloproteinase with ilomastat. Treatment with an inhibitor of Egfr transactivation, AG1478, and an inhibitor of the mitogen-activated protein kinase (MAPK) 3/1 pathway, U0126, increased spontaneous OM and blocked the inhibitory effects of BPA, E2, and the selective GPER agonist, G-1. Western blot analysis showed that BPA (10-200 nM) mimicked the stimulatory effects of E2 and EGF on Mapk3/1 phosphorylation. Tetrabromobisphenol A, 4-nonylphenol, and tetrachlorobisphenol A (5-100 nM) also inhibited OM, an effect blocked by cotreatment with AG1478, as well as with the GPER antagonist, G-15, and displayed similar binding affinities as BPA to zebrafish Gper. The results suggest that BPA and related alkylphenols disrupt zebrafish OM by a novel nongenomic estrogenic mechanism involving activation of the Gper/Egfr/Mapk3/1 pathway. © 2015 by the Society for the Study of Reproduction, Inc.

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants

PubMed Central

Zhang, Cuifeng; Xu, Tingting; Bao, Zhongbin; Chen, Lijun

2017-01-01

Abstract The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer. PMID:29491785

Blank and sample handling troubleshooting in ultratrace analysis of alkylphenols and bisphenol A by liquid chromatography tandem mass spectrometry.

PubMed

Salgueiro-González, N; Concha-Graña, E; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2012-11-15

Blank contamination is a notorious problem in the ultratrace analysis of alkylphenols and bisphenol A. The achievement of low detection limits is complicated due to the high background signals. Furthermore, overestimations and underestimations in the analytical results can occur when blank levels are not stable. Thus, a review of sources of blank contamination in this type of analysis was carried out. Several sources of contamination were identified and useful guidelines are proposed for the determination of these compounds in water samples by liquid chromatography coupled with mass spectrometry. The system contamination was maintained below 0.09 ng (reagent blank) for all compounds and below 0.003 μg L(-1) (procedure blank). The main improvement was obtained by using LC-MS grade solvent in the mobile phase and PTFE syringe filters for the filtration of the sample extracts. Sample handling aspects such as filtration and storage of the water samples were also considered. The filtration of the samples should be avoided because both contamination and adsorption problems were observed when different kinds of filters were assayed. The refrigerated storage of water samples should be limited to 5 days (without addition of methanol) or 8 days (with 5% methanol). Copyright © 2012 Elsevier B.V. All rights reserved.

Bisphenol A and Related Alkylphenols Exert Nongenomic Estrogenic Actions Through a G Protein-Coupled Estrogen Receptor 1 (Gper)/Epidermal Growth Factor Receptor (Egfr) Pathway to Inhibit Meiotic Maturation of Zebrafish Oocytes1

PubMed Central

Fitzgerald, Amanda C.; Peyton, Candace; Dong, Jing; Thomas, Peter

2015-01-01

Xenobiotic estrogens, such as bisphenol A (BPA), disrupt a wide variety of genomic estrogen actions, but their nongenomic estrogen actions remain poorly understood. We investigated nongenomic estrogenic effects of low concentrations of BPA and three related alkylphenols on the inhibition of zebrafish oocye maturation (OM) mediated through a G protein-coupled estrogen receptor 1 (Gper)-dependent epidermal growth factor receptor (Egfr) pathway. BPA (10–100 nM) treatment for 3 h mimicked the effects of estradiol-17beta (E2) and EGF, decreasing spontaneous maturation of defolliculated zebrafish oocytes, an effect not blocked by coincubation with actinomycin D, but blocked by coincubation with a Gper antibody. BPA displayed relatively high binding affinity (15.8% that of E2) for recombinant zebrafish Gper. The inhibitory effects of BPA were attenuated by inhibition of upstream regulators of Egfr, intracellular tyrosine kinase (Src) with PP2, and matrix metalloproteinase with ilomastat. Treatment with an inhibitor of Egfr transactivation, AG1478, and an inhibitor of the mitogen-activated protein kinase (MAPK) 3/1 pathway, U0126, increased spontaneous OM and blocked the inhibitory effects of BPA, E2, and the selective GPER agonist, G-1. Western blot analysis showed that BPA (10–200 nM) mimicked the stimulatory effects of E2 and EGF on Mapk3/1 phosphorylation. Tetrabromobisphenol A, 4-nonylphenol, and tetrachlorobisphenol A (5–100 nM) also inhibited OM, an effect blocked by cotreatment with AG1478, as well as with the GPER antagonist, G-15, and displayed similar binding affinities as BPA to zebrafish Gper. The results suggest that BPA and related alkylphenols disrupt zebrafish OM by a novel nongenomic estrogenic mechanism involving activation of the Gper/Egfr/Mapk3/1 pathway. PMID:26490843

Effects of waterborne exposure to 4-nonylphenol and nonylphenol ethoxylate on secondary sex characteristics and gonads of fathead minnows (Pimephales promelas)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miles-Richardson, S.R.; Pierens, S.L.; Nichols, K.M.

1999-02-01

Fathead minnows were exposed to 4-nonylphenol (NP) or nonylphenol ethoxylate (NPEO) to determine the effects of these weak estrogen agonists on secondary sex characteristics and gonads of sexually mature males and females during 42-day continuous-flow exposures. Neither NP nor NPEO caused statistically significant effects on tubercles or fatpad size at the concentrations tested. Exposure to 1.1 or 3.4 {micro}g NP.L caused changes in the number and size of Sertoli cells and germ cell syncytia. Necrotic aggregates of various stages of germ cells in the spermatogenic sequence were observed in the testes of males exposed to NP. Electron microscopy of themore » testes of NP-exposed males revealed the presence of phagocytic cells in the lumina of seminiferous tubules. The cytoplasm of some Sertoli cells was distended with myelin figures and necrotic spermatozoa. No significant effects on the stages of follicular development were observed in females exposed to NP. There were no differences in the gonads or secondary sex characteristics of males or females exposed to 5.5 {micro}g NPEO/L, the greatest concentration studied. The histologic responses observed are sensitive indicators of waterborne exposure to NP at environmentally relevant concentrations, but not as sensitive as induction of plasma vitellogenin.« less

Effects of a homologous series of linear alcohol ethoxylate surfactants on fathead minnow early life stages.

PubMed

Lizotte, R E; Wong, D C; Dorn, P B; Rodgers, J H

1999-11-01

Effects of a homologous series of three primarily linear alcohol ethoxylate surfactants were studied in laboratory flow-through 28-day early-life-stage tests with fathead minnow (Pimephales promelas Rafinesque). Surfactants were a C(9-11), C(12-13), and C(14-15) with an average of 6, 6.5, and 7 ethylene oxide units per mole of alcohol, respectively. Average measured surfactant recoveries were 103%, 81%, and 79% of nominal concentrations for the C(9-11) EO 6, C(12-13) EO 6.5, and C(14-15) EO 7 studies, respectively. Embryo survival at 48 h was not adversely affected at any of the concentrations tested. Impaired hatching and deformed fry were observed only in the C(12-13) EO 6.5 study. The 28-day LC50 values were 4.87, 2.39, and 1.02 mg/L for the C(9-11) EO 6, C(12-13) EO 6.5, and C(14-15) EO 7 surfactants, respectively. The corresponding NOECs for survival were 1.01, 1.76, and 0.74 mg/L. Posthatch fry growth was more sensitive than survival for the C(12-13) EO 6.5 and C(14-15) EO 7 surfactants. Survival of posthatch fry decreased with increasing surfactant alkyl chain length. Twenty-eight-day laboratory data were compared to 96-h laboratory, 10-day laboratory and 30-day stream mesocosm data for fathead minnow previously determined for these surfactants. Survival endpoints from the different exposures were comparable and only varied within a factor of two. Similarity of results suggests that it is possible to effectively use 96-h, 10-day, or 28-day laboratory data to predict environmental effects concentrations of these surfactants for fish. http://link.springer-ny. com/link/service/journals/00244/bibs/37n4p536.html

Effects of alcohol ethoxylate and pluronic detergents on the development of pasture bloat in cattle and sheep.

PubMed

Stanford, K; Wang, Y; Berg, B P; Majak, W; McCartney, D H; Baron, V; McAllister, T A

2001-01-01

A series of studies was conducted to determine the efficacy and possible modes of action of a water-soluble mixture of alcohol ethoxylate and pluronic detergents (AEPD; Blocare 4511, ANCARE, Auckland, NZ) in preventing pasture bloat in ruminants grazing or fed freshly harvested alfalfa. Ten cannulated Suffolk wethers were offered freshly harvested alfalfa; five were given a daily intraruminal dose of 40 ml of 50% AEPD (vol/vol) 1 h before feeding, and five (controls) were dosed with water. Viscosity of ruminal fluid was reduced (P < 0.001) in AEPD-treated wethers, relative to the controls, for the first 2 h after feeding but not at 4 h after feeding and beyond. Treatment with AEPD did not affect dry matter (DM) intake, digestibility of DM, acid detergent fiber, or neutral detergent fiber, or N digestion and retention, implying that AEPD likely would not affect milk production. In a crossover grazing study, five of the wethers were given AEPD in drinking water (0.1%, vol/vol); treatment with AEPD was 100% effective for preventing bloat in sheep grazing early-bloom alfalfa for 4 h daily. Replicate grazing studies were conducted with cattle in Lethbridge, AB; Lacombe, AB; and Kamloops, BC. Treated animals received AEPD in the water (0.06%, vol/vol) and grazed vegetative alfalfa for 6 h daily. As it did with sheep, AEPD treatment effectively precluded the bloat observed in control animals. Consequently, AEPD may be a valuable tool for alfalfa pasture-based dairy production although further study is required to develop an integrated model for optimal administration under a variety of climatic conditions.

Simultaneous determination of bisphenols and alkylphenols in water by solid phase extraction and ultra performance liquid chromatography-tandem mass spectrometry.

PubMed

Shan, Xiao Mei; Shen, Deng Hui; Wang, Bing Shuang; Lu, Bei Bei; Huang, Fa Yuan

2014-06-01

To establish an analytical method for determination of four bisphenols (BPA, BPB, BPF, and BPS) and two alkylphenols (4-n-OP, 4-n-NP) in water by ultra performance liquid chromatography- tandem mass spectrometry (UPLC/MS/MS). The water samples were extracted and condensed with solid-phase extraction (SPE) using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0 μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%. Relative standard deviations (RSDs) were between 1.26% and 3.67%. Applying this method to detect the source water of Chaohu Lake and drinking water of Hefei, six target compounds were detected in different levels. This method is simple with high sensitivity and selectivity, could be suitable for the determination of these compounds in source and drinking water. Copyright © 2014 The Editorial Board of Biomedical and Environmental Sciences. Published by China CDC. All rights reserved.

Occurrence, distribution, and risk assessment of alkylphenols, bisphenol A, and tetrabromobisphenol A in surface water, suspended particulate matter, and sediment in Taihu Lake and its tributaries.

PubMed

Liu, Dan; Liu, Jining; Guo, Min; Xu, Huaizhou; Zhang, Shenghu; Shi, Lili; Yao, Cheng

2016-11-15

The occurrence and distribution of nine selected compounds were investigated in surface water, suspended particulate matter (SPM), and sediment in Taihu Lake and its tributaries. With the exception of 4-Butylphenol, all compounds were detected in at least two phases, and nonylphenol (NP) and 4-tert-Octylphenol (4-OP) were the predominant alkylphenols (APs) in the lake. A significant correlation was observed between NP and 4-OP, indicating that they may share the same source. Moreover, surface water phase was the dominant sink of Bisphenol A (BPA) in the aquatic environment. The concentrations of BPA between the surface water and SPM phases were closely related to each other. In addition, Tetrabromobisphenol A (TBBPA) exhibited relatively higher concentrations and detection frequencies in the SPM. Risk assessment revealed greater risk associated with the surface water than the sediment, indicating that the discharge of industrial wastewater and domestic sewage poses a serious threat to aquatic ecosystems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fate and metabolism of tetrabromobisphenol A in soil slurries without and with the amendment with the alkylphenol degrading bacterium Sphingomonas sp. strain TTNP3.

PubMed

Li, Fangjie; Wang, Jiajia; Nastold, Peter; Jiang, Bingqi; Sun, Feifei; Zenker, Armin; Kolvenbach, Boris Alexander; Ji, Rong; François-Xavier Corvini, Philippe

2014-10-01

Transformation of ring-(14)C-labelled tetrabromobisphenol-A (TBBPA) was studied in an oxic soil slurry with and without amendment with Sphingomonas sp. strain TTNP3, a bacterium degrading bisphenol-A. TBBPA degradation was accompanied by mineralization and formation of metabolites and bound-residues. The biotransformation was stimulated in the slurry bio-augmented with strain TTNP3, via a mechanism of metabolic compensation, although this strain did not grow on TBBPA. In the absence and presence of strain TTNP3, six and nine metabolites, respectively, were identified. The initial O-methylation metabolite (TBBPA-monomethyl ether) and hydroxytribromobisphenol-A were detected only when strain TTNP3 was present. Four primary metabolic pathways of TBBPA in the slurries are proposed: oxidative skeletal rearrangements, O-methylation, ipso-substitution, and reductive debromination. Our study provides for the first time the information about the complex metabolism of TBBPA in oxic soil and suggests that type II ipso-substitution could play a significant role in the fate of alkylphenol derivatives in the environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Poly-3-hydroxybutyrate (PHB) production from alkylphenols, mono and poly-aromatic hydrocarbons using Bacillus sp. CYR1: A new strategy for wealth from waste.

PubMed

Venkateswar Reddy, M; Mawatari, Yasuteru; Yajima, Yuka; Seki, Chigusa; Hoshino, Tamotsu; Chang, Young-Cheol

2015-09-01

In the present study five different types of alkylphenols, each of the two different types of mono and poly-aromatic hydrocarbons were selected for degradation, and conversion into poly-3-hydroxybutyrate (PHB) using the Bacillus sp. CYR1. Strain CYR1 showed growth with various toxic organic compounds. Degradation pattern of all the organic compounds at 100 mg/l concentration with or without addition of tween-80 were analyzed using high pressure liquid chromatography (HPLC). Strain CYR1 showed good removal of compounds in the presence of tween-80 within 3 days, but it took 6 days without addition of tween-80. Strain CYR1 showed highest PHB production with phenol (51 ± 5%), naphthalene (42 ± 4%), 4-chlorophenol (32 ± 3%) and 4-nonylphenol (29 ± 3%). The functional groups, structure, and thermal properties of the produced PHB were analyzed. These results denoted that the strain Bacillus sp. CYR1 can be used for conversion of different toxic compounds persistent in wastewaters into useable biological polyesters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Determination of nonylphenol and nonylphenol ethoxylates in environmental solid samples by ultrasonic-assisted extraction and high performance liquid chromatography-fluorescence detection.

PubMed

Núñez, L; Turiel, E; Tadeo, J L

2007-04-06

A simple and rapid analytical method for the determination of nonylphenol (NP) and nonylphenol ethoxylates (NPEOx) in solid environmental samples has been developed. This method combines an ultrasonic-assisted extraction procedure in small columns and an enrichment step onto C(18) solid-phase extraction cartridges prior to separation using HPLC with fluorescence detection. Method optimization was carried out using soil samples fortified at different concentration levels (from 0.1 to 100 microg/g). Under optimum conditions, 2g of soil was placed in small glass columns and extraction was performed assisted by sonication (SAESC) at 45 degrees C in two consecutive steps of 15 min using a mixture of H(2)O/MeOH (30/70). The obtained extracts were collected, loaded onto 500 mg C(18) cartridges, and analytes were eluted with 3 x 1 ml of methanol and 1 ml of acetonitrile. Finally, sample extracts were evaporated under a nitrogen stream, redissolved in 500 microl H(2)O/AcN (50/50), and passed though a 0.45 microm nylon filter before final determination by HPLC-FL. The developed procedure allowed to achieve quantitative recoveries for NP and NPEOx, and was properly validated. Finally, the method was applied to the determination of these compounds in soils and other environmental solid samples such as sediments, compost and sludge.

Isolation and Characterization of 4-tert-Butylphenol-Utilizing Sphingobium fuliginis Strains from Phragmites australis Rhizosphere Sediment▿ †

PubMed Central

Toyama, Tadashi; Momotani, Naonori; Ogata, Yuka; Miyamori, Yuji; Inoue, Daisuke; Sei, Kazunari; Mori, Kazuhiro; Kikuchi, Shintaro; Ike, Michihiko

2010-01-01

We isolated three Sphingobium fuliginis strains from Phragmites australis rhizosphere sediment that were capable of utilizing 4-tert-butylphenol as a sole carbon and energy source. These strains are the first 4-tert-butylphenol-utilizing bacteria. The strain designated TIK-1 completely degraded 1.0 mM 4-tert-butylphenol in basal salts medium within 12 h, with concomitant cell growth. We identified 4-tert-butylcatechol and 3,3-dimethyl-2-butanone as internal metabolites by gas chromatography-mass spectrometry. When 3-fluorocatechol was used as an inactivator of meta-cleavage enzymes, strain TIK-1 could not degrade 4-tert-butylcatechol and 3,3-dimethyl-2-butanone was not detected. We concluded that metabolism of 4-tert-butylphenol by strain TIK-1 is initiated by hydroxylation to 4-tert-butylcatechol, followed by a meta-cleavage pathway. Growth experiments with 20 other alkylphenols showed that 4-isopropylphenol, 4-sec-butylphenol, and 4-tert-pentylphenol, which have alkyl side chains of three to five carbon atoms with α-quaternary or α-tertiary carbons, supported cell growth but that 4-n-alkylphenols, 4-tert-octylphenol, technical nonylphenol, 2-alkylphenols, and 3-alkylphenols did not. The rate of growth on 4-tert-butylphenol was much higher than that of growth on the other alkylphenols. Degradation experiments with various alkylphenols showed that strain TIK-1 cells grown on 4-tert-butylphenol could degrade 4-alkylphenols with variously sized and branched side chains (ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, tert-octyl, n-nonyl, and branched nonyl) via a meta-cleavage pathway but not 2- or 3-alkylphenols. Along with the degradation of these alkylphenols, we detected methyl alkyl ketones that retained the structure of the original alkyl side chains. Strain TIK-1 may be useful in the bioremediation of environments polluted by 4-tert-butylphenol and various other 4-alkylphenols. PMID:20802076

Polyethylenimine Interfacial Layers in Inverted Organic Photovoltaic Devices: Effects of Ethoxylation and Molecular Weight on Efficiency and Temporal Stability.

PubMed

Courtright, Brett A E; Jenekhe, Samson A

2015-12-02

We report a comparative study of polyethylenimine (PEI) and ethoxylated-polyethylenimine (PEIE) cathode buffer layers in high performance inverted organic photovoltaic devices. The work function of the indium-tin oxide (ITO)/zinc oxide (ZnO) cathode was reduced substantially (Δφ = 0.73-1.09 eV) as the molecular weight of PEI was varied from 800 g mol(-1) to 750 000 g mol(-1) compared with the observed much smaller reduction when using a PEIE thin film (Δφ = 0.56 eV). The reference inverted polymer solar cells based on the small band gap polymer PBDTT-FTTE (ITO/ZnO/PBDTT-FTTE:PC70BM/MoO3/Ag), without a cathode buffer layer, had an average power conversion efficiency (PCE) of 6.06 ± 0.22%. Incorporation of a PEIE cathode buffer layer in the same PBDTT-FTTE:PC70BM blend devices gave an enhanced performance with a PCE of 7.37 ± 0.53%. In contrast, an even greater photovoltaic efficiency with a PCE of 8.22 ± 0.10% was obtained in similar PBDTT-FTTE:PC70BM blend solar cells containing a PEI cathode buffer layer. The temporal stability of the inverted polymer solar cells was found to increase with increasing molecular weight of the cathode buffer layer. The results show that PEI is superior to PEIE as a cathode buffer layer in high performance organic photovoltaic devices and that the highest molecular weight PEI interlayer provides the highest temporal stability.

Removal of surfactants nonylphenol ethoxylates from municipal sewage-comparison of an A/O process and biological aerated filters.

PubMed

Gao, Dawen; Li, Zhe; Guan, Junxue; Li, Yifan; Ren, Nanqi

2014-02-01

The concentrations of nonylphenol ethoxylates (NPnEO, n=1 to 2) and nonylphenol (NP) in water and sludge samples were measured from a full scale sewage treatment plant (STP) with an Anaerobic/Oxic (A/O) and a Biological Aerated Filter (BAF) process. The A/O process was found to exhibit improved performance in comparison to the BAF process. Mean values of NP, NP1EO and NP2EO concentrations in influents from the STP were similar, ranging from 1.8 to 2.0×10(3)ngL(-1). In the A/O process, the removal efficiency of NP, NP1EO and NP2EO from the aqueous phase was 78%, 84%, and 89%, respectively. In contrast, the removal efficiencies of NP, NP1EO, and NP2EO were relatively lower for the BAF process, at 55%, 76%, and 79%, respectively. High concentrations of NP, NP1EO and NP2EO detected in the sludge samples had a maximum value of 2.7μgg(-1) dw, which indicates that improvement in the overall elimination of NP, NP1EO and NP2EO may be associated with adsorption by the sludge. To further investigate the fate of NP, NP1EO and NP2EO in the STP, our research assessed the degradation characteristics of NP by calculating its transformational loss in the STP. The results demonstrate that the quantity of NP measured in the effluent from the oxic unit increased by 32%, which indicates that NP1EO and NP2EO may undergo degradation in the oxic conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

A combined binding mechanism of nonionic ethoxylated surfactants to bovine serum albumin revealed by fluorescence and circular dichroism.

PubMed

Iovescu, Alina; Băran, Adriana; Stîngă, Gabriela; Cantemir-Leontieş, Anca Ruxandra; Maxim, Monica Elisabeta; Anghel, Dan Florin

2015-12-01

The study systematically investigates aqueous mixtures of fixed bovine serum albumin (BSA) and various ethoxylated nonionic surfactants belonging to a homologous series or not. Mono-disperse tetra-(C12E4), hexa-(C12E6) and octa-ethyleneglycol mono-n-dodecyl ether (C12E8), and poly-disperse eicosa-ethyleneglycol mono-n-tetradecyl ether (C14EO20) are respectively employed. Fluorescence and circular dichroism measurements are performed at surfactant/protein molar ratios (rm)s lower and higher than one. We aim to get new insights into the binding mechanism of these species and to differentiate among the interaction abilities of these surfactants. The relative magnitude of the binding thermodynamic parameters by fluorescence, and the increase of α-helix prove that hydrogen bonding drives the interaction next to the hydrophobic attraction. C12En (n=4,6,8) develop more H bonds with the albumin than C14EO20 owing to a zigzag conformation of their short ethyleneoxide chains. Among the homologous surfactants, C12E6 has a slightly stronger interaction with BSA due to a maximal number of H bonds at a minimal hindering. Static fluorescence and dynamic fluorescence indicate an inter-conversion between the tryptophan (Trp) rotamers which happens around the surfactants critical micellar concentration. For C14EO20, the meander conformation of the polar group determines a less evident conversion of the Trp rotamers and smaller α-helix rise. Binding isotherms of the homologous surfactants and the fluorescence quenching mechanism by C12E6 are also provided. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessment of endocrine-disrupting chemicals attenuation in a coastal plain stream prior to wastewater treatment plant closure

USGS Publications Warehouse

Bradley, Paul M.; Journey, Celeste A.

2014-01-01

The U.S. Geological Survey is conducting a combined pre/post-closure assessment at a long-term wastewater treatment plant (WWTP) site at Fort Gordon near Augusta, Georgia. Here, we assess select endocrine-active chemicals and benthic macroinvertebrate community structure prior to closure of the WWTP. Substantial downstream transport and limited instream attenuation of endocrine-disrupting chemicals (EDCs) was observed in Spirit Creek over a 2.2-km stream segment downstream of the WWTP outfall. A modest decline (less than 20% in all cases) in surface water detections was observed with increasing distance downstream of the WWTP and attributed to partitioning to the sediment. Estrogens detected in surface water in this study included estrone (E1), 17β-estradiol (E2), and estriol (E3). The 5 ng/l and higher mean estrogen concentrations observed in downstream locations indicated that the potential for endocrine disruption was substantial. Concentrations of alkylphenol ethoxylate (APE) metabolite EDCs also remained statistically elevated above levels observed at the upstream control site. Wastewater-derived pharmaceutical and APE metabolites were detected in the outflow of Spirit Lake, indicating the potential for EDC transport to aquatic ecosystems downstream of Fort Gordon. The results indicate substantial EDC occurrence, downstream transport, and persistence under continuous supply conditions and provide a baseline for a rare evaluation of ecosystem response to WWTP closure.

Characterization of the chemicals used in hydraulic fracturing fluids for wells located in the Marcellus Shale Play.

PubMed

Chen, Huan; Carter, Kimberly E

2017-09-15

Hydraulic fracturing, coupled with the advances in horizontal drilling, has been used for recovering oil and natural gas from shale formations and has aided in increasing the production of these energy resources. The large volumes of hydraulic fracturing fluids used in this technology contain chemical additives, which may be toxic organics or produce toxic degradation byproducts. This paper investigated the chemicals introduced into the hydraulic fracturing fluids for completed wells located in Pennsylvania and West Virginia from data provided by the well operators. The results showed a total of 5071 wells, with average water volumes of 5,383,743 ± 2,789,077 gal (mean ± standard deviation). A total of 517 chemicals was introduced into the formulated hydraulic fracturing fluids. Of the 517 chemicals listed by the operators, 96 were inorganic compounds, 358 chemicals were organic species, and the remaining 63 cannot be identified. Many toxic organics were used in the hydraulic fracturing fluids. Some of them are carcinogenic, including formaldehyde, naphthalene, and acrylamide. The degradation of alkylphenol ethoxylates would produce more toxic, persistent, and estrogenic intermediates. Acrylamide monomer as a primary degradation intermediate of polyacrylamides is carcinogenic. Most of the chemicals appearing in the hydraulic fracturing fluids can be removed when adopting the appropriate treatments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of thermodynamic and transport parameters of naphthenic acids and organic process chemicals in oil sand tailings pond water.

PubMed

Wang, Xiaomeng; Robinson, Lisa; Wen, Qing; Kasperski, Kim L

2013-07-01

Oil sand tailings pond water contains naphthenic acids and process chemicals (e.g., alkyl sulphates, quaternary ammonium compounds, and alkylphenol ethoxylates). These chemicals are toxic and can seep through the foundation of the tailings pond to the subsurface, potentially affecting the quality of groundwater. As a result, it is important to measure the thermodynamic and transport parameters of these chemicals in order to study the transport behavior of contaminants through the foundation as well as underground. In this study, batch adsorption studies and column experiments were performed. It was found that the transport parameters of these chemicals are related to their molecular structures and other properties. The computer program (CXTFIT) was used to further evaluate the transport process in the column experiments. The results from this study show that the transport of naphthenic acids in a glass column is an equilibrium process while the transport of process chemicals seems to be a non-equilibrium process. At the end of this paper we present a real-world case study in which the transport of the contaminants through the foundation of an external tailings pond is calculated using the lab-measured data. The results show that long-term groundwater monitoring of contaminant transport at the oil sand mining site may be necessary to avoid chemicals from reaching any nearby receptors.

Mechanism for Biotransformation of Nonylphenol Polyethoxylates to Xenoestrogens in Pseudomonas putida

PubMed Central

John, Dominic M.; White, Graham F.

1998-01-01

A strain of Pseudomonas putida isolated from activated sewage grew aerobically on the xenoestrogen precursor, nonylphenol polyethoxylate (NPEOx, where x is the number of ethoxylate units) as sole carbon source. Comparative growth yields on NPEOav6, NPEOav9, and NPEOav20 (mixtures with average ethoxylate numbers as indicated) were consistent with utilization of all but two ethoxylate units, and the final accumulating metabolite was identified by gas chromatography-mass spectroscopy as nonylphenol diethoxylate (NPEO2). There was no growth on nonylphenol or polyethylene glycols, and there was no evidence for production of carboxylic acid analogs of NPEOx. Biodegradation kinetics measured by high-pressure liquid chromatography (HPLC) for each component in NPEOx mixtures showed that biodegradation proceeded via successive exoscission of the ethoxylate chain and not by direct scission between the second and third ethoxylate residues. The NPEOx-degrading activity was inducible by substrate, and cell extracts of NPEOav9-induced cells were also active on the pure alcohol ethoxylate, dodecyl octaethoxylate (AEO8), producing sequentially, under either aerobic or anaerobic conditions, AEO7, AEO6, AEO5, etc., thus demonstrating that the pathway involved removal of single ethoxylate units. HPLC analysis of 2,4-dinitrophenylhydrazone derivatives revealed acetaldehyde (ethanal) as the sole aldehydic product from either NPEOav9 or AEO8 under either aerobic or anaerobic conditions. We propose a mechanism for biotransformation which involves an oxygen-independent hydroxyl shift from the terminal to the penultimate carbon of the terminal ethoxylate unit of NPEOx and dissociation of the resulting hemiacetal to release acetaldehyde and the next-lower homolog, NPEOx−1, which then undergoes further cycles of the same reaction until x = 2. PMID:9721266

Determination of fatty alcohol ethoxylates and alkylether sulfates by anionic exchange separation, derivatization with a cyclic anhydride and liquid chromatography.

PubMed

Beneito-Cambra, M; Ripoll-Seguer, L; Herrero-Martínez, J M; Simó-Alfonso, E F; Ramis-Ramos, G

2011-11-25

A method for the separation, characterization and determination of fatty alcohol ethoxylates (FAE) and alkylether sulfates (AES) in industrial and environmental samples is described. Separation of the two surfactant classes was achieved in a 50:50 methanol-water medium by retaining AES on a strong anionic exchanger (SAX) whereas most FAE were eluted. After washing the SAX cartridges to remove cations, the residual hydrophobic FAE were eluted by increasing methanol to 80%. Finally, AES were eluted using 80:20 and 95:5 methanol-concentrated aqueous HCl mixtures. Methanol and water were removed from the FAE and AES fractions, and the residues were dissolved in 1,4-dioxane. In this medium, esterification of FAE and transesterification of AES with a cyclic anhydride was performed. Phthalic and diphenic anhydrides were used to derivatizate the surfactants in industrial samples and seawater extracts, respectively. Separation of the derivatized oligomers was achieved by gradient elution on a C8 column with acetonitrile/water in the presence of 0.1% acetic acid. Good resolution between both the hydrocarbon series and the successive oligomers within the series was achieved. Cross-contamination of FAE with AES and vice versa was not observed. Using dodecyl alcohol as calibration standard, and correction of the peak areas of the derivatized oligomers by their respective UV-vis response factors, both FAE and AES were evaluated. After solid-phase extraction on C18, the proposed method was successfully applied to the characterization and determination of the two surfactant classes in industrial samples and in seawater. Copyright © 2011 Elsevier B.V. All rights reserved.

Environmental and industrial factors relating to flavor tainting of fish in the upper Wisconsin river

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heil, T.P.; Lindsay, R.C.

1990-08-01

Extracts from Large Toothed Aspen (Populous grandidenta Michx.) and Jack Pine (Pinus banksiana Lamb.) contained many odor compounds found in flavor-tainted walleye from the Wisconsin River, including alkylphenols. Aspen wood contained 8 ppb of 2-isopropylphenol, and river sediments also contained low ppb levels of many alkylphenols, including 2-isopropylphenol. Thiophenol and thiocresol which sporadically cause offensive sulfury taints in Wisconsin River fish were also found in river sediment. Quantitative analysis of fish for alkylphenols supported a hypothesis involving a food chain-mediated seasonal fluctuation of alkylphenol levels in fish. Thiophenols are postulated to be derived from pulp mill activities on the river.

SCIENTIFIC-RESEARCH WORK IN THE FIELD OF ADDITIVE CHEMISTRY,

DTIC Science & Technology

multifunctional oil additives is reviewed. Antioxidants based on nitrogen-containing compounds were prepared by condensation of alkylphenols with formaldehyde and... alkylphenols or their sulfides with formaldehyde and amines or aniline and reaction with phosphorus trichloride are effective additives. AzNII-10 is based...on p-tert. amylphenol. INKhP-21 and INKhP-25, condensation products of alkylphenols , formaldehyde, and an amine treated with phosphorus pentachloride

Alkylphenol Activity against Candida spp. and Microsporum canis: A Focus on the Antifungal Activity of Thymol, Eugenol and O-Methyl Derivatives.

PubMed

Fontenelle, Raquel O S; Morais, Selene M; Brito, Erika H S; Brilhante, Raimunda S N; Cordeiro, Rossana A; Lima, Ynayara C; Brasil, Nilce V G P S; Monteiro, André J; Sidrim, José J C; Rocha, Marcos F G

2011-07-29

In recent years there has been an increasing search for new antifungal compounds due to the side effects of conventional antifungal drugs and fungal resistance. The aims of this study were to test in vitro the activity of thymol, eugenol, estragole and anethole and some O-methyl-derivatives (methylthymol and methyleugenol) against Candida spp. and Microsporum canis. The broth microdilution method was used to determine the minimum inhibitory concentration (MIC). The minimum fungicidal concentrations (MFC) for both Candida spp. and M. canis were found by subculturing each fungal suspension on potato dextrose agar. Thymol, methylthymol, eugenol, methyl-eugenol, anethole, estragole and griseofulvin respectively, presented the following MIC values against M. canis: 4.8-9.7; 78-150; 39; 78-150; 78-150; 19-39 µg/mL and 0.006-2.5 mg/mL. The MFC values for all compounds ranged from 9.7 to 31 µg/mL. Concerning Candida spp, thymol, methylthymol, eugenol, methyleugenol, anethole, estragole and amphotericin, respectively, showed the following MIC values: 39; 620-1250; 150-620; 310-620; 620; 620-1250 and 0.25-2.0 mg/mL. The MFC values varied from 78 to 2500 µg/mL. All tested compounds thus showed in vitro antifungal activity against Candida spp. and M. canis. Therefore, further studies should be carried out to confirm the usefulness of these alkylphenols in vivo.

Recent advances in analytical methods for the determination of 4-alkylphenols and bisphenol A in solid environmental matrices: A critical review.

PubMed

Salgueiro-González, N; Castiglioni, S; Zuccato, E; Turnes-Carou, I; López-Mahía, P; Muniategui-Lorenzo, S

2018-09-18

The problem of endocrine disrupting compounds (EDCs) in the environment has become a worldwide concern in recent decades. Besides their toxicological effects at low concentrations and their widespread use in industrial and household applications, these pollutants pose a risk for non-target organisms and also for public safety. Analytical methods to determine these compounds at trace levels in different matrices are urgently needed. This review critically discusses trends in analytical methods for well-known EDCs like alkylphenols and bisphenol A in solid environmental matrices, including sediment and aquatic biological samples (from 2006 to 2018). Information about extraction, clean-up and determination is covered in detail, including analytical quality parameters (QA/QC). Conventional and novel analytical techniques are compared, with their advantages and drawbacks. Ultrasound assisted extraction followed by solid phase extraction clean-up is the most widely used procedure for sediment and aquatic biological samples, although softer extraction conditions have been employed for the latter. The use of liquid chromatography followed by tandem mass spectrometry has greatly increased in the last five years. The majority of these methods have been employed for the analysis of river sediments and bivalve molluscs because of their usefulness in aquatic ecosystem (bio)monitoring programs. Green, simple, fast analytical methods are now needed to determine these compounds in complex matrices. Copyright © 2018 Elsevier B.V. All rights reserved.

Occurrence and sources of selected phenolic endocrine disruptors in Ria de Aveiro, Portugal

PubMed Central

Sousa, Ana; Galante-Oliveira, Susana; Barroso, Carlos M.; Kohler, Hans-Peter E.; Giger, Walter

2009-01-01

Background, aim and scope Ria de Aveiro (Portugal) is a shallow coastal lagoon of high economic and ecological importance. Hardly any data on its chemical pollution by polar organic pollutants are available in literature. This study focused on the presence and sources of a series of phenolic endocrine-disrupting compounds (EDCs) in this area, including parabens, alkylphenolic compounds and bisphenol-A (BPA). A number of possible sources of pollution are present in the area, including the large harbours present in the lagoon, the city of Aveiro and the rivers discharging into the area. A recently constructed submarine wastewater outfall, located a few kilometres from the lagoon inlet has also been suggested as a possible source of pollution to Ria de Aveiro in several publications. The aim of the current field study was to investigate the occurrence and main sources of phenolic endocrine disruptors in Ria de Aveiro. Materials and methods An extensive sampling campaign was performed, with surface water and wastewater grab samples taken at over 50 locations, in duplicate on different days. Samples were treated using solid phase extraction and analysed by liquid chromatography tandem mass spectrometry. Results and discussion Concentrations in lagoon water were generally low: not exceeding 20 ng/L for most analytes. Levels in river water exceeded those in the lagoon by a factor 3 to 500 (o-phenylphenol (PhP) and nonylphenoxy ethoxy acetic acids (A9PEC), respectively), with concentrations up to 700 ng/L for BPA and 7,300 ng/L for A9PEC. Samples from the harbours showed EDC levels similar to those in the rest of the lagoon, but in the city of Aveiro, elevated concentrations were observed for alkylphenol ethoxylates (A9PEO), A9PEC, PhP and BPA. Wastewater effluents showed low levels for parabens, whilst alkylphenolic compounds reached several micrograms per litre. The effluents are discharged into the ocean via a submarine outfall, but as marine water near the outfall

Identification, contribution, and estrogenic activity of potential EDCs in a river receiving concentrated livestock effluent in Southern Taiwan.

PubMed

Liu, Yung-Yu; Lin, Yi-Siou; Yen, Chia-Hung; Miaw, Chang-Ling; Chen, Ting-Chien; Wu, Meng-Chun; Hsieh, Chi-Ying

2018-04-27

We assessed 22 selected endocrine-disrupting compounds (EDCs) and other emerging, potentially endocrine-active compounds with estrogenic activity from the waters of the Wuluo River, southern Taiwan. This watershed receives high amounts of livestock and untreated household wastewaters. The river is surrounded by concentrated animal feedlot operations (CAFOs). River water samples were analyzed for selected compounds by liquid chromatography-tandem mass spectrometry (LC-MS/MS), T47D-KBluc reporter gene assay, and E-screen cell proliferation in vitro bioassay. Total concentrations of ∑alkylphenolic compounds (bisphenol A, 4-nonylphenol, t-nonylphenol, octylphenol, nonylphenol mono-ethoxylate, nonylphenol di-ethoxylate) were much higher than ∑estrogens (estrone, 17 β-estradiol, estriol, 17ß-ethynylestradiol, diethylstilbestrol), ∑preservatives (methyl paraben, ethyl paraben, propyl paraben, butyl paraben), ∑UV-filters (benzophenone, methyl benzylidene camphor, benzophenone-3), ∑antimicrobials (triclocarben, triclosan, chloroxylenol), and an insect repellent (diethyltoluamide) over four seasonal sampling periods. The highest concentration was found for bisphenol A with a mean of 302 ng/L. However, its contribution to estrogenic activity was not significant due to its relatively low estrogenic potency. Lower detection rates were found for BP, EE2, TCS, and PCMX, while DES and EP were not detected. E1 and E2 levels in raw water samples were 50% higher than the predicted no-effect concentrations (PNEC) for aquatic organisms of 6 and 2 ng/L, respectively. The potency of estrogenic activity ranged from 11.7 to 190.1 ng/L E2 T47D-Kbluc and 6.63 to 84.5 ng/L E2 E-Screen for extracted samples. Importantly, estrone contributed 50% of the overall activity in 60% and 44% of the samples based on T47D-KBluc and MCF-7 bioassays, followed by 17 ß-estradiol, highlighting the importance of total steroid estrogen loading. This study demonstrates that the estrogenic

Fast Breaking Detergents: Their Role in the Generation of Hydrogen Sulfide in Oily-Water Wastes

DTIC Science & Technology

1993-09-01

central fission would retard the biodegradation of this surfactant under anaerobic conditions. In "Ameroid", the surfactant is an m- alkylphenol ...and glycolic acid) will be small. After E-Chain metabolism is complete, an alkylphenol residue accumulates which has been observed to inhibit further...during the initial biodegradation of the surfactant ( alkylphenols ). Since the "Ameroid" results in these trials were inconsistent, any variations can not

Electrostatic Hazards of Urethane Packed Fuel Tanks.

DTIC Science & Technology

1986-03-01

Monsanto concluded (Appendix D) that the foam was absorbing substances ( alkylphenols ) from the fuel and that the fuel was extracting chemicals (the most...experienced fuel impingement exhibited very strong absorption at 2.9 pm which is attributed to the alkylphenol type substances extracted by the foam...from the foam. - Absorption of alkylphenol type compounds by the foam. The latter of these compositional changes is believed to have a relatively

Chromatographic techniques for the determination of alkyl-phenols, tocopherols and other minor polar compounds in raw and roasted cold pressed cashew nut oils.

PubMed

Gómez-Caravaca, Ana María; Verardo, Vito; Caboni, Maria Fiorenza

2010-11-19

Anacardium occidentale belongs to the family Anacardiaceae and is principally grown in tropical America (Mexico, Peru, Brazil, etc.) and India. Cashew nuts contain low amounts of hydroxy alkyl phenols that come from an oily liquid present in their shell and that is known as cashew-nut shell liquid. This paper reports the alkyl phenols composition of cold pressed raw and roasted cashew nut oil. First of all, cashew nut shell liquid was used for a basic fractionation of the alkyl phenol classes by preparative TLC and definitively identified by GC-MS and GC-FID. Anacardic acids were the major alkylphenols contained in both oils followed by cardol, cardanol and 2-methylcardol compounds, respectively. Raw and roasted oils did not show different compositions except for cardanols. The oil produced from roasted cashew nut reported a higher concentration of cardanols. Furthermore, tocopherols and other minor polar compounds were determined by HPLC-FLD and HPLC-DAD-MS, respectively. Tocopherol content varied in a range of 171.48-29.56mg/100g from raw to roasted cashew nut oil, being β-tocopherol the one which presented a higher decrease (93.68%). Also minor polar compounds in cashew oil decreased after roasting from 346.52 to 262.83mg/kg. Copyright © 2010 Elsevier B.V. All rights reserved.

Magnetic solid phase extraction with CoFe2O4/oleic acid nanoparticles coupled to gas chromatography-mass spectrometry for the determination of alkylphenols in baby foods.

PubMed

Pastor-Belda, Marta; Viñas, Pilar; Campillo, Natalia; Hernández-Córdoba, Manuel

2017-04-15

Magnetic solid phase extraction (MSPE) with cobalt ferrite nanoparticles coated with oleic acid is described for the determination of alkylphenols (APs), 4-tert-butylphenol (TBP), 4-pentylphenol (PP), 4-hexylphenol (HP), 4-tert-octylphenol (TOP), 4-n-octylphenol (OP) and 4-nonylphenol (NP) in baby foods using gas chromatography with mass spectrometry (GC-MS). Prior to MSPE, the sample was treated with trichloroacetic acid, and the APs derivatized with acetic anhydride. Parameters affecting the extraction efficiency: amount of magnetic nanoparticles, extraction time and desorption conditions, were optimized. The enriched phase obtained was evaporated to dryness and the residue reconstituted in 50μL of methanol, 1μL of which was injected into the GC-MS. Samples were quantified applying matrix-matched calibration and using 2-chloro-5-bromoanisole as surrogate standard. The analysis of 0.5g of sample provided detection limits in the 0.4-1.7ngg -1 range. Some samples contained APs at levels of between 3ngg -1 for HP and 122ngg -1 for TOP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Application of the GREAT-ER model for environmental risk assessment of nonylphenol and nonylphenol ethoxylates in China.

PubMed

Zhang, Lai; Cao, Yan; Hao, Xuewen; Zhang, Yongyong; Liu, Jianguo

2015-12-01

The environmental risk presented by "down-the-drain" chemicals to receiving rivers in large urban areas has received increasing attention in recent years. Geo-referenced Regional Environmental Assessment Tool for European Rivers (GREAT-ER) is a typical river catchment model that has been specifically developed for the risk assessment of these chemicals and applied in many European rivers. By utilizing the new version of the model, GREAT-ER 3.0, which is the first completely open source software for worldwide application, this study represents the first attempt to conduct an application of GREAT-ER in the Wenyu River of China. Aquatic exposure simulation and an environmental risk assessment of nonylphenol (NP) and its environmental precursor nonylphenol ethoxylates (NPEOs) were conducted effectively by GREAT-ER model, since NP is one of typical endocrine disrupting chemicals (EDCs) and its environmental precursor NPEOs as a "down-the-drain" chemical are extensively used in China. In the result, the predicted environmental concentrations (PECs) of NP and NPEOs in the water of Wenyu River were 538 and 4320 ng/L, respectively, at the regional scale, and 1210 and 8990 ng/L, respectively, at the local scale. From the results profile of the RCR, the combination of high emissions from large STPs with insufficient dilution of the river caused the high RCR. The PECs of NP in the sediment were in the range of 216.8-8218.3 ng/g (dry weight), which was consistent with the available monitoring data. The study showed the worldwide applicability and reliability of GREAT-ER as a river catchment model for the risk assessment of these chemicals and also revealed the general environmental risks presented by NP and NPEOs in the Wenyu River catchment in Beijing due to the extensive use of these chemicals. The results suggest that specific control or treatment measures are probably warranted for these chemicals to reduce their discharge in major cities.

A survey of alkylphenols, bisphenols, and triclosan in personal care products from China and the United States.

PubMed

Liao, Chunyang; Kannan, Kurunthachalam

2014-07-01

Exposure of humans to environmental phenolic compounds such as bisphenol A (BPA) and alkylphenols is a matter of concern, due to these compounds' ubiquitous occurrence and estrogenic potencies. Little is known about the levels of environmental phenolics in personal care products (PCPs). In this study, nonylphenol, two octylphenols, eight bisphenols (BPA and its analogs), and triclosan (TCS) were determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in PCP samples (n = 231) collected from China and the United States (U.S.). The concentrations of 4-n-nonylphenol (4-NP), 4-n-octylphenol (4-OP), 4-tert-octylphenol (4-t-OP), and TCS were in the ranges of <0.5-39,100 [geometric mean (GM): 21.5], <0.5-315 (0.680), <1.0-10,100 (2.69), and <0.5-53,900 (3.03) ng/g, respectively. The GM concentrations of individual bisphenols, including BPA, bisphenol S (BPS), and bisphenol F (BPF), were generally at sub-nanogram per gram levels. No significant differences in concentrations of the target compounds were found among various PCP categories or between China and the U.S. The estimated GM daily intakes of 4-NP, ∑OPs (sum of 4-OP and 4-t-OP), ∑BPs (sum of eight bisphenols), and TCS through dermal absorption from the use of PCPs were 0.932, 0.093, 0.072, and 0.016 μg/day, respectively, for adult Chinese women and 0.340, 0.054, 0.120, and 0.068 μg/day, respectively, for adult U.S. women. Body lotions, face creams, and liquid foundations accounted for the majority (>85 %) of the dermal exposure doses of the target phenolics.

In-port derivatization coupled to different extraction techniques for the determination of alkylphenols in environmental water samples.

PubMed

Cavalheiro, J; Monperrus, M; Amouroux, D; Preud'Homme, H; Prieto, A; Zuloaga, O

2014-05-02

Large volume injection (LVI)-in port silylation coupled to gas chromatography-mass spectrometry (GC-MS) for the determination of alkylphenols (APs) in water samples applying four different extraction approaches was evaluated. Among the variables studied for in-port derivatization, vent time, cryo-focusing temperature and the ratio solvent volume/N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) volume were optimized using an experimental design approach. Regarding the extraction techniques, different approaches previously optimized in the research group were tested. On the one hand different polymeric materials were tested: silicon rod (SR), polyethersulfone (PES) and polydimethylsiloxane (PDMS), the latter in the stir-bar sorptive extraction format (SBSE-PDMS). PES was chosen among the polymeric materials due to the higher recoveries (compared with SR) and lower price (compared to PDMS in the stir-bar sorptive extraction, SBSE-PDMS). Both MASE and PES protocols were selected at this point for further method validation and application to real samples. Finally, the developed methods were validated and applied to the determination of target analytes in various aqueous environmental matrices, including estuarine water and wastewater. Acceptable repeatability in the case of MASE (5-17%) and PES (7-21%) procedures and method detection limits (MDLs, 5-123 and 28-328 ng L(-1) for PES and MASE, respectively) were obtained for most analytes. In terms of apparent recoveries in the presence of matrix, estuarine and effluent samples showed no significant matrix effect (apparent recoveries in the 73-121% for PES and 74-128% for MASE), while a stronger matrix effect was observed for influent wastewater samples (98-132% for PES and 65-156% for MASE). Both MASE and PES extractions combined with LVI-in-port derivatization-GC-MS were applied to the determination of APs in the estuary of Bilbao (Gulf of Biscay, Spain). Copyright © 2014 Elsevier B.V. All rights reserved.

Electrostatic Safety with Explosion Suppressant Foams.

DTIC Science & Technology

1983-03-01

the foam, and (2) sorption of alkylphenol type substances, present as oxidation inhibitors in the fuel, by the foam. It had been previously reported... alkylphenol type substances. The use of antistatic ingredients in the reticulated polyurethane foam was suggested as a means of minimizing static...foam with JP-4 are: o Removal of diethylhexyl phthalate from the foam. o Sorption of alkylphenol type compounds by the foam. Tne latter of these two

40 CFR 60.667 - Chemicals affected by subpart NNN.

Code of Federal Regulations, 2010 CFR

2010-07-01

... alcohols, ethoxylated, mixed Linear alcohols, ethoxylated, and sulfated, sodium salt, mixed Linear alcohols, sulfated, sodium salt, mixed Linear alkylbenzene 123-01-3 Magnesium acetate 142-72-3 Maleic anhydride 108...

40 CFR 60.667 - Chemicals affected by subpart NNN.

Code of Federal Regulations, 2011 CFR

2011-07-01

... alcohols, ethoxylated, mixed Linear alcohols, ethoxylated, and sulfated, sodium salt, mixed Linear alcohols, sulfated, sodium salt, mixed Linear alkylbenzene 123-01-3 Magnesium acetate 142-72-3 Maleic anhydride 108...

Application of oysters as useful concentration indicators to evaluate the fate of xenoestrogenic alkylphenols along the western coastal areas of Taiwan

NASA Astrophysics Data System (ADS)

Ding, Wanghsien

2016-04-01

The oyster is an important aquacultural species in Taiwan. Since oysters naturally inhabit shelves near the coast, samples from particular "oyster cultural sites" can be applied to evaluate the pollution levels of segments of coastal water. Insufficient wastewater treatment has caused untreated wastewaters to flow into rivers, and hence, into oyster cultural areas in estuaries as well as shallow coastal waters. Therefore, the concentration of pollutants in the oysters can be used as concentration indicators to evaluate the fate of the pollutants on the western coastal areas of Taiwan. In this study, xenoestrogenic alkylphenols were determined in oyster samples by extractive steam distillation prior to their determination by gas chromatography - mass spectrometry. The results show that a group of 4-nonylphenol isomers (4-NPs) were ubiquitous in oysters with concentration levels ranging from 23 to 3370 ng/g (wet weight). The concentrations of 4-NPs varied with different levels of 4-NPs found across unrelated estuaries water samples, and higher level of 4-NPs in water samples caused higher concentration of 4-NPs found in oyster tissue samples. Moreover, at the same oyster sites mentioned previously, the levels of 4-NPs in oysters decreased significantly after the year 2008. This drop in 4-NPs level can be attributed to environmental regulations that banned 4-NPs as additives in household cleaning agents since January 2008 in Taiwan. Due to the mentioned reasons, oysters are concluded to be useful organic pollutant concentration indicators in marine environments.

Method validation and reconnaissance of pharmaceuticals, personal care products, and alkylphenols in surface waters, sediments, and mussels in an urban estuary.

PubMed

Klosterhaus, Susan L; Grace, Richard; Hamilton, M Coreen; Yee, Donald

2013-04-01

Novel methods utilizing liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry were validated for low-level detection of 104 pharmaceuticals and personal care products ingredients (PPCPs) and four alkylphenols (APs) in environmental samples. The methods were applied to surface water, sediment, and mussel tissue samples collected from San Francisco Bay, CA, USA, an urban estuary that receives direct discharge from over forty municipal and industrial wastewater outfalls. Among the target PPCPs, 35% were detected in at least one sample, with 31, 10, and 17 compounds detected in water, sediment, and mussels, respectively. Maximum concentrations were 92 ng/L in water (valsartan), 33 ng/g dry weight (dw) in sediments (triclocarban), and 14 ng/g wet weight (ww) in mussels (N,N-diethyl-m-toluamide). Nonylphenol was detected in water (<2-73 ng/L), sediments (22-86 ng/g dw), and mussels (<0.04-95 ng/g ww), and nonylphenol mono- and diethoxylates were detected in sediments (<1-40 ng/g dw) and mussels (<5-192 ng/g ww). The concentrations of PPCPs and APs detected in the San Francisco Bay samples were generally at least an order of magnitude below concentrations expected to elicit toxic effects in aquatic organisms. This study represents the first reconnaissance of PPCPs in mussels living in an urban estuary and provides the first field-derived bioaccumulation factors (BAFs) for select compounds in aquatic organisms. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigation of nonylphenol and nonylphenol ethoxylates in sewage sludge samples from a metropolitan wastewater treatment plant in Turkey.

PubMed

Ömeroğlu, Seçil; Murdoch, Fadime Kara; Sanin, F Dilek

2015-01-01

Nonylphenol ethoxylates (NPEOs) have drawn significant attention within the last decade for both scientific and legislative reasons. In Turkey, the Regulation Regarding the Use of Domestic and Urban Sludges on Land states a limit value for the sum of nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) as NPE (NPE=NP+NP1EO+NP2EO). Unfortunately a standard method for the determination of these chemicals has not been yet set by the authorities and no data exists about the concentrations of NP and NPEOs in sewage sludge in Turkey. The aim of this study is to propose simple and easily applicable extraction and measurement techniques for 4-n-nonylphenol (4-n-NP), NP, NP1EO and NP2EO in sewage sludge samples and investigate the year round concentrations in a Metropolitan Wastewater Treatment Plant (WWTP) in Turkey. Different extraction techniques and GC/MS methods for sewage sludge were tested. The best extraction method for these compounds was found to be ultrasonication (5 min) using acetone as the solvent with acceptable recovery of analytes suggested by USEPA and other studies. The optimized extraction method showed good repeatability with relative standard deviations (RSDs) less than 6%. The recovery of analytes were within acceptable limits suggested by USEPA and other studies. The limits of detection (LODs) were 6 µg kg(-1) for NP and NP1EO, 12 µg kg(-1) for NP2EO and 0.03 µg kg(-1) for 4-n-NP. The developed method was applied to sewage sludge samples obtained from the Central WWTP in Ankara, Turkey. The sum NPE (NP+NP1EO+NP2EO) was found to be in between 5.5 µg kg(-1) and 19.5 µg kg(-1), values which are in compliance with Turkish and European regulations. Copyright © 2014 Elsevier B.V. All rights reserved.

Determination of Wastewater Compounds in Whole Water by Continuous Liquid-Liquid Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry

USGS Publications Warehouse

Zaugg, Steven D.; Smith, Steven G.; Schroeder, Michael P.

2006-01-01

A method for the determination of 69 compounds typically found in domestic and industrial wastewater is described. The method was developed in response to increasing concern over the impact of endocrine-disrupting chemicals on aquatic organisms in wastewater. This method also is useful for evaluating the effects of combined sanitary and storm-sewer overflow on the water quality of urban streams. The method focuses on the determination of compounds that are indicators of wastewater or have endocrine-disrupting potential. These compounds include the alkylphenol ethoxylate nonionic surfactants, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclic aromatic hydrocarbons, and high-use domestic pesticides. Wastewater compounds in whole-water samples were extracted using continuous liquid-liquid extractors and methylene chloride solvent, and then determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-water samples fortified at 0.5 microgram per liter averaged 72 percent ? 8 percent relative standard deviation. The concentration of 21 compounds is always reported as estimated because method recovery was less than 60 percent, variability was greater than 25 percent relative standard deviation, or standard reference compounds were prepared from technical mixtures. Initial method detection limits averaged 0.18 microgram per liter. Samples were preserved by adding 60 grams of sodium chloride and stored at 4 degrees Celsius. The laboratory established a sample holding-time limit prior to sample extraction of 14 days from the date of collection.

Lubricant-Coolant for Hot Working of Metals,

DTIC Science & Technology

includes calcium acetate, sodium acetate, and polyoxyethylated alkylphenol for added effectiveness, and that its composition includes (in wt. percentage...calcium acetate 5, sodium acetate 4, polyoxyethylated alkylphenol 0.1, graphite 5, and water up to 100. (Author)

An on-line push/pull perfusion-based hollow-fiber liquid-phase microextraction system for high-performance liquid chromatographic determination of alkylphenols in water samples.

PubMed

Chao, Yu-Ying; Jian, Zhi-Xuan; Tu, Yi-Ming; Wang, Hsaio-Wen; Huang, Yeou-Lih

2013-06-07

In this study, we employed a novel on-line method, push/pull perfusion hollow-fiber liquid-phase microextraction (PPP-HF-LPME), to extract 4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-n-nonylphenol, and 4-n-octylphenol from river and tap water samples; we then separated and quantified the extracted analytes through high-performance liquid chromatography (HPLC). Using this approach, we overcame the problem of fluid loss across the porous HF membrane to the donor phase, permitting on-line coupling of HF-LPME to HPLC. In our PPP-HF-LPME system, we used a push/pull syringe pump as the driving source to perfuse the acceptor phase, while employing a heating mantle and an ultrasonic probe to accelerate mass transfer. We optimized the experimental conditions such as the nature of the HF supported intermediary phase and the acceptor phase, the composition of the donor and acceptor phases, the sample temperature, and the sonication conditions. Our proposed method provided relative standard deviations of 3.1-6.2%, coefficients of determination (r(2)) of 0.9989-0.9998, and limits of detection of 0.03-0.2 ng mL(-1) for the analytes under the optimized conditions. When we applied this method to analyses of river and tap water samples, our results confirmed that this microextraction technique allows reliable monitoring of alkylphenols in water samples.

Renal Function, Bisphenol A, and Alkylphenols: Results from the National Health and Nutrition Examination Survey (NHANES 2003–2006)

PubMed Central

You, Li; Zhu, Xiangzhu; Shrubsole, Martha J.; Fan, Hong; Chen, Jing; Dong, Jie; Hao, Chuan-Ming; Dai, Qi

2011-01-01

Background Urinary excretion of bisphenol A (BPA) and alkylphenols (APs) was used as a biomarker in most previous studies, but no study has investigated whether urinary excretion of these environmental phenols differed by renal function. Objective We estimated the association between renal function and urinary excretion of BPA and APs. Methods Analyses were conducted using data from the National Health and Nutrition Examination Survey (NHANES) 2003–2006. Renal function was measured as estimated glomerular filtration rate (eGFR) calculated by the Modification of Diet in Renal Disease (MDRD) Study equation and by the newly developed Chronic Kidney Disease Epidemiology Collaboration (CKD-EPI) equation. Regression models were used to calculate geometric means of urinary BPA and APs excretion by eGFR category (≥ 90, 60–90, < 60 mL/min/m2) after adjusting for potential confounding factors. Results When we used the MDRD Study equation, participants without known renal disease (n = 2,573), 58.2% (n = 1,499) had mildly decreased renal function or undiagnosed chronic kidney disease. The adjusted geometric means for urinary BPA excretion decreased with decreasing levels of eGFR (p for trend = 0.04). The associations appeared primarily in females (p for trend = 0.03). Urinary triclosan excretion decreased with decreasing levels of eGFR (p for trend < 0.01) for both males and females, and the association primarily appeared in participants < 65 years of age. The association between BPA and eGFR was nonsignificant when we used the CKD-EPI equation. Conclusions Urinary excretion of triclosan, and possibly BPA, decreased with decreasing renal function. The associations might differ by age or sex. Further studies are necessary to replicate our results and understand the mechanism. PMID:21147601

76 FR 8895 - Polymerized Fatty Acid Esters With Aminoalcohol Alkoxylates; Exemption From the Requirement of a...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-16

..., reaction products with fatty acid dimers (CAS Reg. No. 1173188-38-9); dimethylaminoethanol, ethoxylated, propoxylated, reaction products with fatty acid dimers (CAS Reg. No. 1173188-42-5 diethylaminoethanol, ethoxylated, reaction product with fatty acid dimers (CAS Reg. No. 1173188-72-1); diethylaminoethanol...

Ipso Nitration. Regiospecific Nitration via Ipso Nitration Products.

DTIC Science & Technology

1985-05-20

products of nitration of alkylbenzenes and alkylphenol derivatives. The general pattern envisioned is shown in Scheme 1. In order to realize this...we have also explored solid state nitration of various alkylphenols . This procedure involves adsorbing concentrated nitric acid on alumina, followed

SYNTHESIS OF MIXED FULL AND SEMIESTERS OF PHOSPHOROUS ACID AS ORGANIC MOTOR OIL ADDITIVES,

DTIC Science & Technology

The synthesis of mixed full and semiesters of phosphonic acid was effected using alkylphenols produced by the chemical industry. By condensation of...industrial alkylphenol or the condensation of acid chloride of di-(alkylphenyl)-phosphorous acid with diethylamine, the corresponding mixed full and semiesters

Fast and selective pressurized liquid extraction with simultaneous in cell clean up for the analysis of alkylphenols and bisphenol A in bivalve molluscs.

PubMed

Salgueiro-González, N; Turnes-Carou, I; Muniategui-Lorenzoa, S; López-Mahía, P; Prada-Rodríguez, D

2012-12-28

A novel and green analytical methodology for the determination of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol technical mixture) and bisphenol A in bivalve mollusc samples was developed and validated. The method was based on selective pressurized liquid extraction (SPLE) with a simultaneous in cell clean up combined with liquid chromatography–electrospray ionization tandem mass spectrometry in negative mode (LC–ESI-MS/MS). Quantitation was performed by standard addition curves in order to correct matrix effects. The analytical features of the method were satisfactory: relative recoveries varied between 80 and 107% and repeatability and intermediate precision were <20% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.34 (4-n-octylphenol) and 3.6 ng g(−1) dry weight (nonylphenol). The main advantages of the method are sensitivity, selectivity, automaticity, low volumes of solvents required and low sample analysis time (according with the principles of Green Chemistry). The method was applied to the analysis of mussel samples of Galicia coast (NW of Spain). Nonylphenol and 4-tert-octylphenol were measured in all samples at concentrations between 9.3 and 372 ng g(−1) dw. As an approach, the human daily intake of these compounds was estimated and no risk for human health was found.

Three-way spectrofluorimetric-assisted multivariate determination of nonylphenol ethoxylate and 2-naphtalene sulfonate in wastewater samples and optimization approach for their photocatalytic degradation by CoTiO3 nanostructure.

PubMed

Mohsenikia, Atefeh; Gholami, Ali; Masoum, Saeed; Abbasi, Saleheh

2017-09-01

This study presents a new strategy for the simultaneous quantification of two industrial contaminants. The excitation-emission fluorescence data matrix combined with a three-way chemometric method, such as parallel factor analysis, was used for the determination of nonylphenol ethoxylate (NPE-9) as a nonionic surfactant and 2-naphthalene sulfonate (2-NS) in waste water samples. It is noticeable that this method can resolve overlapping signal into spectral and relative concentration profiles. By spiking the known concentrations of these compounds in the wastewater samples, the accuracy of the proposed methods was validated and recoveries of the spiked values were calculated. High recoveries (i.e. 90-110%) obtained for the waste water samples indicate the present method can be used successfully to determine the analytes concentration in the environmental contaminations. The photocatalytic degradation of NPE-9 and 2-NS in aqueous solution was studied using the CoTiO 3 nanoparticles catalyst. It was synthesized by the sol-gel technique. The catalytic activity of the prepared nanoparticles was measured in a batch photoreactor containing appropriate solutions of these compounds with UV irradiation. The photodegradation process of these compounds was optimized by using the central composite design. The CoTiO 3 showed high activity for UV-photocatalytic degradation of NPE-9 and 2-NS.

Simultaneous determination of parabens, alkylphenols, phenylphenols, bisphenol A and triclosan in human urine, blood and breast milk by continuous solid-phase extraction and gas chromatography-mass spectrometry.

PubMed

Azzouz, Abdelmonaim; Rascón, Andrés J; Ballesteros, Evaristo

2016-02-05

A highly sensitive gas chromatography-mass spectrometry (GC-MS) method for the determination of endocrine disrupting chemicals (EDCs) including parabens, alkylphenols, phenylphenols, bisphenol A and triclosan in human breast milk, blood and urine samples is proposed. Blood and milk require a pretreatment to remove proteins and other substances potentially interfering with the continuous solid-phase extraction (SPE) system used; on the other hand, urine samples can be directly introduced into the system after filtering. Analytes are retained on a LiChrolut EN column and derivatized by silylation following elution with acetonitrile. The resulting trimethylsilyl derivatives are determined by GC-MS. The proposed method exhibited good linearity (r(2)>0.995) for all target EDCs over the concentration range 0.7-10,000ng/l in urine, and 3.3-50,000ng/l in blood and milk. Also, it provided low limits of detection (0.2-1.8ng/l in urine, and 1.0-9.0ng/l in blood and milk), good precision (relative standard deviations less than 7%) and recoveries from 86 to 104%. A total of 24 human fluid samples were analyzed and most found to contain some target EDC at concentrations from 0.10 to 14μg/l. Copyright © 2015 Elsevier B.V. All rights reserved.

The Chemistry of Deposit Formation in Distillate Fuels,

DTIC Science & Technology

1986-01-01

identified as groups of multiple isomers of the alkylphenols , alkylnaphthols and alkylphenylphenols listed in Table VI. Ion chromatograms for isomers...matching was achieved. For example, Figure 8 shows the reconstructed ion chromatogram for m/z 136 (C3- alkylphenols ), which corresponds to peak cluster 13 in

Anisotropic and Electro-Optical Effects in Liquid Crystals.

DTIC Science & Technology

1981-08-01

alkylphenols and p-alkoxybenzoyl chlorides. Most of the reactants are obtained commercially from either Aldrich Chemical, Frinton, or Eastman Organic. The...phenol intermediates for the R-OOCpR’ compounds are prepared by refluxing the 4- alkylphenol with 4-hydroxybenzoic acid in toluene with sulfuric and

Benzotriazoles, alkylphenols and bisphenol A in municipal wastewaters and in the Glatt River, Switzerland.

PubMed

Voutsa, Dimitra; Hartmann, Paul; Schaffner, Christian; Giger, Walter

2006-09-01

Many organic micropollutants occur at trace concentrations in municipal wastewater effluents and in the aquatic environment. Some of these xenobiotic chemicals can be considered as 'emerging' contaminants and some are suspect to have endocrine disrupting effects. Among the latter are nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), which deserve special attention due to their ubiquitous occurrence in the aquatic environment. The complexing agents benzotriazole (BT) and tolyltriazole (TT) are applied as anticorrosive agents (e.g. in cooling and hydraulic fluids, in antifreezing fluids, in aircraft deicing fluids, in dish washing liquids for silver protection), as antifogging agents and as intermediates for the synthesis of various chemicals. The environmental occurrence of NP and OP is caused by the fact that they are intermediate products (metabolites) in the biodegradation of alkylphenol polyethoxylate surfactants. BPA is globally used for the production of polycarbonate and epoxy resins. BT, TT, NP, OP and BPA were quantitatively determined in municipal wastewater effluents in Switzerland and in the Glatt River. The analytes were enriched by solid-phase enrichment. BT and TT were determined underivatized by electrospray LC/tandem MS. Reversed-phase LC was performed on octylsilica columns with isocratic water/methanol elution. Multiple reaction monitoring of the positive ions provided selective and sensitive detection for reliable quantifications. NP, OP and BPA were determined by GC/MS after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide. BT and TT concentrations in primary and secondary effluents of municipal wastewater treatment plants varied from below 10 to 100 microg/L. The ranges of the concentrations in the Glatt River in ng/L were 636-3,690 for BT, 122-628 for TT, 68-326 for NP, 6-22 for OP and 9-76 for BPA. The corresponding mass flows in g/d were 93-1,870 for BT, 18-360 for TT, 24-183 for NP, 1-16 for OP and 2-72 for BPA

Membrane assisted solvent extraction coupled with liquid chromatography tandem mass spectrometry applied to the analysis of alkylphenols in water samples.

PubMed

Salgueiro-González, N; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2013-03-15

This work describes the development and validation of a novel, simple, sensitive and environmental friendly analytical method for the determination of alkylphenols in different types of water samples. The methodology was based on a membrane assisted solvent extraction of only 15 mL of water sample with 500 μL of hexane in combination with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). Acquisition was performed in the multiple reaction monitoring (MRM) mode recording two transitions for the identification of the target compounds. Quantitation is based on the use of deuterated labelled standards as surrogate standards. The figures of merit were satisfactory in all cases: absolute recoveries were close to 50% for most investigated compounds and relative recoveries varied between 81 and 108%. Repeatability and intermediate precision were <20% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) were lower than 0.04 μg L(-1) in all cases, which allow the achievement of the limits established by the Directive 2008/105/EC for surface and seawater samples and by the new proposal COM (2011) 876 final. The feasibility of the proposed method was demonstrated analyzing seawater, surface water and drinking water samples from different areas of A Coruña (Northwest of Spain). The analyses evidenced the presence of nonylphenol in seawater (MQL-0.13 μg L(-1)) and surface water samples (0.12-0.19 μg L(-1)). The highest concentration was observed in drinking water (0.25 μg L(-1)). Copyright © 2013 Elsevier B.V. All rights reserved.

Simultaneous determination of estrogenic odorant alkylphenols, chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry.

PubMed

Yuan, Su-Fen; Liu, Ze-Hua; Lian, Hai-Xian; Yang, Chuangtao; Lin, Qing; Yin, Hua; Dang, Zhi

2016-10-01

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R (2) > 0.989), low limit of detection (LOD, 0.002-0.5 μg/L), and excellent recoveries (76-126 %) with low relative standard deviation (RSD, 0.7-12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.

Effect of Nonionic Surfactants on the Stability of Hydrophobic Colloids.

DTIC Science & Technology

1987-07-30

as a point of referen e for the data with the polyoxyethlated alkylphenols . The surfactant selected was the C12E12. The reason for the selection was...ccnsequently in the stability of disper- sion. One may expect that the adsorption of polyoxyethylated alkylphenols , with the aromatic ring lying flat on

THE INTERACTION OF PHENOL AND AROMATIC AMINE INHIBITORS IN HYDROCARBON OXIDATION REACTIONS,

DTIC Science & Technology

and the structure of the phenols. This phenomenon is observed for o,o’-substituted alkylphenols and it is not observed for o,o’-nonsubstituted and...o-substituted alkylphenols . The rate of amine reduction by phenol is determined by the activity of the formed phenoxyl radical. The rate constants

Effect of wastewater treatment facility closure on endocrine disrupting chemicals in a Coastal Plain stream

USGS Publications Warehouse

Bradley, Paul M.; Journey, Celeste A.; Clark, Jimmy M.

2016-01-01

Wastewater treatment facility (WWTF) closures are rare environmental remediation events; offering unique insight into contaminant persistence, long-term wastewater impacts, and ecosystem recovery processes. The U.S. Geological Survey assessed the fate of select endocrine disrupting chemicals (EDC) in surface water and streambed sediment one year before and one year after closure of a long-term WWTF located within the Spirit Creek watershed at Fort Gordon, Georgia. Sample sites included a WWTF-effluent control located upstream from the outfall, three downstream effluent-impacted sites located between the outfall and Spirit Lake, and one downstream from the lake's outfall. Prior to closure, the 2.2-km stream segment downstream from the WWTF outfall was characterized by EDC concentrations significantly higher (α = 0.05) than at the control site; indicating substantial downstream transport and limited in-stream attenuation of EDC, including pharmaceuticals, estrogens, alkylphenol ethoxylate (APE) metabolites, and organophosphate flame retardants (OPFR). Wastewater-derived pharmaceutical, APE metabolites, and OPFR compounds were also detected in the outflow of Spirit Lake, indicating the potential for EDC transport to aquatic ecosystems downstream of Fort Gordon under effluent discharge conditions. After the WWTF closure, no significant differences in concentrations or numbers of detected EDC compounds were observed between control and downstream locations. The results indicated EDC pseudo-persistence under preclosure, continuous supply conditions, with rapid attenuation following WWTF closure. Low concentrations of EDC at the control site throughout the study and comparable concentrations in downstream locations after WWTF closure indicated additional, continuing, upstream contaminant sources within the Spirit Creek watershed. 

Determining the Residual Characteristics of Alkylphenols, Arsenic, and Lead as well as Assessing the Exposures of 1,4-Dioxane from Household Food Detergents.

PubMed

Lin, Wan-Ting; Chen, Wun-Ling; Cheng, Wei-Chih; Chang, Hui-Chuan; Tsai, Shih-Wei

2017-07-01

Food detergents are commonly used in households. The main components of detergents include surfactants and water. It has been found that certain compounds, which may cause health concerns, appear in food detergents, such as alkylphenols, arsenic, and lead. After applying food detergents is when people may be exposed to various levels of these chemicals when there are residues. In this study, the Taguchi experimental design was performed to determine the possible factors that might affect the residual characteristics of food detergent on dishware, fruits, and vegetables. The results showed that the variety of detergent was found to be the most significant factor affecting the residue amounts of arsenic (62.9%) and lead (71.6%) on fruits and vegetables, whereas the concentration of detergent used affected the amount of lead residue only (10.5%). On the other hand, dishware material, the concentration of analytes, immersion time, and type of surfactant contributed to arsenic residues on dishware, whereas technical nonylphenol isomer residues on dishware increased as the concentration of spiked analyte increased. In addition, the occurrence of 1,4-dioxane, a possible human carcinogen, in household food detergents in Taiwan was also determined in this research by solid-phase microextraction and GC-MS. Among the 80 detergent samples, 71 contained different concentrations ranges of 1,4-dioxane, from 0.03 to ~3.73 µg/g. In the exposure assessment, it was estimated that the maximum amounts of 1,4-dioxane in contact with the skin from the use of household food detergent in Taiwan was 0.015 µg/kg/day.

Increasing the Quality of Lubricating Grease by Application of Compositions of Certain Additives Containing Sulfur and Phosphorus

DTIC Science & Technology

Additives were prepared from mixtures of diaryl dithiophosphates and triaryl dithiophosphates, obtained by reaction of P2S5 with alkylphenols (I) or...methylenebis( alkylphenols ) (II). Each of the di- and triester mixtures obtained from I and II was reacted with vinyl acetate and with CH2CMeCO2Me to

Advanced Thermally Stable Coal-Derived Jet Fuels Compositional Factors Affecting Thermal Degradation of Jet Fuels

DTIC Science & Technology

1992-12-01

shown in Figure 4.2 and the peaks are identified and quantified in Table 4.2. Phenol and alkylphenols are the most readily visible 137 Cf) C-)" M0 oý...transformation of the catechol and alkylphenolic structures in subbituminous coal is a loss of aryl-( -containing structures and a condensation of the phenols

Spatial distribution of microbial biomass, activity, community structure, and the biodegradation of linear alkylbenzene sulfonate (LAS) and linear alcohol ethoxylate (LAE) in the subsurface.

PubMed

Federle, T W; Ventullo, R M; White, D C

1990-12-01

The vertical distribution of microbial biomass, activity, community structure and the mineralization of xenobiotic chemicals was examined in two soil profiles in northern Wisconsin. One profile was impacted by infiltrating wastewater from a laundromat, while the other served as a control. An unconfined aquifer was present 14 meters below the surface at both sites. Biomass and community structure were determined by acridine orange direct counts and measuring concentrations of phospholipid-derived fatty acids (PLFA). Microbial activity was estimated by measuring fluorescein diacetate (FDA) hydrolysis, thymidine incorporation into DNA, and mixed amino acid (MAA) mineralization. Mineralization kinetics of linear alkylbenzene sulfonate (LAS) and linear alcohol ethoxylate (LAE) were determined at each depth. Except for MAA mineralization rates, measures of microbial biomass and activity exhibited similar patterns with depth. PLFA concentration and rates of FDA hydrolysis and thymidine incorporation decreased 10-100 fold below 3 m and then exhibited little variation with depth. Fungal fatty acid markers were found at all depths and represented from 1 to 15% of the total PLFAs. The relative proportion of tuberculostearic acid (TBS), an actinomycete marker, declined with depth and was not detected in the saturated zone. The profile impacted by wastewater exhibited higher levels of PLFA but a lower proportion of TBS than the control profile. This profile also exhibited faster rates of FDA hydrolysis and amino acid mineralization at most depths. LAS was mineralized in the upper 2 m of the vadose zone and in the saturated zone of both profiles. Little or no LAS biodegradation occurred at depths between 2 and 14 m. LAE was mineralized at all depths in both profiles, and the mineralization rate exhibited a similar pattern with depth as biomass and activity measurements. In general, biomass and biodegradative activities were much lower in groundwater than in soil samples obtained

Engine Oils with a New Composition of Additives

DTIC Science & Technology

A lubricant additive composition IKhP (2.6% BFK, a Ba salt of a CH2O- alkylphenol condensation product; 1.4% SB-3, a Ba sulfonate; 1.2% IN-KhP-21, a...Ba salt of a CH2O-NH3- alkylphenol condensation product; 0.005% PMS-200A; and 0. 5% AzNII) is discussed in relationship to its use as an automobile oil

Chemical Stockpile Disposal Program. Risk Analysis of the Disposal of Chemical Munitions at Regional or National Sites.

DTIC Science & Technology

1987-08-01

THE DISPOSAL OF CNEM.. CU) GA TECHNOLOGIES INC SRN DIEGO CA A H SARSELL ET AL. RUG 97 GA-C- i @563 UNLRSS FIED S APEO-CDE-IS- 9 ?SIGDRAA±5-85-D-822...F/ 15/.3 NL I ihhhhhhhhhhhhlm I fflfflffllfllfllfllf smhhhhhhhhhhh ~1.02 U.,5 A I *Pig- FiLE copy CHEMICAL STOCKPILE DISPOSAL PROGRAM RISK ANALYSIS...vr~. ’ . - a ’ a’ ’- . ,I1 - .V [ N- VW; W UU V. , U .U : , r ,,, - . ..... . SECURITY CLASSIFICATION OF THIS PAGE IM : I omApproved

Monitoring alkylphenols in water using the polar organic chemical integrative sampler (POCIS): Determining sampling rates via the extraction of PES membranes and Oasis beads.

PubMed

Silvani, Ludovica; Riccardi, Carmela; Eek, Espen; Papini, Marco Petrangeli; Morin, Nicolas A O; Cornelissen, Gerard; Oen, Amy M P; Hale, Sarah E

2017-10-01

Polar organic chemical integrative samplers (POCIS) have previously been used to monitor alkylphenol (AP) contamination in water and produced water. However, only the sorbent receiving phase of the POCIS (Oasis beads) is traditionally analyzed, thus limiting the use of POCIS for monitoring a range of APs with varying hydrophobicity. Here a "pharmaceutical" POCIS was calibrated in the laboratory using a static renewal setup for APs (from 2-ethylphenol to 4-n-nonylphenol) with varying hydrophobicity (log K ow between 2.47 and 5.76). The POCIS sampler was calibrated over its 28 day integrative regime and sampling rates (R s ) were determined. Uptake was shown to be a function of AP hydrophobicity where compounds with log K ow  < 4 were preferentially accumulated in Oasis beads, and compounds with log K ow  > 5 were preferentially accumulated in the PES membranes. A lag phase (over a 24 h period) before uptake in to the PES membranes occurred was evident. This work demonstrates that the analysis of both POCIS phases is vital in order to correctly determine environmentally relevant concentrations owing to the fact that for APs with log K ow  ≤ 4 uptake, to the PES membranes and the Oasis beads, involves different processes compared to APs with log K ow  ≥ 4. The extraction of both the POCIS matrices is thus recommended in order to assess the concentration of hydrophobic APs (log K ow  ≥ 4), as well as hydrophilic APs, most effectively. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Wastewater Compounds by Polystyrene-Divinylbenzene Solid-Phase Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry

USGS Publications Warehouse

Zaugg, Steven D.; Smith, Steven G.; Schroeder, Michael P.; Barber, Larry B.; Burkhardt, Mark R.

2002-01-01

A method for the determination of 67 compounds typically found in domestic and industrial wastewater is described. The method was developed in response to increasing concern over the impact of endocrine-disrupting chemicals in wastewater on aquatic organisms. This method also may be useful for evaluating the impact of combined sanitary and storm-sewer overflow on the water quality of urban streams. The method focuses on the determination of compounds that are an indicator of wastewater or that have been chosen on the basis of their endocrine-disrupting potential or toxicity. These compounds include the alkylphenol ethoxylate nonionic surfactants and their degradates, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclicaromatic hydrocarbons, and high-use domestic pesticides. Water samples are filtered to remove suspended particulate matter and then are extracted by vacuum through disposable solid-phase cartridges that contain polystyrene-divinylbenzene resin. Cartridges are dried with nitrogen gas, and then sorbed compounds are eluted with dichloromethane-diethyl ether (4:1) and determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-water samples fortified at 4 micrograms per liter averaged 74 percent ? 7 percent relative standard deviation for all method compounds. Initial method detection limits for single-component compounds (excluding hormones and sterols) averaged 0.15 microgram per liter. Samples are preserved by filtration, the addition of 60 grams NaCl, and storage at 4 degrees Celsius. The laboratory has established a sample-holding time (prior to sample extraction) of 14 days from the date of sample collection until a statistically accepted method can be used to determine the effectiveness of these sample-preservation procedures.

Formation of formaldehyde and peroxides by air oxidation of high purity polyoxyethylene surfactants.

PubMed

Bergh, M; Magnusson, K; Nilsson, J L; Karlberg, A T

1998-07-01

Ethoxylated alcohols are non-ionic surfactants. The majority are used in household cleaners, laundry products, toiletries and in industrial and institutional cleaners. In previous studies, an ethoxylated non-ionic surfactant of technical quality showed allergenic activity in guinea pig experiments. Chemical analysis revealed a content of formaldehyde, a well-known contact allergen, and peroxides in the surfactant. Most cases of occupational contact dermatitis are considered to be of irritant origin, caused by contact with water and surfactants, but if allergenic autoxidation products can be formed, allergic contact dermatitis cannot be excluded. The sensitizing potential of a chemically defined high purity ethoxylated alcohol was investigated and oxidation under various storage and handling conditions was studied for this and a homologous product. The pure surfactant showed no significant allergenic activity on predictive testing in guinea pigs. When ethoxylated alcohols were stored in the refrigerator, their deterioration was limited. At room temperature, their content of peroxides and formaldehyde increased with time. Levels of formaldehyde above those capable of causing positive patch test reactions were found. Since such surfactants have wide applications, resulting exposure to formaldehyde could be more frequent than is generally realized, contributing to persistence of dermatitis in individuals allergic to formaldehyde.

Determination of alkylphenols and bisphenol A in seawater samples by dispersive liquid-liquid microextraction and liquid chromatography tandem mass spectrometry for compliance with environmental quality standards (Directive 2008/105/EC).

PubMed

Salgueiro-González, N; Concha-Graña, E; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

2012-02-03

A fast, simple, sensitive and green analytical chemistry method for the simultaneous determination of alkylphenols (4-tert-octylphenol, 4-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A in seawater was developed and validated. The procedure was based on a dispersive liquid-liquid microextraction (DLLME) of a small volume of seawater sample (30 mL) using only 100 μL of 1-octanol, combined with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). The matrix effect was studied and compensated using deuterated labelled standards as surrogate standards for the quantitation of target compounds. The analytical features of the proposed method were satisfactory: repeatability and intermediate precision were <10% and recoveries were around 84-104% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.005 and 0.03 μg L⁻¹, therefore the levels established in the Directive 2008/105/EC were achieved. The applicability of the proposed method was demonstrated analyzing seawater samples from different sites of A Coruña (Northwest of Spain). The analyses showed the presence of all compounds at levels between 0.035 (bisphenol A) and 0.14 μg L⁻¹ (nonylphenol). Copyright © 2011 Elsevier B.V. All rights reserved.

Determination of alkylphenols and phthalate esters in vegetables and migration studies from their packages by means of stir bar sorptive extraction coupled to gas chromatography-mass spectrometry.

PubMed

Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

2012-06-08

This paper describes a method for the determination of three alkylphenols (APs), 4-tert-octylphenol (tOP), 4-n-octylphenol (OP) and 4-nonylphenol (NP), and six phthalate esters (PEs), dimethylphthalate (DMP), diethylphthalate (DEP), di-n-butylphthalate (DBP), n-butylbenzylphthalate (BBP), di-2-ethylhexylphthalate (DEHP) and di-n-octylphthalate (DOP), in vegetables using stir bar sorptive extraction (SBSE) in combination with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Ultrasonic radiation was used to extract the analytes from the solid food matrix, and the extract obtained was preconcentrated by SBSE. The different parameters affecting both stages were carefully optimized. The method was applied to analyze commercial vegetables, in the form of plastic packed salads and canned greens, as well as the corresponding filling liquids of the canned food. Quantification of the samples was carried out against aqueous standards using an internal standard (anthracene). The analysis of a 2 g vegetable sample provided detection limits between 12.7 and 105.8 pg g⁻¹ for OP and DEHP, respectively. Migration studies from the plastic packages of the vegetables samples analyzed were carried out. DEP, DBP and DEHP were found to have migrated from the bags to the simulant and the same compounds were quantified in lettuce, corn salad, arugula, parsley and chard, at concentration levels in the 8-51 ng g⁻¹ range. However, OP and NP were found in only two vegetable samples and one filling liquid, but neither was detected in any package. The proposed method provided recoveries of 83-118%. Copyright © 2012 Elsevier B.V. All rights reserved.

Tissue distribution and depuration of 4-tert-octylphenol residues in the cyprinid fish, Scardinius erythrophthalmus.

PubMed

Pedersen, Ragnor T; Hill, Elizabeth M

2002-08-01

Alkylphenols are present in the aquatic environment through the degradation of alkylphenolpolyethoxylate surfactants in sewage treatment works. Branched chain 4-alkylphenols have been shown to retard testicular growth and stimulate vitellogenin synthesis in freshwater fish. We conducted in vivo studies in order to determine the fate and persistence of radiolabeled 4-tert-octylphenol (tOP) in the cyprinid fish, rudd (Scardinius erythrophthalmus). Sexually mature rudd were exposed to a concentration of 4.7 microg/L of [14C] tOP in a flow through system for 10 days. Radioactive residues were extracted from soft tissues and analyzed by radio-high-performance liquid chromatography. tOP accumulated as the major residue in muscle, ovary, and testis with bioconcentration factors of 24, 85, and 169, respectively. tOP residues in blood, gill, kidney, liver, and bile were extensively metabolized. Analysis of tOP residues in bile revealed 10 major metabolites, which were identified by GC-MS as products of aromatic and aliphatic hydroxylation, glucuronidation, and glucosidation. Depuration studies with exposed fish placed in clean water for up to 10 days resulted in a rapid loss of soluble residues from the tissues with half-lives of between 0.7 and 1.0 days (muscle, testis, ovary, gill, blood, kidney), 1.7 days (liver), and 5.9 days (bile). A further portion of radioactive residues was extracted from blood, gill, kidney, and liver after alkaline digestion, suggesting the formation of covalently bound protein adducts in these tissues. This study suggests that although para-alkyphenolic xenoestrogens can accumulate in muscle and the gonads of adult fish, residues are rapidly depurated from these tissues. Furthermore, analysis of the parent alkylphenol in bile, after hydrolysis of the conjugates, is likely to significantly underestimate the total concentration of alkylphenol residues and may not serve as an appropriate biomarker for quantifying the exposure of wild fish to

Occurrence of surfactants in wastewater: hourly and seasonal variations in urban and industrial wastewaters from Seville (Southern Spain).

PubMed

Camacho-Muñoz, Dolores; Martín, Julia; Santos, Juan Luís; Aparicio, Irene; Alonso, Esteban

2014-01-15

Surfactants are daily discharged to the environment from urban and industrial activities. The assessment of the risk derived from the presence of these compounds in the environment requires a deep knowledge about their sources and their distribution in wastewater treatment plants (WWTPs). However, in spite of several studies reporting their presence in WWTPs, only a small number is focused on their different sources. In this work, the distribution of anionic (linear alkylbenzene sulfonates) and non-ionic (nonylphenol ethoxylates) surfactants in WWTPs and in urban and industrial wastewater collection systems has been investigated. Seasonal and daily variability was also assessed. Concentrations of linear alkylbenzene sulfonates in influent and effluent wastewaters ranged from 1155 to 9200 μg L(-1), and from below limit of detection to 770 μg L(-1), respectively, whereas the concentrations of nonylphenol ethoxylates were significantly lower. Linear alkylbenzene sulfonates were efficiently removed (>96%), while mean removal rates of nonylphenol ethoxylates were significantly lower (<20%). Studies carried out in different seasons revealed seasonal discharge patterns from both urban and industrial activities. The analysis of wastewater collection systems showed a major contribution of linear alkylbenzene sulfonates from urban areas while, in the case of nonylphenol ethoxylates, their major contribution came from industrial activities. In all cases the discharge patterns of surfactants were related with the water consumption. © 2013.

Sensitized photooxidation of phenols by fulvic acid and in natural waters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Faust, B.C.; Hoigne, J.

1987-10-01

In addition to singlet oxygen, irradiation of fulvic acid solutions and lake water with UV and visible light (lambda > 315 nm) produces another transient oxidant species. This transient oxidant (probably an organic peroxy radical) is derived from natural dissolved organic material (DOM) and controls DOM-sensitized photooxidations of various alkylphenols. On the basis of kinetic data for the transient oxidant, DOM-sensitized photooxidation half-lives of alkylphenols are estimated to range from 1 day to several months in middle-latitude shallow surface waters.

Occurrence of contaminants of emerging concern in mussels (Mytilus spp.) along the California coast and the influence of land use, storm water discharge, and treated wastewater effluent.

PubMed

Dodder, Nathan G; Maruya, Keith A; Lee Ferguson, P; Grace, Richard; Klosterhaus, Susan; La Guardia, Mark J; Lauenstein, Gunnar G; Ramirez, Juan

2014-04-30

Contaminants of emerging concern were measured in mussels collected along the California coast in 2009-2010. The seven classes were alkylphenols, pharmaceuticals and personal care products, polybrominated diphenyl ethers (PBDE), other flame retardants, current use pesticides, perfluorinated compounds (PFC), and single walled carbon nanotubes. At least one contaminant was detected at 67 of the 68 stations (98%), and 67 of the 167 analytes had at least one detect (40%). Alkylphenol, PBDE, and PFC concentrations increased with urbanization and proximity to storm water discharge; pesticides had higher concentrations at agricultural stations. These results suggest that certain compounds; for example, alkylphenols, lomefloxacin and PBDE, are appropriate for inclusion in future coastal bivalve monitoring efforts based on maximum concentrations >50 ng/g dry weight and detection frequencies >50%. Other compounds, for example PFC and hexabromocyclododecane (HBCD), may also be suggested for inclusion due to their >25% detection frequency and potential for biomagnification. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nonylphenol-mediated CYP induction is PXR-dependent: The use of humanized mice and human hepatocytes suggests that hPXR is less sensitive than mouse PXR to nonylphenol treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mota, Linda C.; Barfield, Christina; Hernandez, Juan P.

2011-05-01

Nonylphenol (NP), a by-product of alkylphenol ethoxylates, is a pervasive surfactant that activates the xenosensing nuclear receptor, the pregnane X-receptor (PXR) in transactivation assays in vitro. We are interested in determining if NP activates PXR in vivo, determining if hPXR and mPXR act similarly, and investigating the role of PXR in protecting individuals from NP. Wild-type (WT), PXR-null, and humanized PXR (hPXR) mice were treated with NP at 0, 50 or 75 mg/kg/day for one week, and cytochrome P450 (CYP) induction, liver histopathology, and serum NP concentrations were examined. WT mice treated with NP showed induction of Cyp2b, and male-specificmore » induction of Cyp2c and Cyp3a. CYPs were not induced in PXR-null mice, demonstrating that PXR is necessary for NP-mediated CYP induction. CAR-mediated CYP induction was not observed in the PXR-null mice despite previous data demonstrating that NP is also a CAR activator. hPXR mice only showed moderate Cyp induction, suggesting that hPXR is not as sensitive to NP as mPXR in vivo. NP-mediated Cyp3a induction from three human hepatocyte donors was not significant, confirming that hPXR is not very sensitive to NP-mediated CYP induction. Lastly, mice with PXR (mPXR and hPXR) showed lower NP serum concentrations than PXR-null mice treated with NP suggesting that PXR plays a role in decreasing liver toxicity by basally regulating phase I-III detoxification enzymes that promote the metabolism and elimination of NP. In summary, PXR is required for NP-mediated CYP-induction, mPXR mediates greater CYP induction than hPXR in vivo, and the presence of PXR, especially mPXR, is associated with altered histopathology and increased clearance of NP.« less

Nonylphenol-mediated CYP induction is PXR-dependent: The use of humanized mice and human hepatocytes suggests that hPXR is less sensitive than mouse PXR to nonylphenol treatment

PubMed Central

Mota, Linda C; Barfield, Christina; Hernandez, Juan P; Baldwin, William S.

2011-01-01

Nonylphenol (NP), a by-product of alkylphenol ethoxylates, is a pervasive surfactant that activates the xenosensing nuclear receptor, the pregnane X-receptor (PXR) in transactivation assays in vitro. We are interested in determining if NP activates PXR in vivo, determining if hPXR and mPXR act similarly, and investigating the role of PXR in protecting individuals from NP. Wild-type (WT), PXR-null, and humanized PXR (hPXR) mice were treated with NP at 0, 50 or 75 mg/kg/day for one week, and cytochrome P450 (CYP) induction, liver histopathology, and serum NP concentrations were examined. WT mice treated with NP showed induction of Cyp2b, and male-specific induction of Cyp2c and Cyp3a. CYPs were not induced in PXR-null mice, demonstrating that PXR is necessary for NP-mediated CYP induction. CAR-mediated CYP induction was not observed in the PXR-null mice despite previous data demonstrating NP is also a CAR activator. hPXR mice only showed moderate Cyp induction, suggesting that hPXR is not as sensitive to NP as mPXR in vivo. NP-mediated Cyp3a induction from three human hepatocyte donors was not significant, confirming that hPXR is not very sensitive to NP-mediated CYP induction. Lastly, mice with PXR (mPXR and hPXR) showed lower NP serum concentrations than PXR-null mice treated with NP suggesting that PXR plays a role in decreasing liver toxicity by basally regulating Phase I-III detoxification enzymes that promote the metabolism and elimination of NP. In summary, PXR is required for NP-mediated CYP-induction, and mPXR mediates greater CYP induction than hPXR in vivo, and the presence of PXR, especially mPXR, is associated with altered histopathology and increased clearance of NP. PMID:21376070

Potential hazards of environmental contaminants to avifauna residing in the Chesapeake Bay estuary

USGS Publications Warehouse

Rattner, Barnett A.; McGowan, Peter C.

2007-01-01

A search of the Contaminant Exposure and Effects-Terrestrial Vertebrates (CEE-TV) database revealed that 70% of the 839 Chesapeake Bay records deal with avian species. Studies conducted on waterbirds in the past 15 years indicate that organochlorine contaminants have declined in eggs and tissues, although p,p'-DDE, total polychlorinated biphenyls (PCBs) and coplanar PCB congeners may still exert sublethal and reproductive effects in some locations. There have been numerous reports of avian die-off events related to organophosphorus and carbamate pesticides. More contemporary contaminants (e.g., alkylphenols, ethoxylates, perfluorinated compounds, polybrominated diphenyl ethers) are detectable in bird eggs in the most industrialized portions of the Bay, but interpretation of these data is difficult because adverse effect levels are incompletely known for birds. Two moderaterized oil spills resulted in the death of several hundred birds, and about 500 smaller spill events occur annually in the watershed. With the exception of lead, concentrations of cadmium, mercury, and selenium in eggs and tissues appear to be below toxic thresholds for waterbirds. Fishing tackle and discarded plastics, that can entangle and kill young and adults, are prevalent in nests in some Bay tributaries. It is apparent that exposure and potential effects of several classes of contaminants (e.g., dioxins, dibenzofurans, rodenticides, pharmaceuticals, personal care products, lead shot, and some metals) have not been systematically examined in the past 15 years, highlighting the need for toxicological evaluation of birds found dead, and perhaps an avian ecotoxicological monitoring program. Although oil spills, spent lead shot, some pesticides, and industrial pollutants occasionally harm Chesapeake avifauna, contaminants no longer evoke the population level effects that were observed in Ospreys (Pandion haliaetus) and Bald Eagles (Haliaeetus leucocephalus) through the 1970s.

Development of a multiple-class analytical method based on the use of synthetic matrices for the simultaneous determination of commonly used commercial surfactants in wastewater by liquid chromatography-tandem mass spectrometry.

PubMed

Alexandre, Bergé; Barbara, Giroud; Laure, Wiest; Bruno, Domenjoud; Adriana, Gonzalez-Ospina; Emmanuelle, Vulliet

2016-06-10

Discharges of surfactants from wastewater treatment plants are often considered as the principal vector of pollution into the environment. The analysis of complex matrices, such as urban wastewater, suspended solids and biological sludge requires careful preparation of the sample to obtain a sensitive, selective and reproducible analysis. A simple, fast, effective and multi-residue method based on the SPE (water) and QuEChERS (solid matrices) approaches using synthetic matrices for validation and quantification, has been developed for the determination of 16 surfactants in wastewater, suspended solids and biological sludge. This work resulted in an innovative method that was validated to detect and assess several classes of surfactants such as quaternary ammonium compounds, betaïns, alkylphenols and their ethoxylated or sulfated derivatives in urban wastewater and solid matrices. The optimised extraction method exhibited recoveries comprised between 83% and 120% for all the tested compounds in the dissolved matrix and between 50% and 109% for particulate matrix. The limits of quantification of all compounds were comprised between 0.1 and 1.0μg/L for dissolved matrix and between 2 and 1000ng/g (dry weight) in particulate matrix. Linearity was assessed for all compounds within the [LOQ-250LOQ] range. Confidence intervals were also computed in real matrices with less than 15% margin of error for all studied surfactants. This work has confirmed, first and foremost, that surfactants are indeed highly concentrated in urban wastewater. As expected, linear alkylbenzene sulfonates were present at significant concentrations (up to 1-2mg/L). In addition, although biological processing results in significant removal of the total pollution, the residual concentrations at output of WWTP remain significant (up to 100μg/L). Copyright © 2016 Elsevier B.V. All rights reserved.

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

NASA Technical Reports Server (NTRS)

Kumar, Nitin; Couzis, Alex; Maldareili, Charles; Singh, Bhim (Technical Monitor)

2001-01-01

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which

Hoechst plans Mexican unit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, A.; Alperowicz, N.

1996-05-22

Hoechst is considering plans to build its first ethoxylates project in Mexico, Mark Sijthoff, head of surfactants and auxiliaries for Hoechst`s specialty chemical business unit, tells CW. The company expects to make a decision on the 30,000-m.t./year project by the end of the year. Sijthoff would not disclose the site or where ethylene oxide (EO) feed would be obtained. The plan may depend on results of the privatization of Petroleos Mexicanos (Pemex), which is the only producer of EO in Mexico. Hoechst is part of a consortium bidding on the privatization. Sources say the unit will be built at Quimicamore » Hoechst`s Coatzacoalcos site, close to Pemex`s EO plants at Cangregera and Morelos. A planned EO expansion at Morelos will probably move ahead when the sell-off is completed. Sijthoff says that Hoechst is also looking at improving its US surfactants position, although the company has no plans to expand ethoxylates, as there is {open_quotes}plenty of capacity.{close_quotes} Hoechst started up a 150-million lbs/year plant at Clear Lake, TX last year, ending a tolling agreement with Union Carbide. In addition, Rhone-Poulenc recently started a unit at Marcus Hook, PA, and Condea Vista is doubling its ethoxylation capacity at Lake Charles, LA. Meanwhile, Hoechst is still considering construction of 30,000-m.t./year ethoxylation plant in India or China. A decision is expected later this year.« less

Quality survey of natural mineral water and spring water sold in France: Monitoring of hormones, pharmaceuticals, pesticides, perfluoroalkyl substances, phthalates, and alkylphenols at the ultra-trace level.

PubMed

Le Coadou, Laurine; Le Ménach, Karyn; Labadie, Pierre; Dévier, Marie-Hélène; Pardon, Patrick; Augagneur, Sylvie; Budzinski, Hélène

2017-12-15

The aim of the present study, one of the most complete ever performed in France, was to carry out an extensive survey on the potential presence of a large amount of emerging contaminants in 40 French bottled waters, including parent compounds and metabolites. The studied samples represented 70% of the French bottled water market in volume. Six classes of compounds were investigated, most of them being unregulated in bottled waters: pesticides and their transformation products (118), pharmaceutical substances (172), hormones (11), alkylphenols (APs) (8), phthalates (11) and perfluoroalkyl substances (PFAS) (10). One of the objectives of this work was to achieve low and reliable limits of quantification (LOQs) (87% of the LOQs were below 10ng/L) using advanced analytical technologies and reliable sample preparation methodologies, including stringent quality controls. Among the 14,000 analyses performed, 99.7% of the results were below the LOQs. None of the hormones, pharmaceutical substances and phthalates were quantified. Nineteen compounds out of the 330 investigated were quantified in 11 samples. Eleven were pesticides including 7 metabolites, 6 were PFAS and 2 were APs. As regards pesticides, their sum was at least twice lower than the quality standards applicable for bottled waters in France. The presence of a majority of pesticide metabolites suggested a former use in the recharge areas of the exploited aquifers. The quantification of a few unregulated emerging compounds at the nano-trace level, such as PFAS, raised the issue of their potential sources, including long-range atmospheric transport and deposition. This study confirmed that the groundwater aquifers exploited for bottling were well-preserved from chemicals, as compared to less geologically protected groundwaters, and also underlined the need to pursue the protection policies implemented in recharge areas in order to limit the anthropogenic pressure. Copyright © 2016. Published by Elsevier B.V.

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River.

PubMed

Chen, Xiaojiao; Chen, Minjian; Xu, Bo; Tang, Rong; Han, Xiumei; Qin, Yufeng; Xu, Bin; Hang, Bo; Mao, Zhilei; Huo, Weiwei; Xia, Yankai; Xu, Zhengfeng; Wang, Xinru

2013-09-01

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR)=2.09, 95% Confidence Interval (CI), 1.05-4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR=2.21, 95% CI, 1.02-4.80; OR=2.81, 95% CI, 1.39-5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans. Copyright © 2013 Elsevier Ltd. All rights reserved.

An organic thin film photodiode as a portable photodetector for the detection of alkylphenol polyethoxylates by a flow fluorescence-immunoassay on magnetic microbeads in a microchannel.

PubMed

Ishimatsu, Ryoichi; Naruse, Azusa; Liu, Rong; Nakano, Koji; Yahiro, Masayuki; Adachi, Chihaya; Imato, Toshihiko

2013-12-15

An organic thin film photodiode (OPD) was successfully employed as a portable photodetector in a competitive enzyme-linked immunosorbent assay (ELISA) of a class of nonionic surfactants, namely alkylphenol polyethoxylates (APnEOs) which are an environmental pollutant. Microbeads that were chemically immobilized with an anti-APnEOs antibody were used in the assay. The OPD consisted of a layer of copper phthalocyanine (CuPc), C60 and a second layer of bathocuproine (BCP) with a bulk heterojunction composed of CuPc and C60 prepared by a vapor deposition method on an indium-tin oxide coated glass substrate. The OPD showed an incident photon-current efficiency (IPCE) of approximately 19% for light at a wavelength of 585 nm. This relatively high IPCE at 585 nm makes it suitable for detecting the fluorescence of resorufin (λem=585 nm), the product of the competitive ELISA, produced through the enzymatic reaction of Amplex Red with horseradish peroxidase (HRP) and H2O2. A fluorometric detector was assembled on a microchip by combining the fabricated OPD and a commercial LED as a photodetector and a light source, respectively. The photocurrent of the OPD due to the fluorescence of resorufin was proportional to the concentration of resorufin in the concentration range from 0 to 8 μM. When the fabricated OPD was used as a portable photodetector, the competitive ELISA of APnEOs using HRP labeled APnEOs (HRP-APnEOs) was performed on magnetic microbeads on which surface an anti-APnEOs antibody had been immobilized. A typical sigmoidal calibration curve was obtained and the data were in good agreement with a numerical simulation, where the photocurrent of the OPD was plotted against the concentration of APnEOs, determined via the competitive ELISA. The detection limit of the immunoassay for APnEOs was approximately 2 and 4 ppb in batch and flow system, respectively. © 2013 Elsevier B.V. All rights reserved.

Determination of homologous distributions of bisEMA dimethacrylates in bulk-fill resin-composites by GC-MS.

PubMed

Durner, Jürgen; Schrickel, Klaus; Watts, David C; Ilie, Nicoleta

2015-04-01

Ethoxylated bisphenol A dimethacrylate (bisEMA) is a basis monomer in several dental resin composites. It was the aim of the present study to develop a method allowing detection of bisEMA and its different degrees of ethoxylation eluted from polymerized resin composites. High-temperature gas chromatography/mass spectrometry (HT-GC/MS) by direct on-column injection was used to identify ethoxylated bisEMA in ethanol/water (3:1) eluates from polymerized specimen of four bulk-fill resin composites - Venus(®) bulk fill, Surefil(®) SDR™ flow, Filtek™ Bulk Fill and Sonic Fill™. Additionally, the unpolymerised pastes were analysed. The developed method allowed identification of a homologous series of bisEMA up to twelve ethoxy groups in the unpolymerised materials. The molecular masses of the homologous bisEMA varied between 452 g/mol and 892 g/mol and were detected for retention times from 9.43 min to 13.36 min. Analysis of eluates from polymerised materials identified bisEMA monomers with less than 6 ethoxy groups. Chromatograms showed larger peak areas for the lower volatile bisEMA with 4-6 ethoxy groups compared with higher volatile bisEMA with 2 or 3 ethoxy groups, thus indicating that the amounts of these homologues in the pastes were higher. Ethoxylated bisEMA with up to twelve ethoxy groups can be identified by HT-GC/MS. In all eluates bisEMA was found. The higher the number of ethoxy groups the lower are the peak areas from bisEMA in the gas chromatogram. These findings may be significant for toxicological analysis of resin-composites incorporating bis-EMA. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Sorption and degradation of petroleum hydrocarbons, polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachate using sand, activated carbon and peat filters.

PubMed

Kalmykova, Yuliya; Moona, Nashita; Strömvall, Ann-Margret; Björklund, Karin

2014-06-01

Landfill leachates are repeatedly found contaminated with organic pollutants, such as alkylphenols (APs), phthalates and polycyclic aromatic hydrocarbons (PAHs) at levels exceeding water quality standards. It has been shown that these pollutants may be present in the colloidal and truly dissolved phase in contaminated water, making particle separation an inefficient removal method. The aim of this study was to investigate sorption and degradation of petroleum hydrocarbons (PHCs), selected APs, bisphenol A (BPA), phthalates and PAHs from landfill leachate using sand, granulated activated carbon (GAC) and peat moss filters. A pilot plant was installed at an inactive landfill with mixed industrial and household waste and samples were collected before and after each filter during two years. Leachate pre-treated in oil separator and sedimentation pond failed to meet water quality standards in most samples and little improvement was seen after the sand filter. These techniques are based on particle removal, whereas the analysed pollutants are found, to varying degrees, bound to colloids or dissolved. However, even highly hydrophobic compounds expected to be particle-bound, such as the PHCs and high-molecular weight PAHs, were poorly removed in the sand filter. The APs and BPA were completely removed by the GAC filter, while mass balance calculations indicate that 50-80% of the investigated phenols were removed in the peat filter. Results suggest possible AP degradation in peat filters. No evidence of phthalate degradation in the landfill, pond or the filters was found. The PHCs were completely removed in 50% and 35% of the measured occasions in the GAC and peat filters, respectively. The opposite trend was seen for removal of PAHs in GAC (50%) and peat (63%). Oxygenated PAHs with high toxicity were found in the leachates but not in the pond sediment. These compounds are likely formed in the pond water, which is alarming because sedimentation ponds are commonly used

Absorption properties of carbon dioxide enhanced-oil-recovery additives. Final Technical report, 12 May 1987-31 August 1989

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patton, J.T.; Holbrook, S.T.

1990-01-01

The selection of the optimum foaming agent (surfactant) for enhancing oil production by carbon dioxide flooding is based on foamability and adsorption. Measurement of adsorption on carbonate cores from New Mexico reservoirs showed large adsorption differences between three commercial, high-foaming surfactants. An ethoxylated alcohol structure was least adsorbed, 0.64 mg/cc pore volume; an ethoxylated alcohol sulfate was next, 0.74 mg/cc pore volume; the highest adsorbed was a glyceryl sulfonate, 2.30 mg/cc pore volume. Commercial application of the foaming additive involves injecting alternate slugs of surfactant solution and carbon dioxide. Surfactant concentration should be determined to allow for the adsorption above.

A Fungal P450 (CYP5136A3) Capable of Oxidizing Polycyclic Aromatic Hydrocarbons and Endocrine Disrupting Alkylphenols: Role of Trp129 and Leu324

PubMed Central

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Yadav, Jagjit S.

2011-01-01

The model white rot fungus Phanerochaete chrysosporium, which is known for its versatile pollutant-biodegradation ability, possesses an extraordinarily large repertoire of P450 monooxygenases in its genome. However, the majority of these P450s have hitherto unknown function. Our initial studies using a genome-wide gene induction strategy revealed multiple P450s responsive to individual classes of xenobiotics. Here we report functional characterization of a cytochrome P450 monooxygenase, CYP5136A3 that showed common responsiveness and catalytic versatility towards endocrine-disrupting alkylphenols (APs) and mutagenic/carcinogenic polycyclic aromatic hydrocarbons (PAHs). Using recombinant CYP5136A3, we demonstrated its oxidation activity towards APs with varying alkyl side-chain length (C3-C9), in addition to PAHs (3–4 ring size). AP oxidation involves hydroxylation at the terminal carbon of the alkyl side-chain (ω-oxidation). Structure-activity analysis based on a 3D model indicated a potential role of Trp129 and Leu324 in the oxidation mechanism of CYP5136A3. Replacing Trp129 with Leu (W129L) and Phe (W129F) significantly diminished oxidation of both PAHs and APs. The W129L mutation caused greater reduction in phenanthrene oxidation (80%) as compared to W129F which caused greater reduction in pyrene oxidation (88%). Almost complete loss of oxidation of C3-C8 APs (83–90%) was observed for the W129L mutation as compared to W129F (28–41%). However, the two mutations showed a comparable loss (60–67%) in C9-AP oxidation. Replacement of Leu324 with Gly (L324G) caused 42% and 54% decrease in oxidation activity towards phenanthrene and pyrene, respectively. This mutation also caused loss of activity towards C3-C8 APs (20–58%), and complete loss of activity toward nonylphenol (C9-AP). Collectively, the results suggest that Trp129 and Leu324 are critical in substrate recognition and/or regio-selective oxidation of PAHs and APs. To our knowledge, this is the first

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Monomethyl Ether *Dimer Acids Dioxane Ethane Ethylene Glycol Monophenyl Ether *Ethoxylates, Misc. Ethylene Glycol Dimethyl Ether Ethylene Glycol Monobutyl Ether Ethylene Glycol Monoethyl Ether Ethylene Glycol...

Adsorption properties of carbon dioxide enchanced oil recovery additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patton, J.T.; Holbrook, S.T.

1990-01-01

The selection of the optimum foaming agent (surfactant) for enhancing oil production by carbon dioxide flooding is based on foamability and adsorption. Measurements of adsorption on carbonate cores from New Mexico reservoirs showed large adsorption differences between three commercial, high-foaming surfactants. An ethoxylated alcohol structure was at least adsorbed, 0.64 mg/cc pore volume; an ethoxylated alcohol sulfate was next, 0.74 mg/cc pore volume; the highest adsorbed was a glyceryl sulfonate, 2.30 mg/cc pore volume. Commercial application of the foaming additive involves injecting alternate slugs of surfactant solution and carbon dioxide. Surfactant concentration should be determined to allow for the adsorptionmore » above. 9 refs., 27 figs., 6 tabs.« less

Natural Attenuation of Nonionic Surfactants Used in Hydraulic Fracturing Fluids: Degradation Rates, Pathways, and Mechanisms.

PubMed

Heyob, Katie M; Blotevogel, Jens; Brooker, Michael; Evans, Morgan V; Lenhart, John J; Wright, Justin; Lamendella, Regina; Borch, Thomas; Mouser, Paula J

2017-12-05

Hydraulic fracturing fluids are injected into shales to extend fracture networks that enhance oil and natural gas production from unconventional reservoirs. Here we evaluated the biodegradability of three widely used nonionic polyglycol ether surfactants (alkyl ethoxylates (AEOs), nonylphenol ethoxylates (NPEOs), and polypropylene glycols (PPGs)) that function as weatherizers, emulsifiers, wetting agents, and corrosion inhibitors in injected fluids. Under anaerobic conditions, we observed complete removal of AEOs and NPEOs from solution within 3 weeks regardless of whether surfactants were part of a chemical mixture or amended as individual additives. Microbial enzymatic chain shortening was responsible for a shift in ethoxymer molecular weight distributions and the accumulation of the metabolite acetate. PPGs bioattenuated the slowest, producing sizable concentrations of acetone, an isomer of propionaldehyde. Surfactant chain shortening was coupled to an increased abundance of the diol dehydratase gene cluster (pduCDE) in Firmicutes metagenomes predicted from the 16S rRNA gene. The pduCDE enzymes are responsible for cleaving ethoxylate chain units into aldehydes before their fermentation into alcohols and carboxylic acids. These data provide new mechanistic insight into the environmental fate of hydraulic fracturing surfactants after accidental release through chain shortening and biotransformation, emphasizing the importance of compound structure disclosure for predicting biodegradation products.

A survey of emerging contaminants in the estuarine receiving environment around Auckland, New Zealand.

PubMed

Stewart, Michael; Olsen, Greg; Hickey, Christopher W; Ferreira, Bianca; Jelić, Aleksandra; Petrović, Mira; Barcelo, Damia

2014-01-15

Increasing urbanisation in the future will put mounting stresses on the receiving environments around those urban centres due to increased sedimentation and contaminant runoff. Emerging contaminants (ECs) are an extensive array of chemicals and many are not under regulatory action. Within New Zealand likely future pressures from ECs will be in both urban centres and rural areas due to intensive agriculture, although at present there is a lack of information on the state of the environment in both sectors. This study was initiated to gauge the distribution of ECs in the urban environment by measuring concentrations of flame retardants, plasticisers, alkylphenols, herbicides and pesticides, steroid oestrogens, pharmaceuticals and heavy metals in sediment from 13 estuarine sites around Auckland, New Zealand's biggest city. Total polybrominated diphenyl ether (PBDE) flame retardant concentrations ((7)ΣPBDE) ranged from 0.55 to 573 ng/g (dw). The phthalate plasticiser di(2-ethylhexyl)phthalate (DEHP) was measured at up to 11,500 ng/g from one site. Nonylphenol (NP) was found at up to 32,000 ng/g at one site adjacent to the city's major wastewater treatment plant (WWTP). However, median concentrations of NP were 153 ng/g, suggesting this site was not representative of the region. Nonylphenol mono- and di-ethoxylates (NPEO1,2) had highest concentrations (1600 ng/g) at a marina. Highest glyphosate concentrations (up to 950 ng/g) were observed at residential sites. Steroid oestrogens were detected at extremely low concentrations (maximum 2.2 ng/g), while all other pesticides or herbicides were not detected at any sites. Multi-residue analysis of 46 pharmaceuticals showed presence of 21 compounds at one or more sites, with average concentrations ranging from 0.16 to 7.66 ng/g. Generally, environmental concentrations of ECs were similar to those reported world-wide. However, comparisons for pharmaceuticals were problematic, due to very few studies on pharmaceutical

Effects of Surfactant on the Transport of Toxoplasma gondii in Saturated Sandy Porous Media: Experimental Tests and Modeling

NASA Astrophysics Data System (ADS)

Darnault, C. J. G.; Mutty, T.; L'Ollivier, C.; Dubey, J. P.; Aurélien, D.; Pullano, C. P.

2017-12-01

Understanding the transport of pathogens in the subsurface environment is essential for the risk assessment of groundwater contamination and the potential threat to human health. Currently, there is a lack of research in particular concerning the fate and transport of Toxoplasma gondii in porous media. The purpose of this research will be to characterize and model the transport and retention of Toxoplasma gondii in saturated silica-sand porous media in the presence of surfactant. Surfactants are chemicals commonly used as detergents and soaps, however they are able to impact flow properties in porous media and the interactions between surfaces, such as oocysts walls with sand grains. Therefore, we chose to characterize the changes that two surfactants have on the transport and fate of T. gondii. A total of 14 Column experiments were conducted including replicates as follows: 6 columns with an anionic-surfactant solution, 6 with a nonionic-surfactant solution, and 2 columns without surfactant to act as controls. All of the columns contained fine sand as the dominant grain size and each was run with a specified saturated flow rate in order to analyze the change with surfactant and disregard change as a result of a variation in the pore velocity. We chose to determine the retention and flow using the classic clean-bed colloid filtration model, and implemented sources for both adsorption and desorption of the particles which is known to happen on other biocolloids including oocysts. We implemented both Linear alkylbenzene sulphonic acid and Alkylphenol ethoxylate as our surfactants since they are the anionic and nonionic surfactants most commonly found in wastewater. Three different Critical Micelle Concentrations (CMC's) were run through the columns prior to the T. gondii oocysts injection followed by sequential injection of surfactant only and then deionized water only. The study compares the breakthrough of T. gondii with surfactant, without surfactant, as well as a

Hoechst readies US capacity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Coeyman, M.

1995-02-08

Hoechst Celanese`s (Somerville, NJ) 150 million lbs/year alcohol ethoxylates plant at Clear lake, TX is in start-up and has begun trial production. The company says it plans to begin shipping product to customers by the end of the first quarter. The plant replaces production facilities previously leased from Union Carbide at Texas City. Meanwhile, Union Carbide has completed the purchase of certain ICI ethylene oxide (EO) derivatives businesses, including ethylene glycol, glycol ethers and acetates, ethanomalamines, and brake fluids. ICI will retain the ethoxylates business. Carbide and ICI will jointly fund an expansion of an EO unit and Wilton, U.K.more » from 240,000 m.t./year to 300,000 m.t./year.« less

ACADEMY OF SCIENCES AZERBAYDZHAN. INSTITUTE OF ADDITIVE CHEMISTRY. ADDITIVES AND LUBRICANTS, QUESTIONS OF SYNTHESIS, RESEARCH ON THE APPLICATION OF ADDITIVES AND LUBRICANTS, FUELS, AND POLYMER MATERIALS (SELECTED ARTICLES),

DTIC Science & Technology

an alkylphenol ); Synthesis and investigation of the new antioxidative INKhP-40 Additive; Synthesis and investigation of N-butylurethane-based antioxidative additive; and Synthesis of mixed esters of dithiophosphoric acid.

Effects of alkylphenols on the biotransformation of diuron and enzymes involved in the synthesis and clearance of sex steroids in juvenile male tilapia (Oreochromus mossambica).

PubMed

Felício, Andréia A; Crago, Jordan; Maryoung, Lindley A; Almeida, Eduardo A; Schlenk, Daniel

2016-11-01

Previous studies using in vivo bioassay guided fractionation indicated that the herbicide diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and alkylphenol (AP)-containing surfactants were detected in fractions of extracts that induced the estrogenic biomarker, vitellogenin in fish exposed to surface water extracts from the United States. However, when the compounds were evaluated individually using in vivo estrogenic assays or in vitro estrogen receptor assays, estrogenic activity was not observed. Since APs have been shown to alter activity and content of cytochrome P450s (CYP) which convert diuron to potential estrogenic metabolites, the hepatic biotransformation of diuron was measured with and without a 7day pretreatment of p-Octylphenol (OP) and p-Nonylphenol (NP) at low (OP 13ng/L+NP 91ng/L), and high concentrations (OP 65ng/L+NP 455ng/L) in juvenile male Nile tilapia (Oreochromus niloticus). Pre-treatment with the OP/NP (AP) mixture caused elevated levels of NADPH-catalyzed formation of 3,4-dichlorophenyl-N-methylurea (DCPMU) but not 3,4-dichlorophenylurea (DCPU). Fish were also treated with nominal concentrations of low (40ng/L) and high (200ng/L) diuron and each of its three degradates/metabolites: DCPMU, DCPU and 3,4-dichloroaniline (DCA). Additional treatments were conducted with APs and Diuron as a mixture at the low concentrations which mimicked concentrations observed in surface waters. Hepatic vitellogenin (Vtg) mRNA was induced by exposure to the high concentrations of Diuron, as well as DCPMU and DCPU in both concentrations. Brain cytochrome P450 aromatase activity was generally diminished by diuron, its metabolites, and the AP/diuron mixtures. 17β-Hydroxysteroid dehydrogenase (17βHSD) levels were also reduced by DCPMU and DCA in the lower concentrations, but not by higher concentrations. While the AP mixture reduced 17βHSD, the AP/diuron mixture induced testosterone (T) biosynthesis at the single concentration tested. Although CYP3A expression

Do the monomers release from the composite resins after artificial aging?

PubMed

Tokay, Ugur; Koyuturk, Alp Erdin; Aksoy, Abdurrahman; Ozmen, Bilal

2015-04-01

The aim of this study is to measure the effect of thermal cycling on the amount of monomer released from three different composite materials by HPLC analysis method. Three different composite materials, inlay composite, posterior composite and micro-hybrid composite were used. Sixty cylinder specimens each with a dimension of approximately 1 cm width and 3 mm depth, were prepared before experiments were carried out. Inlay composite material was polymerized according to manufacturers' instructions. Thermal cycling device was used to simulate thermal differences which occur in the mouth media. Monomers were analyzed using HPLC technic after thermal cycling process. The amount of ethoxylated Bis-GMA and urethane dimethacrylate (UDMA) in inlay composite material, the amount of ethoxylated Bis-GMA in posterior composite material, the amount of ethoxylated Bis-GMA and triethyleneglycol dimethacrylate (TEGDMA) in micro-hybrid composite material were investigated. Monomer release of thermal cycles levels showed a linear increase in UDMA and TEGDMA (P < 0.05). In terms of thermal cycles levels, Bis-EMA released from posterior composite showed a cubic change (P < 0.001). It was observed that use of additional polymerization processes might have positive effect on the decrease of residual monomer. In the light of the results, we suggest that indirect composite resins have more outstanding features than direct composite resins in terms of biocompatibility. © 2015 Wiley Periodicals, Inc.

JD-2000™

EPA Pesticide Factsheets

Technical product bulletin: this dispersant used in oil spill cleanups is free of phosphates, aromatic chlorinated solvents, branched ethoxylated alcohols, and hydrotreated distillates. Timely application even at low rates can counter mousse forming.

HCN1 Channels as Targets for Anesthetic and Nonanesthetic Propofol Analogs in the Amelioration of Mechanical and Thermal Hyperalgesia in a Mouse Model of Neuropathic Pain

PubMed Central

Tibbs, Gareth R.; Rowley, Thomas J.; Sanford, R. Lea; Herold, Karl F.; Proekt, Alex; Hemmings, Hugh C.; Andersen, Olaf S.; Flood, Pamela D.

2013-01-01

Chronic pain after peripheral nerve injury is associated with afferent hyperexcitability and upregulation of hyperpolarization-activated, cyclic nucleotide-regulated (HCN)–mediated IH pacemaker currents in sensory neurons. HCN channels thus constitute an attractive target for treating chronic pain. HCN channels are ubiquitously expressed; analgesics targeting HCN1-rich cells in the peripheral nervous system must spare the cardiac pacemaker current (carried mostly by HCN2 and HCN4) and the central nervous system (where all four isoforms are expressed). The alkylphenol general anesthetic propofol (2,6-di-iso-propylphenol) selectively inhibits HCN1 channels versus HCN2–HCN4 and exhibits a modest pharmacokinetic preference for the periphery. Consequently, we hypothesized that propofol, and congeners, should be antihyperalgesic. Alkyl-substituted propofol analogs have different rank-order potencies with respect to HCN1 inhibition, GABAA receptor (GABAA-R) potentiation, and general anesthesia. Thus, 2,6- and 2,4-di-tertbutylphenol (2,6- and 2,4-DTBP, respectively) are more potent HCN1 antagonists than propofol, whereas 2,6- and 2,4-di-sec-butylphenol (2,6- and 2,4-DSBP, respectively) are less potent. In contrast, DSBPs, but not DTBPs, enhance GABAA-R function and are general anesthetics. 2,6-DTBP retained propofol’s selectivity for HCN1 over HCN2–HCN4. In a peripheral nerve ligation model of neuropathic pain, 2,6-DTBP and subhypnotic propofol are antihyperalgesic. The findings are consistent with these alkylphenols exerting analgesia via non-GABAA-R targets and suggest that antagonism of central HCN1 channels may be of limited importance to general anesthesia. Alkylphenols are hydrophobic, and thus potential modifiers of lipid bilayers, but their effects on HCN channels are due to direct drug-channel interactions because they have little bilayer-modifying effect at therapeutic concentrations. The alkylphenol antihyperalgesic target may be HCN1 channels in the

Perfluorinated Compounds In The Ohio River Basin

EPA Science Inventory

Contaminants of emerging concern (CECs) in waterways include pharmaceuticals and personal care products (PPCPs), alkylphenols, endocrine disrupting chemicals (EDCs) and perfluorinated alkyl compounds (PFCs). Their distributions and persistence in the aquatic environment remain p...

Lubricating Lapping Fluid,

DTIC Science & Technology

35-36% conservation grease containing (%): oidized petrolatum 2.5, lithium hydroxide 0.3, synthetic rubber 1.0, barium disulfide alkylphenolate 2.5, calcium sulfonate 10, diphenyl amine 0.3 and mineral oil to 100%. (Author)

Mass spectral analysis of long chain alkyl aromatic compounds synthesized from alpha-olefin alkylation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, M.T.; Hudson, J.D.

1994-12-31

Long chain alkyl aromatic compounds are important petrochemicals with many applications. They are generally synthesized by alkylating the corresponding aromatic nucleus. In this report, the authors will describe the mass spectral fragmentation of alkylphenols and alkylsalicylates.

Mineralization of Surfactants by the Microbiota of Submerged Plant Detritus

PubMed Central

Federle, Thomas W.; Ventullo, Roy M.

1990-01-01

In wetlands and canopied bodies of water, plant detritus is an important source of carbon and energy. Detrital materials possess a large surface area for sorption of dissolved organics and are colonized by a large and diverse microbiota. To examine the biodegradation of surfactants by these microorganisms, submerged oak leaves were obtained from a laundromat wastewater pond, its overflow, and a pristine control pond. Leaves were cut into disks and incubated in sterile water amended with 50 μg of 14C-labeled linear alkylbenzene sulfonate (LAS), linear alcohol ethoxylate, stearyltrimethyl ammonium chloride, distearyldimethyl ammonium chloride, benzoic acid, or mixed amino acids per liter. Sorption of the test compounds to the detritus and evolution of 14CO2 were followed with time. All of the compounds sorbed to the detritus to various degrees, with LAS and stearyltrimethyl ammonium chloride the most sorptive and benzoic acid the least. All compounds were mineralized without a lag. With leaves from the laundromat wastewater pond, half-lives were 12.6 days for LAS, 8.4 days for linear alcohol ethoxylate, 14.2 days for stearyltrimethyl ammonium chloride, 1.0 days for benzoic acid, and 2.7 days for mixed amino acids. Mineralization of LAS and linear alcohol ethoxylate by control pond leaves was slower and exhibited an S-shaped rather than a typical first-order pattern. This study shows that detritus represents a significant site of surfactant removal in detritus-rich systems. Images PMID:16348111

Mineralization of surfactants by the microbiota of submerged plant detritus.

PubMed

Federle, T W; Ventullo, R M

1990-02-01

In wetlands and canopied bodies of water, plant detritus is an important source of carbon and energy. Detrital materials possess a large surface area for sorption of dissolved organics and are colonized by a large and diverse microbiota. To examine the biodegradation of surfactants by these microorganisms, submerged oak leaves were obtained from a laundromat wastewater pond, its overflow, and a pristine control pond. Leaves were cut into disks and incubated in sterile water amended with 50 mug of C-labeled linear alkylbenzene sulfonate (LAS), linear alcohol ethoxylate, stearyltrimethyl ammonium chloride, distearyldimethyl ammonium chloride, benzoic acid, or mixed amino acids per liter. Sorption of the test compounds to the detritus and evolution of CO(2) were followed with time. All of the compounds sorbed to the detritus to various degrees, with LAS and stearyltrimethyl ammonium chloride the most sorptive and benzoic acid the least. All compounds were mineralized without a lag. With leaves from the laundromat wastewater pond, half-lives were 12.6 days for LAS, 8.4 days for linear alcohol ethoxylate, 14.2 days for stearyltrimethyl ammonium chloride, 1.0 days for benzoic acid, and 2.7 days for mixed amino acids. Mineralization of LAS and linear alcohol ethoxylate by control pond leaves was slower and exhibited an S-shaped rather than a typical first-order pattern. This study shows that detritus represents a significant site of surfactant removal in detritus-rich systems.

Simple and rapid analysis of endocrine disruptors in liquid medicines and intravenous injection solutions by automated in-tube solid-phase microextraction/high performance liquid chromatography.

PubMed

Mitani, Kurie; Narimatsu, Shizuo; Izushi, Fumio; Kataoka, Hiroyuki

2003-07-14

A simple and rapid method was developed for analyzing contamination of endocrine disruptors in liquid medicines and intravenous injection solutions. Endocrine disrupting compounds such as bisphenol A (BPA), alkylphenols and phthalates were quantitated by on-line in-tube solid-phase microextraction coupled with high performance liquid chromatography (in-tube SPME/HPLC) with UV detection. The liquid medicines and intravenous injection solutions could be used directly without any pretreatment, and the BPA, alkylphenols and phthalates in these solutions were automatically analyzed. The limits of quantification for these compounds were 1-10 ng/ml. Recoveries of these compounds spiked to the intravenous injection solutions was over 80%, except for some phthalates. Di-n-butyl phthalate (DBP) was detected at a concentration of 7-60 ng/ml in most intravenous injection solutions in plastic containers, but it was not detected in solutions in glass bottles. Diethyl phthalate, di-n-propyl phthalate, DBP and di-2-ethylhexyl phthalate (DEHP) were also detected in syrup, lotion and eye drops in plastic containers. On the other hand, BPA and alkylphenols were not detected at all in these solutions. DEHP contamination from an administration set increased when total vitamin formulation was added to the infusion solution. DEHP was easily leached from polyvinyl chloride tubing by polysorbate 80. The in-tube SPME/HPLC method is simple, rapid and automatic, and it provides a useful tool for the screening and determination of endocrine disruptor contamination in liquid medicines and intravenous injection solutions.

Fact Sheet: Nonylphenols and Nonylphenol Ethoxylates

EPA Pesticide Factsheets

EPA's existing chemicals programs address pollution prevention, risk assessment, hazard and exposure assessment and/or characterization, and risk management for chemicals substances in commercial use.

Oxidation of octylphenol by ferrate(VI).

PubMed

Anquandah, George A K; Sharma, Virender K

2009-01-01

The rates of the oxidation of octylphenols (OP) by potassium ferrate(VI) (K(2)FeO(4)) in water were determined as a function of pH (8.0-10.9) at 25 degrees C. The rate law for the oxidation of OP by Fe(VI) was found to be first order with each reactant. The observed second-order rate constants, k(obs), for the oxidation of alkylphenols decreased with an increase in pH. The speciation of Fe(VI) (HFeO(4)(-) and FeO(4)(2 -)) and OP (OP-OH and OP-O(-)) species were used to determine individual rate constants of the reactions. Comparison of rate constants and half-lives of oxidation of OP by Fe(VI) with nonylphenol (NP) and bisphenol-A (BPA) were conducted to demonstrate that Fe(VI) efficiently oxidizes environmentally relevant alkylphenols in water.

Tree nut phytochemicals: composition, antioxidant capacity, bioactivity, impact factors. A systematic review of almonds, Brazils, cashews, hazelnuts, macadamias, pecans, pine nuts, pistachios and walnuts

USDA-ARS?s Scientific Manuscript database

Tree nuts contain an array of phytochemicals including carotenoids, phenolic acids, phytosterols and polyphenolic compounds such as flavonoids, proanthocyanidins (PAC) and stilbenes, all of which are included in nutrient databases, as well as phytates, sphingolipids, alkylphenols and lignans, which ...

Contaminants Of Emerging Concern Within The Ohio River And Its Tributaries

EPA Science Inventory

Contaminants of emerging concern such as PPCPs, alkylphenols, EDCs, and PFCs in waterways have been increasing public concern. The extent and persistence of their occurrence in surface waters remains unclear. Though ther are many sources of these contaminants, research has focu...

Contaminants Of Emerging Concern Within The Mainstem Of The Ohio River And its Tributaries

EPA Science Inventory

Contaminants of emerging concern such as PPCPs, alkylphenols, EDCs, and PFCs in waterways have been of increasing public concern. The extent and persistence of their occurrence in surface waters remains unclear. Though there are many sources of these contaminants, research has ...

Asymmetrical flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry for sizing SeNPs for packaging applications

NASA Astrophysics Data System (ADS)

Palomo-Siguero, María; Vera, Paula; Echegoyen, Yolanda; Nerin, Cristina; Cámara, Carmen; Madrid, Yolanda

2017-06-01

This paper describes the application of Asymmetrical Flow Field-Flow Fractionation (AF4) coupled to diode array detector (DAD) and inductively coupled plasma mass spectrometry (AF4-UV-ICP-MS) to characterize selenium nanoparticles (SeNPs) in an aqueous acrylic adhesive to be used in a multilayer food packaging material. SeNPs were synthesized using a solution-phase approach based on the reduction of selenite with ascorbic acid in presence of different stabilizers compatible with food industry such as polysaccharides (chitosan (poly(D-glucosamine) and hydroxyethylcellulose (HEC)) and non-ionic surfactants (Triton X-100 (t-octylphenoxypolyethoxyethanol), 2,4,7,9-tetramethyl 5decyne-4,7-diol ethoxylate, and isotridecanol ethoxylate). Several parameters such as pH, ascorbic acid and stabilizers concentration, and compatibility of the stabilizer with the adhesive were evaluated. SeNPs suspensions with spherical morphology were obtained except when isotridecanol ethoxylate was employed which provides SeNPs with a nanorod morphology. AF4-DAD-ICP-MS was further applied for sizing the different SeNPs preparations. DAD was used as detector for selecting the best AF4 separation conditions before coupling to ICP-MS to ensure unequivocal identification of NPs. AF4 calibration with polystyrene latex (PSL) beads of known sizes allowed size determination of the different SeNPs. The following estimated hydrodynamic sizes (expressed as the mean ± standard deviation, n = 6 replicates) were found: chitosan-SeNPs- (26 ± 3 nm), TritonX100-SeNPs (22 ± 10 nm) HEC- SeNPs (91 ± 8 nm) and 2,4,7,9-tetramethyl 5decyne-4,7-diol ethoxylate- SeNPs (59 ± 4 nm). The proposed methodology was successfully applied to the characterization in terms of size of aqueous acrylic adhesives containing SeNPs Results from AF4-ICP-MS and TEM shown that only those SeNPs obtained with non-ionic surfactants and HEC were compatible with the adhesive. The results reported here evidence the usefulness of AF4-ICP

76 FR 53372 - Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or on Various...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-26

... requirement of a tolerance for residues of 2- propanoic acid, 2-methyl-, polymer with methyl 2-methyl-2... of a tolerance for residues of Nonylphenol Ethoxylate Phosphate and Sulfate Derivatives (NPEPSD...-49-1). NPE Sulfate Derivatives (NPESD): [alpha]-(p-nonylphenol)-[omega]- hydroxypoly(oxyethylene...

In Vitro Assessment of Eight Oil Dispersants for Estrogenic, Androgenic, Anti-androgenic and Cytotoxicity in Cell-Based Assays.

EPA Science Inventory

Large amounts of dispersants have been used on the oil from the Deepwater Horizon spill and concern has arisen about the toxicity of the dispersants. Some of the dispersants reportedly contain nonylphenol ethoxylates which can degrade to estrogenic compounds, thus the potential...

ACUTE TOXICITY OF PARA-NONYLPHENOL TO SALTWATER ANIMALS

EPA Science Inventory

?para-Nonylphenol (PNP), a mixture of alkylphenols used in producing nonionic surfactants, is distributed widely in surface waters and aquatic sediments, where it can affect saltwater species. This article describes a database for acute toxicity of PNP derived for calculating a n...

Comparison of Relative Binding Affinities for Trout and Human Estrogen Receptor Based upon Different Competitive Binding Assays

EPA Science Inventory

The development of a predictive model based upon a single aquatic species inevitably raises the question of whether this information is valid for other species. To partially address this question, relative binding affinities (RBA) for six alkylphenols (para-substituted, n- and b...

The determination of nonylphenol and its precursors in a trickling filter wastewater treatment process.

PubMed

Petrie, Bruce; McAdam, Ewan J; Whelan, Mick J; Lester, John N; Cartmell, Elise

2013-04-01

An ultra performance liquid chromatography method coupled to a triple quadrupole mass spectrometer was developed to determine nonylphenol and 15 of its possible precursors (nonylphenol ethoxylates and nonylphenol carboxylates) in aqueous and particulate wastewater matrices. Final effluent method detection limits for all compounds ranged from 1.4 to 17.4 ng l(-1) in aqueous phases and from 1.4 to 39.4 ng g(-1) in particulate phases of samples. The method was used to measure the performance of a trickling filter wastewater treatment works, which are not routinely monitored despite their extensive usage. Relatively good removals of nonylphenol were observed over the biological secondary treatment process, accounting for a 53 % reduction. However, only an 8 % reduction in total nonylphenolic compound load was observed. This was explained by a shortening in ethoxylate chain length which initiated production of shorter polyethoxylates ranging from 1 to 4 ethoxylate units in length in final effluents. Modelling the possible impact of trickling filter discharge demonstrated that the nonylphenol environmental quality standard may be exceeded in receiving waters with low dilution ratios. In addition, there is a possibility that the EQS can be exceeded several kilometres downstream of the mixing zone due to the biotransformation of readily degradable short-chained precursors. This accentuates the need to monitor 'non-priority' parent compounds in wastewater treatment works since monitoring nonylphenol alone can give a false indication of process performance. It is thus recommended that future process performance monitoring and optimisation is undertaken using the full suite of nonylphenolic moieties which this method can facilitate.

Determination of Wastewater Compounds in Sediment and Soil by Pressurized Solvent Extraction, Solid-Phase Extraction, and Capillary-Column Gas Chromatography/Mass Spectrometry

USGS Publications Warehouse

Burkhardt, Mark R.; Zaugg, Steven D.; Smith, Steven G.; ReVello, Rhiannon C.

2006-01-01

A method for the determination of 61 compounds in environmental sediment and soil samples is described. The method was developed in response to increasing concern over the effects of endocrine-disrupting chemicals in wastewater and wastewater-impacted sediment on aquatic organisms. This method also may be used to evaluate the effects of combined sanitary and storm-sewer overflow on the water and sediment quality of urban streams. Method development focused on the determination of compounds that were chosen on the basis of their endocrine-disrupting potential or toxicity. These compounds include the alkylphenol ethoxylate nonionic surfactants and their degradates, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclic aromatic hydrocarbons, and high-use domestic pesticides. Sediment and soil samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from interfering matrix components by high-pressure water/isopropyl alcohol extraction. The compounds were isolated using disposable solid-phase extraction (SPE) cartridges containing chemically modified polystyrene-divinylbenzene resin. The cartridges were dried with nitrogen gas, and then sorbed compounds were eluted with methylene chloride (80 percent)-diethyl ether (20 percent) through Florisil/sodium sulfate SPE cartridge, and then determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-sand samples fortified at 4 to 72 micrograms averaged 76 percent ?13 percent relative standard deviation for all method compounds. Initial method reporting levels for single-component compounds ranged from 50 to 500 micrograms per kilogram. The concentrations of 20 out of 61 compounds initially will be reported as estimated with the 'E' remark code for one of three reasons: (1) unacceptably low-biased recovery (less than 60 percent) or highly variable method performance

21 CFR 177.1400 - Hydroxyethyl cellulose film, water-insoluble.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Hydroxyethyl cellulose film, water-insoluble. 177... cellulose film, water-insoluble. Water-insoluble hydroxyethyl cellulose film may be safely used for... cellulose film consists of a base sheet manufactured by the ethoxylation of cellulose under controlled...

75 FR 27434 - [alpha]-(p-Nonylphenol)-[omega]-hydroxypoly(oxyethylene) Sulfate and Phosphate Esters; Time...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-17

.... study with the reproduction/ developmental toxicity screening test in rats (NPEPSD) LOAEL = 300 mg/kg... toxicity screening test. In the Harmonized Guideline 870.3650 study with the nonylphenol ethoxylate... Guideline 870.3650 study in rats following pre- and post-natal exposure to NPEPSDs. E. Aggregate Risks and...

Characterization of polyoxyethylene tallow amine surfactants in technical mixtures and glyphosate formulations using ultra-high performance liquid chromatography and triple quadrupole mass spectrometry

USGS Publications Warehouse

Tush, Daniel; Loftin, Keith A.; Meyer, Michael T.

2013-01-01

Little is known about the occurrence, fate, and effects of the ancillary additives in pesticide formulations. Polyoxyethylene tallow amine (POEA) is a non-ionic surfactant used in many glyphosate formulations, a widely applied herbicide both in agricultural and urban environments. POEA has not been previously well characterized, but has been shown to be toxic to various aquatic organisms. Characterization of technical mixtures using ultra-high performance liquid chromatography (UHPLC) and mass spectrometry shows POEA is a complex combination of homologs of different aliphatic moieties and ranges of ethoxylate units. Tandem mass spectrometry experiments indicate that POEA homologs generate no product ions readily suitable for quantitative analysis due to poor sensitivity. A comparison of multiple high performance liquid chromatography (HPLC) and UHPLC analytical columns indicates that the stationary phase is more important in column selection than other parameters for the separation of POEA. Analysis of several agricultural and household glyphosate formulations confirms that POEA is a common ingredient but ethoxylate distributions among formulations vary.

Effect of oxygen compounds addition on the hydrocracking of coal derived liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sato, Yoshiki; Kodera, Yoichi; Kamo, Tohru

1998-12-31

Coal derived liquid from liquefaction, coking and low temperature pyrolysis contains considerable amounts of alkylphenols with alkylbenzenes and alkylnaphthalenes. To produce and purify useful chemicals from coal-derived liquid, hydrocracking and hydrotreating of alkylphenol mixture is a very important process. In this study the effects of oxygen compounds such as dimethylcarbonate (DMC) addition on the hydrocracking of alkylphenols and coal-derived liquid were investigated to decrease hydrogen consumption due to the production of water from the removal of OH group. From the hydrocracking of 3,5-dimethylphenol (3,5-DMP) without DMC at 700 C, residence time of 3--10 sec under hydrogen-to-reactant molar ratio of moremore » than 10 using atmospheric flow apparatus with quartz reactor, m-xylene and m-cresol were produced with the production ratio of 1:1.8. However the dehydroxylation to produce m-xylene was decreased by the addition of 10% DMC with the 50% increased production ratio of 1:2.7. These are considered due to the strong interaction between OH group and DMC. Similar reaction behavior was observed in the hydrocracking of 2,5-DMP and the production ratio of (o-cresol + m-cresol)/p-xylene slightly increased from 3.0 to 3.5 by the addition of DMC. On the other hand, the products distribution did not change with and without DMC in the case of 2,6-DMP. This indicates the interaction is hindered by steric effect by the neighboring CH{sub 3} group. The effect of other oxygen compounds on the hydrocracking and the products distribution from the hydrocracking of coal-derived liquids is also discussed.« less

DETERMINATION OF SURFACTANT SODIUM LAURYL ETHER SULFATE BY ION PAIRING CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY DETECTION

EPA Science Inventory

A method for the determination of the anionic Steol CS-330 surfactant is described. CS-330 is a complex mixture of oligomers due to the various sizes of fatty alcohols and the number of moles of the ethoxylation. The main component of CS-330 is sodium lauryl ether sulfate (SLES)....

40 CFR 721.5800 - Sulfurized alkylphenol.

Code of Federal Regulations, 2010 CFR

2010-07-01

... information on methods for protecting against such risk, into an MSDS as described in § 721.72(c) within 90... Section 721.5800 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... substance is any manner or method of manufacture, import, or processing associated with any use of this...

Toxicity Ranking and Toxic Mode of Action Evaluation of Commonly Used Agricultural Adjuvants on the Basis of Bacterial Gene Expression Profiles

PubMed Central

Nobels, Ingrid; Spanoghe, Pieter; Haesaert, Geert; Robbens, Johan; Blust, Ronny

2011-01-01

The omnipresent group of pesticide adjuvants are often referred to as “inert” ingredients, a rather misleading term since consumers associate this term with “safe”. The upcoming new EU regulation concerning the introduction of plant protection products on the market (EC1107/2009) includes for the first time the demand for information on the possible negative effects of not only the active ingredients but also the used adjuvants. This new regulation requires basic toxicological information that allows decisions on the use/ban or preference of use of available adjuvants. In this study we obtained toxicological relevant information through a multiple endpoint reporter assay for a broad selection of commonly used adjuvants including several solvents (e.g. isophorone) and non-ionic surfactants (e.g. ethoxylated alcohols). The used assay allows the toxicity screening in a mechanistic way, with direct measurement of specific toxicological responses (e.g. oxidative stress, DNA damage, membrane damage and general cell lesions). The results show that the selected solvents are less toxic than the surfactants, suggesting that solvents may have a preference of use, but further research on more compounds is needed to confirm this observation. The gene expression profiles of the selected surfactants reveal that a phenol (ethoxylated tristyrylphenol) and an organosilicone surfactant (ethoxylated trisiloxane) show little or no inductions at EC20 concentrations, making them preferred surfactants for use in different applications. The organosilicone surfactant shows little or no toxicity and good adjuvant properties. However, this study also illustrates possible genotoxicity (induction of the bacterial SOS response) for several surfactants (POEA, AE, tri-EO, EO FA and EO NP) and one solvent (gamma-butyrolactone). Although the number of compounds that were evaluated is rather limited (13), the results show that the used reporter assay is a promising tool to rank commonly used

75 FR 27443 - [alpha]-[p-(1,1,3,3-Tetramethylbutyl)phenyl]-[omega]- hydroxypoly(oxyethylene); Time-Limited...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-17

... infants and children in the case of threshold effects to account for pre-natal and post-natal toxicity and... the choice of a different factor. 2. Pre-natal and post-natal sensitivity. In the case of octylphenol ethoxylate, there was no increased susceptibility to the offspring of rats following pre-natal and post-natal...

Growth of Pseudomonas sp. TX1 on a wide range of octylphenol polyethoxylate concentrations and the formation of dicarboxylated metabolites.

PubMed

Lin, Yi-Wen; Guo, Gia-Luen; Hsieh, Hsiao-Cheng; Huang, Shir-Ly

2010-04-01

Pseudomonas sp. TX1, is able to use octylphenol polyethoxylates (OPEO(n), or Triton X-100; average n = 9.5) as a sole carbon source. It can grow on 0.05-20% of OPEO(n) with a specific growth rate of 0.34-0.44 h(-1). High-performance liquid chromatography-mass spectrometer analysis of OPEO(n) degraded metabolites revealed that strain TX1 was able to shorten the ethoxylate chain and produce octylphenol (OP). Furthermore, formation of the short carboxylate metabolites, such as carboxyoctylphenol polyethoxylates (COPEO(n), n = 2, 3) and carboxyoctylphenol polyethoxycarboxylates (COPEC(n), n = 2, 3) began at the log stage, while octylphenol polyethoxycarboxylates (OPEC(n), n = 1-3) was formed at the stationary phase. All the short-ethoxylated metabolites, OPEO(n), OPEC(n), COPEO(n), and COPEC(n), accumulated when the cells were in the stationary phase. This study is the first to demonstrate the formation of COPEO(n) and COPEC(n) from OPEO(n) by an aerobic bacterium. Copyright 2009 Elsevier Ltd. All rights reserved.

Combined effects of pharmaceuticals, personal care products, biocides and organic contaminants on the growth of Skeletonema pseudocostatum.

PubMed

Petersen, Karina; Heiaas, Harald Hasle; Tollefsen, Knut Erik

2014-05-01

Organisms in the environment are exposed to a number of pollutants from different compound groups. In addition to the classic pollutants like the polychlorinated biphenyls, polyaromatic hydrocarbons (PAHs), alkylphenols, biocides, etc. other compound groups of concern are constantly emerging. Pharmaceuticals and personal care products (PPCPs) can be expected to co-occur with other organic contaminants like biocides, PAHs and alkylphenols in areas affected by wastewater, industrial effluents and intensive recreational activity. In this study, representatives from these four different compound groups were tested individually and in mixtures in a growth inhibition assay with the marine algae Skeletonema pseudocostatum (formerly Skeletonema costatum) to determine whether the combined effects could be predicted by models for additive effects; the concentration addition (CA) and independent action (IA) prediction model. The eleven tested compounds reduced the growth of S. pseudocostatum in the microplate test in a concentration-dependent manner. The order of toxicity of these chemicals were irgarol>fluoxetine>diuron>benzo(a)pyrene>thioguanine>triclosan>propranolol>benzophenone 3>cetrimonium bromide>4-tert-octylphenol>endosulfan. Several binary mixtures and a mixture of eight compounds from the four different compound groups were tested. All tested mixtures were additive as model deviation ratios, the deviation between experimental and predicted effect concentrations, were within a factor of 2 from one or both prediction models (e.g. CA and IA). Interestingly, a concentration dependent shift from IA to CA, potentially due to activation of similar toxicity pathways at higher concentrations, was observed for the mixture of eight compounds. The combined effects of the multi-compound mixture were clearly additive and it should therefore be expected that PPCPs, biocides, PAHs and alkylphenols will collectively contribute to the risk in areas contaminated by such complex

Alkyl Phenols and Diethylhexyl Phthalate in Tissues of Sheep Grazing Pastures Fertilized with Sewage Sludge or Inorganic Fertilizer

PubMed Central

Rhind, Stewart M.; Kyle, Carol E.; Telfer, Gillian; Duff, Elizabeth I.; Smith, Alistair

2005-01-01

We studied selected tissues from ewes and their lambs that were grazing pastures fertilized with either sewage sludge (treated) or inorganic fertilizer (control) and determined concentrations of alkylphenols and phthalates in these tissues. Mean tissue concentrations of alkylphenols were relatively low (< 10–400 μg/kg) in all animals and tissues. Phthalates were detected in tissues of both control and treated animals at relatively high concentrations (> 20,000 μg/kg in many tissue samples). The use of sludge as a fertilizer was not associated with consistently increased concentrations of either alkylphenols or phthalates in the tissues of animals grazing treated pastures relative to levels in control animal tissues. Concentrations of the two classes of chemicals differed but were of a similar order of magnitude in liver and muscle as well as in fat. Concentrations of each class of compound were broadly similar in tissues derived from ewes and lambs. Although there were significant differences (p < 0.01 or p < 0.001) between years (cohorts) in mean tissue concentrations of both nonylphenol (NP) and phthalate in each of the tissues from both ewes and lambs, the differences were not attributable to either the age (6 months or 5 years) of the animal or the duration of exposure to treatments. Octylphenol concentrations were generally undetectable. There was no consistent cumulative outcome of prolonged exposure on the tissue concentrations of either class of pollutant in any ewe tissue. Mean tissue concentrations of phthalate were higher (p < 0.001) in the liver and kidney fat of male compared with female lambs. We suggest that the addition of sewage sludge to pasture is unlikely to cause large increases in tissue concentrations of NP and phthalates in sheep and other animals with broadly similar diets and digestive systems (i.e., domestic ruminants) grazing such pasture. PMID:15811823

On-site GC/MS analysis of Chapman gasification separator liquor. Final report Jul 80-Mar 81

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thielen, C.J.; Magee, R.A.; Collins, R.V.

1981-08-01

The report gives results of a characterization of a wastewater stream from a coal gasification plant, using on-site extraction and GC/MS analysis. Extractable material in the wastewater was primarily phenols and alkylphenols, accounting for about 99% of the total mass identified. Several polynuclear aromatic compounds were also identified. The composition of the sample deteriorated even though the water was held in amber bottles at 4C: this was most evident in the concentration of dimethylphenols which dropped about 75% during 2 weeks of refrigerated storage. Ambient sample storage produced a greater decrease in the concentration of phenol, but did not appearmore » to affect the alkylphenols or the base/neutral compounds as much. The observed changes in composition should hamper any off-site wastewater treatbility studies with waters of this type. Diisopropyl ether (DIPE) extraction confirmed the 99-plus % removal efficiency of phenol which had been demonstrated in previous studies. Wet oxidation removed organics almost as efficiently as DIPE extraction, but may have limited use because of its high operating cost.« less

Chemicals of emerging concern in the Great Lakes Basin: an analysis of environmental exposures.

PubMed

Klecka, Gary; Persoon, Carolyn; Currie, Rebecca

2010-01-01

This review and statistical analysis was conducted to better understand the nature and significance of environmental exposures in the Great Lakes Basin and watershed to a variety of environmental contaminants. These contaminants of interest included current-use pesticides, pharmaceuticals, organic wastewater contaminants, alkylphenol ethoxylates, perfluorinated surfactants, flame retardants, and chlorinated paraffins. The available literature was critically reviewed and used to develop a database containing 19,611 residue values for 326 substances. In many papers, sampling locations were characterized as being downstream from municipal wastewater discharges, receiving waters for industrial facilities, areas susceptible to agricultural or urban contamination, or harbors and ports. To develop an initial assessment of their potential ecological significance, the contamination levels found were compared with currently available regulatory standards, guidelines, or criteria. This review was prepared for the IJC multi-board work group, and served as background material for an expert consultation, held in March, 2009, in which the significance of the contaminants found was discussed. Moreover, the consultation attempted to identify and assess opportunities for strengthening future actions that will protect the Great Lakes. Based on the findings and conclusions of the expert consultation, it is apparent that a wide variety of chemicals of emerging concern have been detected in environmental media (air, water, sediment, biota) from the Great Lakes Basin, although many are present at only trace levels. Although the presence of these contaminants raises concerns in the public and among the scientific community, the findings must be placed in context. Significant scientific interpretation is required to understand the extent to which these chemicals may pose a threat to the ecosystem and to human health. The ability to detect chemicals in environmental media greatly surpasses

Final report on the safety assessment of octoxynol-1, octoxynol-3, octoxynol-5, octoxynol-6, octoxynol-7, octoxynol-8, octoxynol-9, octoxynol-10, octoxynol-11, octoxynol-12, octoxynol-13, octoxynol-16, octoxynol-20, octoxynol-25, octoxynol-30, octoxynol-33, octoxynol-40, octoxynol-70, octoxynol-9 carboxylic acid, octoxynol-20 carboxylic acid, potassium octoxynol-12 phosphate, sodium octoxynol-2 ethane sulfonate, sodium octoxynol-2 sulfate, sodium octoxynol-6 sulfate, and sodium octoxynol-9 sulfate.

PubMed

Johnson, Wilbur

2004-01-01

Octoxynols are ethoxylated alkylphenols in which the size of the molecule is related to the number of moles of ethylene oxide used in synthesis. Reactions are performed at elevated temperature, under pressure, and in the presence of NaOH. It is possible that the synthesis may leave trace amounts of ethylene oxide, 1,4-dioxane, and unreacted C9 phenols. Octoxynols of various chain lengths as well as octoxynol salts and organic acids function in cosmetics either as surfactants--emulsifying agents, surfactants--cleansing agents, surfactant--solubilizing agents, or surfactants--hydrotropes in a wide variety of cosmetic products at concentrations ranging from 0.0008% to 25%, with most less than 5.0%. The octoxynols are chemically similar to nonoxynols, the safety of which were previously considered. Long-chain nonoxynols (9 and above) were considered safe as used, whereas short-chain nonoxynols (8 and below) were considered safe as used in rinse-off products and safe at concentrations less than 5% in leave-on formulations. Acute exposure of hamsters to Octoxynol-9 by bronchopulmonary lavage produced pneumonia, pulmonary edema, and intra-alveolar hemorrhage. Octoxynol-9 at doses over 1 g/kg was toxic in rats and in mice in acute oral toxicity studies. No significant effects were noted in short-term oral studies of Octoxynol-9 in rats, in subchronic oral studies of Octoxynol-40 in rats and dogs, or in chronic oral studies of Octoxynol-40 in rats. The intraperitoneal LD50 of Octoxynol-9 in rats and mice was around 100 mg/kg. In skin irritation studies, octoxynols ranged from nonirritating to moderately irritating. Octoxynols were not ocular irritants in one rabbit study, but in others there was ocular irritation. No immune system toxicity in CF-1 female mice was noted following the intraperitoneal injection of Octoxynol-9 followed by subcutaneous immunization with sheep red blood cells (SRBCs). Octoxynol-9 produced no humoral and cell-mediated immune responses, or

21 CFR 172.834 - Ethoxylated mono- and diglycerides.

Code of Federal Regulations, 2013 CFR

2013-04-01

... emulsions intended for use as substitutes for milk or cream in beverage coffee Not to exceed 0.4 percent by weight of the finished vegetable fat-water emulsions. (d) When the name “polyglycerate 60” is used in...

21 CFR 172.834 - Ethoxylated mono- and diglycerides.

Code of Federal Regulations, 2012 CFR

2012-04-01

... emulsions intended for use as substitutes for milk or cream in beverage coffee Not to exceed 0.4 percent by weight of the finished vegetable fat-water emulsions. (d) When the name “polyglycerate 60” is used in...

21 CFR 172.834 - Ethoxylated mono- and diglycerides.

Code of Federal Regulations, 2014 CFR

2014-04-01

... of the finished frozen desserts. 6. As an emulsifier in edible vegetable fat-water emulsions intended... finished vegetable fat-water emulsions. (d) When the name “polyglycerate 60” is used in labeling it shall...

21 CFR 172.834 - Ethoxylated mono- and diglycerides.

Code of Federal Regulations, 2011 CFR

2011-04-01

... emulsifier in whipped vegetable oil toppings and topping mixes Not to exceed 0.45 percent by weight of the finished whipped vegetable oil toppings. 4. As an emulsifier in icings and icing mixes Not to exceed 0.5... by weight of the finished frozen desserts. 6. As an emulsifier in edible vegetable fat-water...

In vitro OECD test methods applied to screen the estrogenic effect of chemicals, used in Korea.

PubMed

Lee, Hee-Seok; Park, Eun-Jung; Han, Songyi; Oh, Gyeong-Yong; Kim, Min-Hee; Kang, Hui-Seung; Suh, Jin-Hyang; Oh, Jae-Ho; Lee, Kwang-Soo; Hwang, Myung-Sil; Moon, Guiim; Hong, Jin-Hwan; Hwang, In-Gyun

2016-09-01

In this study, 27 chemicals found in household products, which became an issue in Korea were screened for the agonistoc and antagonistic effects against human estrogen receptor using official Organization for Economic Cooperation and Development (OECD) in vitro assays, STTA assay using ERα-HeLa-9903 cell line and BG1Luc ER TA assay. In the case of human ER agonist screening by two assays, all tested chemicals did not show agonist effect against ER. In ER antagonist test by BG1Luc ER TA assay, five surfactants α-dodecyl-ω-hydroxypoly(oxyethylene), alcohols C16-18 ethoxylated, nonylphenol, ethoxylated, 3,6,9,12,15,18,21-heptaoxatritriacontan-1-ol, and α-dodecyl-ω-hydroxypoly(oxy-1,2-ethanediyl)) were found to exhibit weak antagonistic activities. The agonist/antagonist effects against human estrogen receptor of various chemicals, used in Korea by OECD test guideline are reported in this study. These results indicated that two OECD in vitro assays will can be applied in Korea by screening of agonistic/antagonistic effects against human ER of various chemicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystallization and X-ray analysis of the salmon-egg lectin SEL24K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murata, Kenji; Fisher, Andrew J.; Hedrick, Jerry L., E-mail: jlhedrick@ucdavis.edu

2007-05-01

The 24 kDa egg lectin of Chinook salmon (Oncorhynchus tshawytscha) was purified by affinity chromatography from salmon eggs and crystallized by the hanging-drop vapor-diffusion method using 15/4 EO/OH (pentaerythritol ethoxylate) as a precipitant. The 24 kDa egg lectin of Chinook salmon (Oncorhynchus tshawytscha) is released from the egg during the cortical reaction. The lectin functions in blocking polyspermy during the fertilization process. The egg lectin was purified by affinity chromatography from salmon eggs and crystallized by the hanging-drop vapor-diffusion method using 15/4 EO/OH (pentaerythritol ethoxylate) as a precipitant. The crystal diffracted synchrotron-radiation X-rays to 1.63 Å resolution. The crystal belongsmore » to the monoclinic space group P2{sub 1}, with unit-cell parameters a = 93.0, b = 73.6, c = 113.6 Å, α = 90, β = 92.82, γ = 90°. The crystal is likely to contain eight molecules in the asymmetric unit (V{sub M} = 2.3 Å{sup 3} Da{sup −1}), corresponding to a solvent content of 45.5%. A self-rotation function suggests an arrangement with 222 point symmetry within the asymmetric unit.« less

Assessment of priority pesticides, degradation products, and pesticide adjuvants in groundwaters and top soils from agricultural areas of the Ebro river basin.

PubMed

Hildebrandt, Alain; Lacorte, Sílvia; Barceló, Damià

2007-02-01

Gas chromatography-mass spectrometry (GC/MS) was employed for the determination of 30 widely used pesticides including various transformation products and alkylphenols in water and agricultural soils with the aim of assessing the impact of these compounds in agricultural soils and the underlying aquifer. The extraction, clean-up, and analytical procedures were optimized for both water and soil samples to provide a highly robust method capable of determining target analytes at the ppb-ppt level with high precision. For water samples, different solid-phase extraction cartridges and conditions were optimized; similarly, pressurized liquid extraction conditions were tested to provide interference-free extracts and high sensitivity. Instrumental LODs of 3-4 pg were obtained. The multi-residue extraction procedures were applied to the analysis of groundwaters and agricultural soils from the Ebro river basin (NE Spain). Most ubiquitous herbicides detected were triazines but some acetanilides and organophosphorus pesticides were also found; the pesticide additive tributylphosphate was found in all water samples. Levels varied between 0.57 and 5.37 microg/L in groundwater, whereas nonylphenol was the sole compound detected in soil. Alkylphenols are used as adjuvants in pesticide formulations and are present in sludges employed as soil fertilizers. Occurrence was found to be similar to other environmental studies.

Endocrine-Disrupting Chemicals: Associated Disorders and Mechanisms of Action

PubMed Central

De Coster, Sam; van Larebeke, Nicolas

2012-01-01

The incidence and/or prevalence of health problems associated with endocrine-disruption have increased. Many chemicals have endocrine-disrupting properties, including bisphenol A, some organochlorines, polybrominated flame retardants, perfluorinated substances, alkylphenols, phthalates, pesticides, polycyclic aromatic hydrocarbons, alkylphenols, solvents, and some household products including some cleaning products, air fresheners, hair dyes, cosmetics, and sunscreens. Even some metals were shown to have endocrine-disrupting properties. Many observations suggesting that endocrine disruptors do contribute to cancer, diabetes, obesity, the metabolic syndrome, and infertility are listed in this paper. An overview is presented of mechanisms contributing to endocrine disruption. Endocrine disruptors can act through classical nuclear receptors, but also through estrogen-related receptors, membrane-bound estrogen-receptors, and interaction with targets in the cytosol resulting in activation of the Src/Ras/Erk pathway or modulation of nitric oxide. In addition, changes in metabolism of endogenous hormones, cross-talk between genomic and nongenomic pathways, cross talk with estrogen receptors after binding on other receptors, interference with feedback regulation and neuroendocrine cells, changes in DNA methylation or histone modifications, and genomic instability by interference with the spindle figure can play a role. Also it was found that effects of receptor activation can differ in function of the ligand. PMID:22991565

75 FR 44917 - Castor Oil, Ethoxylated, Dioleate; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-30

... of pesticide use in residential settings. If EPA is able to determine that a finite tolerance is not... of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed in...

75 FR 40751 - Castor Oil, Ethoxylated, Oleate; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-14

... a finite tolerance is not necessary to ensure that there is a reasonable certainty that no harm will... contain as an integral part of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other...

New reagent for extraction photomeric determination of anionic surface-active substances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chernova, R.K.; Yastrebova, N.I.; Pankratov, A.N.

1995-02-01

The new reagent 2,6-diphenyl-4-(4-dimethylamino)styrylpyryl chloride is suggested for extraction photometric determination of anionic surface-active substances (SAS). This reagent possesses high sensitivity and selectivity, and can be used for the determination of both individual SAS of any kind and the total amount of anionic SAS. The reagent was used in analysis of highly mineralized statal waters and for the determination of sulfated products in polyoxyethylated alkylphenols.

Biotransformation of potentially persistent alkylphenols in natural seawater.

PubMed

Lofthus, Synnøve; Almås, Inger K; Evans, Peter; Pelz, Oliver; Brakstad, Odd Gunnar

2016-08-01

Produced water (PW) discharged to the marine environment may contain both natural substances and industrial chemicals that are potentially persistent, bioaccumulating and toxic (PBT). Identification of substances as PBT is dependent upon accurate assessment of biodegradation rates, but these measurements can be impeded where substances exhibit inherently low solubility in water. Examples of substances of this kind include some alkylated phenols (APs). Biotransformation of three APs, suspected to be PBT compounds in PW, was investigated by adopting a new methodology in which they were immobilized to hydrophobic adsorbents submerged in natural seawater. These compounds were not ready biodegradable by conventional screening biochemical oxygen demand (BOD) methods at high concentrations (2 mg/L). However, potential biodegradability for two of the three APs were demonstrated by the immobilization method at low concentrations (appr. 100 μg/L), with biotransformation half-lives <50 days. Thus, standard screening tests should be supplemented by biodegradation methods suited for testing of poorly soluble substances before the persistence of potential PBT substances are defined. Copyright © 2016 Elsevier Ltd. All rights reserved.

Alkylation of phenol by alcohols in the presence of aluminum phenolate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koshchii, V.A.; Kozlikovskii, Ya.B.; Matyusha, A.A.

1988-12-20

The reaction of phenol with alcohols in the presence of aluminum phenolate leads to a mixture of 2- and 4-alkylphenols, of which the former predominate in the case of benzyl, tert-butyl, and cyclohexyl alcohols, and the latter in the case of dimethylphenyl- and diphenylmethylcarbinols. Only triphenyl(4-hydroxyphenyl)-methane is formed during the alkylation of phenol by triphenylcarbinol. In individual experiments the formation of small amounts of alkyl phenyl ethers and 2,6-dialkylphenols was observed.

Nonylphenolethoxylates as Malarial Chloroquine Resistance Reversal Agents

PubMed Central

Crandall, Ian; Charuk, Jeffrey; Kain, Kevin C.

2000-01-01

Malaria-associated morbidity and mortality are increasing because of widespread resistance to one of the safest and least expensive antimalarials, chloroquine. The availability of an inexpensive agent that is capable of reversing chloroquine resistance would have a major impact on malaria treatment worldwide. The interaction of nonylphenolethoxylates (NPEs, commercially available synthetic surfactants) with drug-resistant Plasmodium falciparum was examined to determine if NPEs inhibited the growth of the parasites and if NPEs could sensitize resistant parasites to chloroquine. NPEs inhibited the development of the parasite when present in the low- to mid-micromolar range (5 to 90 μM), indicating that they possess antimalarial activity. Further, the presence of <10 μM concentrations of NPEs caused the 50% inhibitory concentrations for chloroquine-resistant lines to drop to levels (≤12 nM) observed for sensitive lines and generally considered to be achievable with treatment courses of chloroquine. Long-chain (>30 ethoxylate units) NPEs were found to be most active in P. falciparum, which contrasts with previously observed maximal activity of short-chain (∼9 ethoxylate units) NPEs in multidrug-resistant mammalian cell lines. NPEs may be attractive chloroquine resistance reversal agents since they are inexpensive and may be selectively directed against P. falciparum without inhibiting mammalian tissue P glycoproteins. Antimalarial preparations that include these agents may prolong the effective life span of chloroquine and other antimalarials. PMID:10952591

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

NASA Technical Reports Server (NTRS)

Simoneit, B. R.; Leif, R. N.; Ishiwatari, R.

1996-01-01

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.

Influence of heavy metals and 4-nonylphenol on reproductive function in fish.

PubMed

Popek, Włodzimierz; Dietrich, Grzegorz; Glogowski, Jan; Demska-Zakeś, Krystyna; Drag-Kozak, Ewa; Sionkowski, Jan; Łuszczek-Trojan, Ewa; Epler, Piotr; Demianowicz, Wiesław; Sarosiek, Beata; Kowalski, Radosław; Jankun, Małgorzata; Zakeś, Zdzisław; Król, Jarosław; Czerniak, Stanisław; Szczepkowski, Mirosław

2006-01-01

Many industrial and agricultural chemicals (including heavy metals and alkylphenols) present in the environment have adverse effects on the reproductive function in fish. Three studies were conducted to assess toxicity of these chemicals towards reproduction of freshwater fish. It was shown that heavy metals added to the diets accumulate in brain tissue of carp, and this accumulation results in inhibition of the secretion of noradrenaline and stimulation of the secretion of dopamine in the hypothalamus. These processes results in a disturbance of hormonal equilibrium of the hypothalamo-pituitary system, which can unfavorably influence the efficiency of artificial spawning in fish. Quality of salmonid and sturgeon sperm was impaired after in vitro exposure to heavy metals. The degree of this toxic effect was species-specific. It was demonstrated that sperm motility parameters appeared to be good indicators of adverse effects of heavy metals fish sperm. The protection role of seminal plasma against toxic effects of heavy metals was suggested for salmonid fish. Oral application of 4-nonylphenol (NP) disrupted reproduction in pikeperch. In juvenile fish a decrease in the percentage of males and an increase of intersex fish was observed in relation to dose of NP and time of exposure to this alkylphenol. Exposure of adult males to the NP led to the reduction in fecundity, milt quality and fertility.

Design, Synthesis, and Evaluation of Novel 2,6-Disubstituted Phenol Derivatives as General Anesthetics.

PubMed

Qin, Linlin; Ren, Lei; Wan, Songlin; Liu, Guoliang; Luo, Xinfeng; Liu, Zhenhong; Li, Fangqiong; Yu, Yan; Liu, Jianyu; Wei, Yonggang

2017-05-11

A novel series of optically active 2,6-disubstituted alkylphenols with improved anesthetic profiles compared to widely used propofol were synthesized. The incorporation of the cyclopropyl group not only increased the steric effect but also introduced stereoselective effects over their anesthetic properties. Compounds 1, 2, and 6 were selected as potential candidates for further preclinical development including studies of their water-soluble prodrugs. Clinical studies of candidate compound 6 (Haisco HSK3486) as a general anesthetic are being performed in Australia and China.

Human biological monitoring of suspected endocrine-disrupting compounds

PubMed Central

Faniband, Moosa; Lindh, Christian H; Jönsson, Bo AG

2014-01-01

Endocrine-disrupting compounds are exogenous agents that interfere with the natural hormones of the body. Human biological monitoring is a powerful method for monitoring exposure to endocrine disrupting compounds. In this review, we describe human biological monitoring systems for different groups of endocrine disrupting compounds, polychlorinated biphenyls, brominated flame retardants, phthalates, alkylphenols, pesticides, metals, perfluronated compounds, parabens, ultraviolet filters, and organic solvents. The aspects discussed are origin to exposure, metabolism, matrices to analyse, analytical determination methods, determinants, and time trends. PMID:24369128

Designing new functional cosmetic ingredients from polyglycerol, a versatile bio-based platform for improved sustainability.

PubMed

Fevola, Michael J; Sun, Frank C; York, Stacey E

Polyglycerol (PG) is a well-known cosmetic ingredient and important precursor for the synthesis of a variety of cosmetic ingredients, such as surfactants, emulsifiers, and conditioning agents for hair and skin. When derived from renewable resources, PG can provide a more sustainable platform for the development of new ingredients with improved performance in cosmetic applications. This paper will discuss recent advances in the utilization of bio-based PG ingredients as alternatives to traditional ethoxylate chemistries for mild nonionic surfactants, substantive humectants, and micellar thickeners.

Resonance Enhanced Multi-Photon Ionization and Uv-Uv Hole-Burning Spectroscopic Studies of Jet-Cooled Acetanilide Derivatives

NASA Astrophysics Data System (ADS)

Moon, Ceol Joo; Min, Ahreum; Ahn, Ahreum; Lee, Seung Jun; Choi, Myong Yong; Kim, Seong Keun

2013-06-01

Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.

Developmental Toxicity of the Organic Fraction from Hydraulic Fracturing Flowback and Produced Waters to Early Life Stages of Zebrafish ( Danio rerio).

PubMed

He, Yuhe; Sun, Chenxing; Zhang, Yifeng; Folkerts, Erik J; Martin, Jonathan W; Goss, Greg G

2018-03-20

Hydraulic fracturing (HF) has emerged as a major recovery method of unconventional oil and gas reservoirs and concerns have been raised regarding the environmental impact of releases of Flowback and Produced Water (FPW) to aquatic ecosystems. To investigate potential effects of HF-FPW on fish embryo development, HF-FPW samples were collected from two different wells and the organic fractions were isolated from both aqueous and particle phases to eliminate the confounding effects of high salinity. Each organic extract was characterized by non-target analysis with HPLC-Orbitrap-MS, with targeted analysis for polycyclic aromatic hydrocarbons provided as markers of petroleum-affected water. The organic profiles differed between samples, including PAHs and alkyl PAHs, and major substances identified by non-target analysis included polyethylene glycols, alkyl ethoxylates, octylphenol ethoxylates, and other high molecular weight (C 49-79 ) ethylene oxide polymeric material. Zebrafish embryos were exposed to various concentrations of FPW organic extracts to investigate acute (7-day) and developmental toxicity in early life stages. The acute toxicity (LD 50 ) of the extracted FPW fractions ranged from 2.8× to 26× the original organic content. Each extracted FPW fraction significantly increased spinal malformation, pericardial edema, and delayed hatch in exposed embryos and altered the expression of a suite of target genes related to biotransformation, oxidative stress, and endocrine-mediation in developing zebrafish embryos. These results provide novel information on the variation of organic profiles and developmental toxicity among different sources and fractions of HF-FPWs.

Potential of pure and mixed cultures of Cladosporium cladosporioides and Geotrichum candidum for application in bioremediation and detergent industry.

PubMed

Jakovljević, Violeta D; Vrvić, Miroslav M

2018-03-01

The effect of ethoxylated oleyl-cetyl alcohol (Henkel, "Merima", Serbia) on the growth and metabolic activity of Cladosporium cladosporioides , Geotrichum candidum and their mixed culture was in the focus of this paper. The cultures were grown in Czapek-Dox liquid nutrient medium with the addition of 0.5% pollutant and without it. The physico-chemical and biochemical changes of pH, the total biomass dry weight, the quantity of free and total organic acids, proteolytic activity and the quality of carbohydrates were evaluated from 4th to 19th day of fungal growth. The pollutant caused an inhibitory effect on biomass dry weight of C. cladosporioides and G. candidum for 10.36% and 4.65% respectively, and stimulatory effect on biomass of mixed culture for 3.80%. The pollutant had influence on the decrease in pH value of the media in the phase of culture growth, and pH changes were correlated with the amount of excreted total organic acids. The highest quantity of free and total organic acids was noted in media with pollutant of mixed culture and C. cladosporioides , respectively. The alkaline protease activities of C. cladosporioides , G. candidum and mixed culture were enhanced by addition of pollutant for 56.88%, 55.84% and 30.94% respectively. The obtained results indicate the potential of both pure and mixed cultures in mycoremediation environment contaminated by alcohol ethoxylated and detergent industry.

Determination of trace endocrine active phenolic compounds by GC/MS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gang Sun; Geno, P.W.

1997-12-31

4-Nonylphenol ethoxylates (NPEOs) and 4-octylphenol ethoxylates (OPEOs) are widely used as nonionic surfactants, Due to the potential estrogenic properties of these compounds and their biodegradation products, there is increasing concern about their presence in ground and drinking water. To assess their prevalence in drinking and ground water, a simple, highly sensitive and accurate analytical method for determination of trace amounts of 4-nonylphenol, 4-nonylphenol monoethoxylate (NP1EO), 4-nonylphenol diethoxylate (NP2EO), 4-nonylphenol monoethoxycarboxylate (NP1EC), 4-octylphenol, 4-octylphenol monoethoxylate (OP1EO), 4-octylphenol diethoxylate (OP2EO), and other 15 phenolic compounds has been developed and validated. One liter of drinking water sample was extracted and concentrated into dichloromethane.more » The analytes in the extracts were converted to their trimethylsilyl derivatives by reacting with N,O-bis(trimethylsilyl) trifluoroacetamine (BSTFA) and 10 % trimethylchlorosilane (TMCS) at 90{degrees}C. The derivatized extracts were then directly analyzed by gas chromatography-mass spectrometry operating in a selected-ion monitoring mode (GUMS-SIM). Method detection limits (MDLs) were 0.01 to 0.02 {mu}g/L for 4-nonylphenol, NP1EO, 2PNEO; 0.064 {mu}g/L for NP1EC; 0.005 to 0.02 {mu}g/L for 4-octylphenol, OP1EO, OP2EO; and 0.001 to 0.003 {mu}g/L, for other 15 phenolic compounds.« less

Liquid chromatography fractionation with gas chromatography/mass spectrometry and preparative gas chromatography-nuclear magnetic resonance analysis of selected nonylphenol polyethoxylates.

PubMed

Wu, Ze-ying; Rühle, Christian P G; Marriott, Philip J

2011-07-01

Commercial nonylphenol polyethoxylates, designated as NPnEOs, where n is the number of ethoxy groups, comprise a range of ethoxylate groups. According to the starting material nonylphenol, they may also be composed of a complex mix of isomeric nonyl substituents. In order to study more fully the heterogeneity arising from both the ethoxylate and nonyl groups, a mixture of NPnEOs is first fractionated by normal phase liquid chromatography (NPLC) into separate fractions comprising individual ethoxymers, n. Preparative collection of each early elution ethoxymer fraction allows further separation of different isomeric nonyl group components by using analytical gas chromatography/mass spectrometry (GC/MS). The nonyl isomers are not resolved in the NPLC method. The distribution of the isomeric nonyl side chain of different ethoxymers bears close resemblance with each other, and also with the original nonylphenol starting material, although separation efficiency of the nonyl isomers for each ethoxymer decreases with increasing ethoxymer number. Mass spectrometry of the separated isomers display close similarity for presumed equivalent isomers in each fraction, based on elution order of the nonyl isomers. This suggests that each corresponding peak has the same isomer structure. Mass spectra are interpreted based on branching within the nonyl side chain. Preparative GC coupled with MS and nuclear magnetic resonance spectroscopy elucidated the molecular structure of one of the resolved isomers as 4-(1,3-dimethyl-1-propyl-butyl)-phenol diethoxylate. Copyright © 2011 Elsevier B.V. All rights reserved.

Exploring the Behavior and Metabolic Transformations of SeNPs in Exposed Lactic Acid Bacteria. Effect of Nanoparticles Coating Agent

PubMed Central

Palomo-Siguero, Maria; Madrid, Yolanda

2017-01-01

The behavior and transformation of selenium nanoparticles (SeNPs) in living systems such as microorganisms is largely unknown. To address this knowledge gap, we examined the effect of three types of SeNP suspensions toward Lactobacillus delbrueckii subsp. bulgaricus LB-12 using a variety of techniques. SeNPs were synthesized using three types of coating agents (chitosan (CS-SeNPs), hydroxyethyl cellulose (HEC-SeNPs) and a non-ionic surfactant, surfynol (ethoxylated-SeNPs)). Morphologies of SeNPs were all spherical. Transmission electron microscopy (TEM) was used to locate SeNPs in the bacteria. High performance liquid chromatography (HPLC) on line coupled to inductively coupled plasma mass spectrometry (ICP-MS) was applied to evaluate SeNP transformation by bacteria. Finally, flow cytometry employing the live/dead test and optical density measurements at 600 nm (OD600) were used for evaluating the percentages of bacteria viability when supplementing with SeNPs. Negligible damage was detected by flow cytometry when bacteria were exposed to HEC-SeNPs or CS-SeNPs at a level of 10 μg Se mL−1. In contrast, ethoxylated-SeNPs were found to be the most harmful nanoparticles toward bacteria. CS-SeNPs passed through the membrane without causing damage. Once inside, SeNPs were metabolically transformed to organic selenium compounds. Results evidenced the importance of capping agents when establishing the true behavior of NPs. PMID:28783048

Aqueous solubilities of alkylphenols and methoxyphenols at 25 C

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varhanickova, D.; Shiu, W.Y.; Mackay, D.

1995-03-01

The aqueous solubilities of 25 phenolic substances (2-methylphenol; 3-methylphenol; 4-methylphenol; 2,3-dimethylphenol; 2,4-dimethylphenol; 2,5-dimethylphenol; 2,6-dimethylphenol; 3,4-dimethylphenol; 3,5dimethylphenol; 2-ethylphenol: 4-ethylphenol; 2,3,5-trimethylphenol; 2,4,6-trimethylphenol; 3,4,5-trimethylphenol; 4-propylphenol; 2-isopropylphenol; 4-isopropylphenol; 4-butylphenol; 3-tert-butylphenol; 4-tert-butylphenol; 4-hexylphenol; 3,5-di-tert-butylphenol; 4-octylphenol; 3-methoxyphenol; and 4-methoxyphenol) were determined at 25 C, by a conventional shake-flask, batch contacting method with analysis by high-pressure liquid chromatography with LTV detection. Satisfactory agreement was obtained between measured and previously reported solubilities for 10 of these substances. The liquid or supercooled liquid solubilities are satisfactorily correlated with the solute`s LeBas molar volume and with first-order valence molecular connectivity, yielding structure-property relationships that may be useful for predictive purposes.

[Survey of alkylphenols in aquatic environment of Zhujiang Delta].

PubMed

Duan, Jing-chun; Chen, Bing; Mai, Bi-xian; Yang, Qing-shu; Sheng, Guo-ying; Fu, Jia-mo

2004-05-01

The summer contamination of dissolved nonylphenols (NPs) and octylphenol (OP) in surface water of Zhujiang estuary and other rivers of Zhujiang Delta was analyzed. The result reveals that NPs concentration in The Pearl River remains < 20-40 ng/L, apart from the NPs concentrations of the mouth of The Pingzhou Channel the mouth of The Shawan Channel and Hutiaomen reaching a higher level of 98.84, 129.82 and 164.98 ng/L respectively. The Lingding Sea and open sea surface water keep at a lower level with the NPs concentration of < 10-14 ng/L. In terms of OP concentration in The Pearl River, any other sampling location is below LOD 2 ng/L, except for Baiertan, the mouth of The Shawan Channel and Hutiaomen being 2.89, 2.44, 2.12 ng/L respectively and inside Macao harbor being the highest level of 8.54 ng/L. The OP concentrations of The Lingding Sea and open sea surface water are lower than LOD 1 ng/L.

Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

PubMed

Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

2016-06-25

Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%. Copyright © 2016 Elsevier B.V. All rights reserved.

Bisphenol A, 4-tert-octylphenol, and 4-nonylphenol in the Gulf of Gdańsk (Southern Baltic).

PubMed

Staniszewska, Marta; Falkowska, Lucyna; Grabowski, Paweł; Kwaśniak, Justyna; Mudrak-Cegiołka, Stella; Reindl, Andrzej R; Sokołowski, Adam; Szumiło, Emilia; Zgrundo, Aleksandra

2014-10-01

The organic derivatives of phenol are classed as dangerous compounds, and their presence has been detected in surface water, bottom water, phytoplankton, zooplankton, and mussel as well as liver and muscle of fish from the Gulf of Gdańsk and in liver, muscle, and guano of gulls residing in the coastal zone of this basin. The greatest sources of bisphenol A (BPA), 4-tert-octylphenol (OP), and 4-nonylphenol (NP) were found to be the Vistula River and the water purification plant in Dębogórze. In living organisms, concentrations of BPA, OP, and NP ranged between the limit of quantification and several hundred ng g(-1) dry weight (dw), and the highest concentrations were found for BPA. Prolonged alimentary exposure to BPA, OP, and NP in fish and birds was indicated by liver/muscle concentration ratios generally >1. The most influential factors on BPA and alkylphenol concentrations in the tissues of fishes and gulls were mainly diet and habitat. The study confirmed possible bioaccumulation in the food web. High BPA and NP concentrations in guano (≤2,700 and ≤300 ng g(-1) dw, respectively) indicated the ability of birds to detoxify and signalled the reintroduction of these compounds to seawater. Herring, flounder, and cod from the Southern Baltic are a safe food source for human consumption because their BPA and alkylphenol contents are low.

Priority and emerging pollutants in sewage sludge and fate during sludge treatment.

PubMed

Mailler, R; Gasperi, J; Chebbo, G; Rocher, V

2014-07-01

This paper aims at characterizing the quality of different treated sludges from Paris conurbation in terms of micropollutants and assessing their fate during different sludge treatment processes (STP). To achieve this, a large panel of priority and emerging pollutants (n=117) have been monitored in different STPs from Parisian wastewater treatment plants including anaerobic digestion, thermal drying, centrifugation and a sludge cake production unit. Considering the quality of treated sludges, comparable micropollutant patterns are found for the different sludges investigated (in mg/kg DM - dry matter). 35 compounds were detected in treated sludges. Some compounds (metals, organotins, alkylphenols, DEHP) are found in every kinds of sludge while pesticides or VOCs are never detected. Sludge cake is the most contaminated sludge, resulting from concentration phenomenon during different treatments. As regards treatments, both centrifugation and thermal drying have broadly no important impact on sludge contamination for metals and organic compounds, even if a slight removal seems to be possible with thermal drying for several compounds by abiotic transfers. Three different behaviors can be highlighted in anaerobic digestion: (i) no removal (metals), (ii) removal following dry matter (DM) elimination (organotins and NP) and iii) removal higher than DM (alkylphenols - except NP - BDE 209 and DEHP). Thus, this process allows a clear removal of biodegradable micropollutants which could be potentially significantly improved by increasing DM removal through operational parameters modifications (retention time, temperature, pre-treatment, etc.). Copyright © 2014 Elsevier Ltd. All rights reserved.

Semivolatile Endocrine-Disrupting Compounds in Paired Indoor and Outdoor Air in Two Northern California Communities

PubMed Central

2010-01-01

Interest in the health effects of potential endocrine-disrupting compounds (EDCs) that are high production volume chemicals used in consumer products has made exposure assessment and source identification a priority. We collected paired indoor and outdoor air samples in 40 nonsmoking homes in urban, industrial Richmond, CA, and 10 in rural Bolinas, CA. Samples were analyzed by GC-MS for 104 analytes, including phthalates (11), alkylphenols (3), parabens (3), polybrominated diphenyl ether (PBDE) flame retardants (3), polychlorinated biphenyls (PCBs) (3), polycyclic aromatic hydrocarbons (PAHs) (24), pesticides (38), and phenolic compounds (19). We detected 39 analytes in outdoor air and 63 in indoor air. For many of the phenolic compounds, alkylphenols, phthalates, and PBDEs, these represent some of the first outdoor measures and the first analysis of the relative importance of indoor and outdoor sources in paired samples. Data demonstrate higher indoor concentrations for 32 analytes, suggesting primarily indoor sources, as compared with only 2 that were higher outdoors. Outdoor air concentrations were higher in Richmond than Bolinas for 3 phthalates, 10 PAHs, and o-phenylphenol, while indoor air levels were more similar between communities, except that differences observed outdoors were also seen indoors. Indoor concentrations of the most ubiquitous chemicals were generally correlated with each other (4-t-butylphenol, o-phenylphenol, nonylphenol, several phthalates, and methyl phenanthrenes; Kendall correlation coefficients 0.2−0.6, p < 0.05), indicating possible shared sources and highlighting the importance of considering mixtures in health studies. PMID:20681565

Determination of alkylbenzenesulfonate surfactants in groundwater using macroreticular resins and carbon-13 nuclear magnetic resonance spectrometry

USGS Publications Warehouse

Thurman, E.M.; Willoughby, T.; Barber, L.B.; Thorn, K.A.

1987-01-01

Alkylbenzenesulfonate surfactants were determined in groundwater at concentrations as low as 0.3 mg/L. The method uses XAD-8 resin for concentration, followed by elution with methanol, separation of anionic and nonionic surfactants by anion exchange, quantitation by titration, and identification by 13C nuclear magnetic resonance spectrometry. Laboratory standards and field samples containing straight-chain and branched-chain alkylbenzenesulfonates, sodium dodecyl sulfate, and alkylbenzene ethoxylates were studied. The XAD-8 extraction of surfactants from groundwater was completed in the field, which simplified sample preservation and reduced the cost of transporting samples.

Occurrence and temporal variations of TMDD in the river Rhine, Germany.

PubMed

Guedez, Arlen A; Frömmel, Stephan; Diehl, Peter; Püttmann, Wilhelm

2010-02-01

The chemical substance 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) is a non-ionic surfactant used as an industrial defoaming agent and in various other applications. Its commercial name is Surynol 104 and the related ethoxylates are also available as Surfynol 420, 440, 465 and 485 which are characterized by different grades of ethoxylation of TMDD at both hydroxyl functional groups. TMDD and its ethoxylates offer several advantages in waterborne industrial applications in coatings, inks, adhesives as well as in paper industries. TMDD and its ethoxylates can be expected to reach the aquatic environment due its widespread use and its physico-chemical properties. TMDD has previously been detected in several rivers of Germany with concentrations up to 2.5 microg/L. In the United States, TMDD was also detected in drinking water. However, detailed studies about its presence and distribution in the aquatic environment have not been carried out so far. The aim of the present study was the analysis of the spatial and temporal concentration variations of TMDD in the river Rhine at the Rheingütestation Worms (443.3 km). Moreover, the transported load in the Rhine was investigated during two entire days and 7 weeks between November 2007 and January 2008. The sampling was carried out at three different sampling points across the river. Sampling point MWL1 is located in the left part of the river, MWL2 in the middle part, and MWL4 in the right part. One more sampling site (MWL3) was run by the monitoring station until the end of 2006, but was put out of service due to financial constrains. The water at the left side of the river Rhine (MWL1) is influenced by sewage from a big chemical plant in Ludwigshafen and by the sewage water from this city. The water at the right side of the river Rhine (MWL4) is largely composed of the water inflow from river Neckar, discharging into Rhine 14.9 km upstream from the sampling point and of communal and industrial wastewater from the city

Characterization and quantitative analysis of surfactants in textile wastewater by liquid chromatography/quadrupole-time-of-flight mass spectrometry.

PubMed

González, Susana; Petrović, Mira; Radetic, Maja; Jovancic, Petar; Ilic, Vesna; Barceló, Damià

2008-05-01

A method based on the application of ultra-performance liquid chromatography (UPLC) coupled to hybrid quadrupole-time-of-flight mass spectrometry (QqTOF-MS) with an electrospray (ESI) interface has been developed for the screening and confirmation of several anionic and non-ionic surfactants: linear alkylbenzenesulfonates (LAS), alkylsulfate (AS), alkylethersulfate (AES), dihexyl sulfosuccinate (DHSS), alcohol ethoxylates (AEOs), coconut diethanolamide (CDEA), nonylphenol ethoxylates (NPEOs), and their degradation products (nonylphenol carboxylate (NPEC), octylphenol carboxylate (OPEC), 4-nonylphenol (NP), 4-octylphenol (OP) and NPEO sulfate (NPEO-SO4). The developed methodology permits reliable quantification combined with a high accuracy confirmation based on the accurate mass of the (de)protonated molecules in the TOFMS mode. For further confirmation of the identity of the detected compounds the QqTOF mode was used. Accurate masses of product ions obtained by performing collision-induced dissociation (CID) of the (de)protonated molecules of parent compounds were matched with the ions obtained for a standard solution. The method was applied for the quantitative analysis and high accuracy confirmation of surfactants in complex mixtures in effluents from the textile industry. Positive identification of the target compounds was based on accurate mass measurement of the base peak, at least one product ion and the LC retention time of the analyte compared with that of a standard. The most frequently surfactants found in these textile effluents were NPEO and NPEO-SO4 in concentrations ranging from 0.93 to 5.68 mg/L for NPEO and 0.06 to 4.30 mg/L for NPEO-SO4. AEOs were also identified.

Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography-mass spectrometry.

PubMed

Quintana, José Benito; Rodil, Rosario; Muniategui-Lorenzo, Soledad; López-Mahía, Purificación; Prada-Rodríguez, Darío

2007-12-07

The feasibility of stir-bar sorptive extraction (SBSE) followed by liquid desorption in combination with large volume injection (LVI)-in port silylation and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of a broad range of 46 acidic and polar organic pollutants in water samples has been evaluated. The target analytes included phenols (nitrophenols, chlorophenols, bromophenols and alkylphenols), acidic herbicides (phenoxy acids and dicamba) and several pharmaceuticals. Experimental variables affecting derivatisation yield and peak shape as a function of different experimental PTV parameters [initial injection time, pressure and temperature and the ratio solvent volume/N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) volume] were first optimised by an experimental design approach. Subsequently, SBSE conditions, such as pH, ionic strength, agitation speed and extraction time were investigated. After optimisation, the method failed only for the extraction of most polar phenols and some pharmaceuticals, being suitable for the determination of 37 (out of 46) pollutants, with detection limits for these analytes ranging between 1 and 800 ng/L and being lower than 25 ng/L in most cases. Finally, the developed method was validated and applied to the determination of target analytes in various aqueous environmental matrices, including ground, river and wastewater. Acceptable accuracy (70-130%) and precision values (<20%) were obtained for most analytes independently of the matrix, with the exception of some alkylphenols, where an isotopically labelled internal standard would be required in order to correct for matrix effects. Among the drawbacks of the method, carryover was identified as the main problem even though the Twisters were cleaned repeatedly.

RELATIVE BINDING AFINITY OF ALKYLPHENOLS TO RAINBOW TROUT ESTROGEN RECEPTOR

EPA Science Inventory

The USEPA has been mandated to screen industrial chemicals and pesticides for potential endocrine activity. The appropriateness of extrapolating mammalian results to non-mammalian species is uncertain; primarily due to the lack of non-mammalian data for making such an assessment....

In vitro toxicity testing with microplate cell cultures: Impact of cell binding.

PubMed

Gülden, Michael; Schreiner, Jeannine; Seibert, Hasso

2015-06-05

In vitro generated data on toxic potencies are generally based on nominal concentrations. However, cellular and extracellular binding and elimination processes may reduce the available free fraction of a compound. Then, nominal effective concentrations do not represent appropriate measures of toxic exposure in vitro and underestimate toxic potencies. In this study it was investigated whether cell binding can affect the availability of chemicals in microplate based toxicity assays. To this end the cytotoxicity of compounds like mercury chloride, digitonin and alcohol ethoxylates, accumulated by cells via different modes, was investigated in 96-well microplate cultures with varying concentrations of Balb/c 3T3 cells. The median effective nominal concentrations of all but one of the tested compounds depended linearly from the cell concentration. Applying a previously developed equilibrium distribution model cell concentration-independent median effective extracellular concentrations and cell burdens, respectively, could be calculated. The compounds were accumulated by the cells with bioconcentration factors, BCF, between 480 and ≥ 25,000. Cell binding of the alcohol ethoxylates was correlated with their lipophilicity. The results show that significant cell binding can occur even at the small cell volume fractions (∼ 1 × 10(-5) to 3 × 10(-3) L/L) encountered in microplate assays. To what extent cell binding affects the bioavailability depends on the BCF and the cell volume fraction. EC50 measurements in the presence of at least two different cell concentrations allow for excluding or detecting significant cell binding and for determining more appropriate measures of toxic exposure in vitro like median effective extracellular (free) concentrations or cell burdens. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Occurrence and distribution of nonionic surfactants, their degradation products, and linear alkylbenzene sulfonates in coastal waters and sediments in Spain.

PubMed

Petrovic, Mira; Fernández-Alba, Amadeo Rodrigez; Borrull, Francisco; Marce, Rosa Maria; González, Mazo Eduardo; Barceló, Damià

2002-01-01

Spain is one of the European countries that still discharges untreated wastewaters and sewage sludge to the sea. A total of 35 samples of coastal waters and 39 samples of harbor sediments was analyzed. Samples were collected from several hot spots on the Spanish coast, such as the harbors of Tarragona, Almería, and Barcelona, the mouths of the Besos and Llobregat rivers, the Bay of Cadiz, and various yacht harbors at the Mediterranean coast. A generic analytical procedure based on solid-phase extraction-liquid chromatography-atmospheric pressure chemical ionization/electrospray ionization mass spectrometry (SPE-LC-APCI/ESI-MS) was employed for determining the concentrations of alcohol ethoxylates (AEO), nonylphenol ethoxylates (NPEO), coconut diethanol amides (CDEA), nonylphenoxy-monocarboxylates (NPEC), nonylphenol (NP), octylphenol (OP), and linear alkylbenzene sulfonates (LAS) in sediment and water samples. The analysis revealed the presence of considerably high concentrations of NPEOs and NP near the points of discharge of industrial and urban wastewaters. Nonylphenol was found in 47% of water samples and in 77% of all sediment samples analyzed. Values for NP ranged from <0.15 to 4.1 microg/L in seawater and from <8 to 1,050 microg/kg in sediments. Levels of AEOs and CDEAs in seawater and marine sediments are reported for the first time. Concentrations of CDEAs in sediment, which were predominated by C11 through C15 homologues, ranged from 30 to 2,700 microg/kg, while in seawater, concentrations found were up to 24 microg/L. The AEOs were found to accumulate in a bottom sediment and they were detected in all analyzed sediment samples in concentrations from 37 to 1,300 microg/kg.

Numerical simulation of surfactant-enhanced remediation using UTCHEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freeze, G.A.; Fountain, J.C.; Pope, G.A.

1995-12-31

The UTCHEM multiphase compositional simulator was used to model the migration and surfactant-enhanced remediation of perchloroethylene (PCE) in a test cell at Canadian Forces Base Borden, Ontario. A line of five injection wells was installed on one side of the test cell and a line of five withdrawal wells was installed on the opposite side of the cell. The injection and withdrawal wells penetrated the entire depth of the sand aquifer. A total of 231 liters of PCE was injected into a shallow well in the center of the test cell. Prior to surfactant flushing, 47 liters of free-phase PCE,more » which flowed into the injection and withdrawal wells over a two week period, was removed using a small-diameter plastic tube and a peristaltic pump. One to two months of water flooding (pump-and-treat), using the injection-withdrawal well system, flushed an additional 12 liters of PCE. Following the water flooding, an aqueous surfactant solution of 1% nonyl phenol ethoxylate and 1% phosphate ester of the nonyl phenol ethoxylate was circulated through the test cell via the injection-withdrawal wells. Between November 11, 1990 and May 29, 1991, a total of 130,000 liters of surfactant solution were recirculated through the test cell, during which time 62 liters of PCE were recovered. This paper describes preliminary scoping simulations of the surfactant flushing process at the Borden test site to demonstrate the capability of UTCHEM to model surfactant-enhanced remediation of a non-aqueous-phase liquid (NAPL). A discussion of efforts to simulate PCE migration is also presented.« less

Multi-residue analysis of 36 priority and emerging pollutants in marine echinoderms (Holothuria tubulosa) and marine sediments by solid-liquid extraction followed by dispersive solid phase extraction and liquid chromatography-tandem mass spectrometry analysis.

PubMed

Martín, J; Zafra-Gómez, A; Hidalgo, F; Ibáñez-Yuste, A J; Alonso, E; Vilchez, J L

2017-05-01

Marine echinoderms are filter-feeding invertebrates widely distributed along the coasts, and which are therefore extensively exposed to anthropogenic xenobiotics. They can serve as good sentinels for monitoring a large variety of contaminants in marine ecosystems. In this context, a multi-residue analytical method has been validated and applied to Holothuria tubulosa specimens and marine sediments for the determination of 36 organic compounds, which belong to some of the most problematic groups of emerging and priority pollutants (perfluoroalkyl compounds, estrogens, parabens, benzophenones, plasticizers, surfactants, brominated flame retardants and alkylphenols). Lyophilization of samples prior to solvent extraction and clean-up of extracts with C18, followed by liquid chromatography-tandem mass spectrometry analysis, is proposed. A Box-Behnken design was used for optimization of the most influential variables affecting the extraction and clean-up steps. For validation, matrix-matched calibration and recovery assay were applied. Linearity (% r 2 ) higher than 99%, recoveries between 80% and 114% (except in LAS and NP1EO), RSD (precision) lower than 15% and limits of quantification between 0.03 and 12.5ngg -1 dry weight (d.w.) were achieved. The method was applied to nine samples of Holothuria collected along the coast of Granada (Spain), and to marine sediments around the animals. The results demonstrated high bioaccumulation of certain pollutants. A total of 25 out of the 36 studied compounds were quantified, being surfactants, alkylphenols, perfluoroalkyl compounds, triclocarban and parabens the most frequently detected. Nonylphenol was found in the highest concentration (340 and 323ngg -1 d.w. in sediment and Holothuria samples, respectively). Copyright © 2017 Elsevier B.V. All rights reserved.

Association between Polyphenol Intake and Hypertension in Adults and Older Adults: A Population-Based Study in Brazil

PubMed Central

Miranda, Andreia Machado; Steluti, Josiane; Fisberg, Regina Mara; Marchioni, Dirce Maria

2016-01-01

Background/Objective Hypertension is an important risk factor for cardiovascular disease, and diet has been identified as a modifiable factor for preventing and controlling hypertension. Besides, epidemiological studies have suggested an inverse association between polyphenol intake and cardiovascular diseases. The aim of this study was to evaluate the association between the intake of polyphenols and hypertension in a general population of Sao Paulo. Methods Data came from the ‘Health Survey of Sao Paulo (ISA-Capital)’ among 550 adults and older adults in Sao Paulo, Brazil. Diet was assessed by two 24-hour dietary recalls (24HR). Usual intakes were calculated using the Multiple Source Method. Polyphenol intake was calculated by matching food consumption data from the 24HR with the Phenol-Explorer database. The associations between the hypertension and tertiles of the total and classes of polyphenols intake were tested by multivariate logistic regression analysis. Results After multivariate adjustment for potential confounding factors the findings showed an inverse and linearly association between the hypertension and highest tertiles of tyrosols (OR = 0.33; 95%CI 0.18, 0.64), alkylphenols (OR = 0.45; 95%CI 0.23, 0.87), lignans (OR = 0.49; 95%CI 0.25, 0.98), as well as stilbenes (OR = 0.60; 95%CI 0.36, 0.98), and other polyphenols (OR = 0.33; 95%CI 0.14, 0.74). However, total polyphenol intake, and phenolic acids were significantly associated only in the middle tertile with hypertension and flavonoids were not significant associated. Conclusion There is an inverse and linearly association between the highest tertile of some classes of polyphenols, such as, tyrosols, alkylphenols, lignans, stilbenes, other polyphenols and hypertension. PMID:27792767

Influence of the land use pattern on the concentrations and fluxes of priority pollutants in urban stormwater.

PubMed

Zgheib, S; Moilleron, R; Chebbo, G

2011-01-01

This paper presents the results of the concentrations (μg/L) and fluxes (g/ha) of priority substances in stormwater from three watersheds with different land use patterns (namely, residential, urban dense, high urban density). Samples were collected at the outlet of these watersheds. Thirteen chemical groups were investigated corresponding to 88 individual substances before treatment. Results showed that stormwater discharges contained 55 substances, among them some metals, organotins, PAHs, PCBs, alkylphenols, pesticides, phthalates, cholorophenols and volatile organic compounds. Therefore, stormwater was highly contaminated. However, this contamination was often comparable from site to site, since no significant difference of the pollutant load was observed between the land use patterns.

75 FR 74628 - Tristyrylphenol Ethoxylates; Exemption From the Requirement of a Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-01

... to EPA under the Federal Food, Drug, and Cosmetic Act (FFDCA), requesting the establishment of an... be potentially affected by this action if you are an agricultural producer, food manufacturer, or... (NAICS code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide...

Survey of selected personal care products in surface water of coral reefs in Kenting National Park, Taiwan.

PubMed

Kung, Te An; Lee, Shu Hui; Yang, Ting Chi; Wang, Wei Hsien

2018-04-23

Kenting National Park (KNP) located in the Hengchun Peninsula in southern Taiwan is a popular tourist spot, annually attracting millions of visitors, who engage in water sport and amusement activities. In this region, sewage is directly discharged into the marine environment. In this study, the concentrations of five organic UV filters [benzophenone (BP), 2,4-dihydroxy benzophenone (BP-1), 2-hydroxy-4-methoxy benzophenone (BP-3), 2,2'-dihydroxy-4-methoxy benzophenone (BP-8), and 4-methylbenzylidene camphor], five preservatives [methylparaben (MeP), ethylparaben, propylparaben (PrP), butylparaben, and benzylparaben], one disinfectant [triclosan (TCS)], and twenty-four detergent derivatives [nonylphenol (NP), nonylphenol ethoxylates (NP2EO-NP12EO), octylphenol (OP) and octylphenol ethoxylates OP2EO-OP12EO] were detected in seawater and river water samples collected from eight beaches in KNP and two major river estuaries in the Hengchun Peninsula. BP-3 was detected at all sampling sites and was higher in concentration than the other organic UV filters. The highest concentration of BP-3 was 1233 ng/L collected from Wanlitong Beach. MeP and PrP were the main preservative components in seawater. The highest total content of preservative agents was 164 ng/L collected from Houwan Beach. Moreover, NP was detected at all sampling sites, with the highest concentration found at Sail Rock Beach (26.5 ng/L). The highest concentration of OP was 113 ng/L in the Boli River estuary. The widespread use of personal care products (PCPs) has resulted in the release of their major ingredients into natural ecosystems. Therefore, the potential long-term effects of multi-PCPs at low concentration exposure to on the coral reef ecosystem in KNP must be considered and monitored. Copyright © 2018 Elsevier B.V. All rights reserved.

Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

PubMed

Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

2016-09-01

Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis and occurrence of endocrine-disrupting compounds and estrogenic activity in the surface waters of Central Spain.

PubMed

Esteban, S; Gorga, M; Petrovic, M; González-Alonso, S; Barceló, D; Valcárcel, Y

2014-01-01

Endocrine-disrupting compounds (EDCs) are chemical compounds with the ability to alter the hormonal systems of organisms. Such compounds are used in several industrial and domestic activities and reach the aquatic environment via wastewater discharge. The aim of this study is to assess the occurrence of 30 EDCs and related compounds in the surface waters of central Spain and to determine the overall estrogenic activity of environmental samples. This study analyzed a large number of EDCs and other emergent or suspected compounds with endocrine-disrupting activity. The results have shown the presence of 19 EDCs at concentrations ranging from 2 to 5928 ng L(-1). Organophosphorus-based flame retardants, alkylphenolic compounds and anticorrosives were found at the highest concentrations. Furthermore, although insufficient data are available to calculate an average over time, these preliminary results show the need to monitor the waters in both rivers studied. Alkylphenolic compounds, particularly nonylphenol, were the main contributors to overall estrogenicity. A higher concentration of the compounds studied was detected in the river Jarama, although the estrogenicity expressed as estradiol equivalents (EEQs) was higher in the river Manzanares due to a higher concentration of nonylphenol. However, the total estrogenicity did not exceed 1 ng L(-1) (EEQ), which is the level that may cause estrogenic effects in aquatic organisms, in any of the samples. In conclusion, the potential estrogenic risk in both rivers is low, although organophosphorus-based flame retardants may increase this risk as they were found at high levels in all samples. Unfortunately, these compounds could not be taken into account when calculating the estrogenic activity due to the lack of activity data for them. For future investigations, it will be important to assess the estrogenicity provided by these flame retardants. Due to the significant concentrations of EDCs detected in both rivers, further

In vivo and In vitro neurochemical-based assessments of wastewater effluents from the Maumee River area of concern.

PubMed

Arini, Adeline; Cavallin, Jenna E; Berninger, Jason P; Marfil-Vega, Ruth; Mills, Marc; Villeneuve, Daniel L; Basu, Niladri

2016-04-01

Wastewater treatment plant (WWTP) effluents contain potentially neuroactive chemicals though few methods are available to screen for the presence of such agents. Here, two parallel approaches (in vivo and in vitro) were used to assess WWTP exposure-related changes to neurochemistry. First, fathead minnows (FHM, Pimephales promelas) were caged for four days along a WWTP discharge zone into the Maumee River (Ohio, USA). Grab water samples were collected and extracts obtained for the detection of alkylphenols, bisphenol A (BPA) and steroid hormones. Second, the extracts were then used as a source of in vitro exposure to brain tissues from FHM and four additional species relevant to the Great Lakes ecosystem (rainbow trout (RT), river otter (RO), bald eagle (BE) and human (HU)). The ability of the wastewater (in vivo) or extracts (in vitro) to interact with enzymes (monoamine oxidase (MAO) and glutamine synthetase (GS)) and receptors (dopamine (D2) and N-methyl-D-aspartate receptor (NMDA)) involved in dopamine and glutamate-dependent neurotransmission were examined on brain homogenates. In vivo exposure of FHM led to significant decreases of NMDA receptor binding in females (24-42%), and increases of MAO activity in males (2.8- to 3.2-fold). In vitro, alkylphenol-targeted extracts significantly inhibited D2 (66% in FHM) and NMDA (24-54% in HU and RT) receptor binding, and induced MAO activity in RT, RO, and BE brains. Steroid hormone-targeted extracts inhibited GS activity in all species except FHM. BPA-targeted extracts caused a MAO inhibition in FHM, RT and BE brains. Using both in vivo and in vitro approaches, this study shows that WWTP effluents contain agents that can interact with neurochemicals important in reproduction and other neurological functions. Additional work is needed to better resolve in vitro to in vivo extrapolations (IVIVE) as well as cross-species differences. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rapid detection of hazardous chemicals in textiles by direct analysis in real-time mass spectrometry (DART-MS).

PubMed

Antal, Borbála; Kuki, Ákos; Nagy, Lajos; Nagy, Tibor; Zsuga, Miklós; Kéki, Sándor

2016-07-01

Residues of chemicals on clothing products were examined by direct analysis in real-time (DART) mass spectrometry. Our experiments have revealed the presence of more than 40 chemicals in 15 different clothing items. The identification was confirmed by DART tandem mass spectrometry (MS/MS) experiments for 14 compounds. The most commonly detected hazardous substances were nonylphenol ethoxylates (NPEs), phthalic acid esters (phthalates), amines released by azo dyes, and quinoline derivates. DART-MS was able to detect NPEs on the skin of the person wearing the clothing item contaminated by NPE residuals. Automated data acquisition and processing method was developed and tested for the recognition of NPE residues thereby reducing the analysis time.

‘GREENER’ SURFACTANTS FROM BIO-BASED WASTE AS EFFICIENT ALTERNATIVES TO NONYLPHENOL ETHOXYLATES

EPA Science Inventory

All bio-based surfactants synthesized over the course of the project will be tested for their ability to lower the surface tension at the air-water interface using a Du Nüoy ring tensiometer. The cleaning efficiency of the surfactants will be tested at the Toxics Use Reduc...

77 FR 65834 - Residues of Fatty Acids, Tall-Oil, Ethoxylated Propoxylated; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-31

... in residential settings. If EPA is able to determine that a finite tolerance is not necessary to... integral part of its composition the atomic elements carbon, hydrogen, and oxygen. 3. The polymer does not contain as an integral part of its composition, except as impurities, any element other than those listed...

Method for removing elemental sulfur in sour gas wells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sample, T.E. Jr.

1975-09-30

A process is described for removing sulfur deposits from sour gas wells. The formation, well, and surface equipment are contacted with a chemical composition whose aqueous solution will solubilize the sulfur by primary chemical reaction and contains a wetting agent to facilitate and accelerate the sulfur dissolution and removal. The wetting agent or surfactant may be any of a wide variety of surface-active substances such as soaps, sodium or ammonium salts of alkyl or alkyl-aryl sulfates and sulfonates. Nonionic surfactants are preferred, such as ethoxylated substituted phenols. The aqueous solvents are capable of chemically reacting with sulfur to form water-solublemore » sulfur derivatives and include aqueous solutions of alkalies, bases (both inorganic and organic), ammonia, sulfites, bisulfites, etc. (6 claims)« less

Dissipative particle dynamics: Systematic parametrization using water-octanol partition coefficients

NASA Astrophysics Data System (ADS)

Anderson, Richard L.; Bray, David J.; Ferrante, Andrea S.; Noro, Massimo G.; Stott, Ian P.; Warren, Patrick B.

2017-09-01

We present a systematic, top-down, thermodynamic parametrization scheme for dissipative particle dynamics (DPD) using water-octanol partition coefficients, supplemented by water-octanol phase equilibria and pure liquid phase density data. We demonstrate the feasibility of computing the required partition coefficients in DPD using brute-force simulation, within an adaptive semi-automatic staged optimization scheme. We test the methodology by fitting to experimental partition coefficient data for twenty one small molecules in five classes comprising alcohols and poly-alcohols, amines, ethers and simple aromatics, and alkanes (i.e., hexane). Finally, we illustrate the transferability of a subset of the determined parameters by calculating the critical micelle concentrations and mean aggregation numbers of selected alkyl ethoxylate surfactants, in good agreement with reported experimental values.

Overview of air pollution and endocrine disorders

PubMed Central

Darbre, Philippa D

2018-01-01

Over recent years, many environmental pollutant chemicals have been shown to possess the ability to interfere in the functioning of the endocrine system and have been termed endocrine disrupting chemicals (EDCs). These compounds exist in air as volatile or semi-volatile compounds in the gas phase or attached to particulate matter. They include components of plastics (phthalates, bisphenol A), components of consumer goods (parabens, triclosan, alkylphenols, fragrance compounds, organobromine flame retardants, fluorosurfactants), industrial chemicals (polychlorinated biphenyls), products of combustion (polychlorinated dibenzodioxins/furans, polyaromatic hydrocarbons), pesticides, herbicides, and some metals. This review summarizes current knowledge concerning the sources of EDCs in air, measurements of levels of EDCs in air, and the potential for adverse effects of EDCs in air on human endocrine health. PMID:29872334

Chemical composition of shale oil. 1; Dependence on oil shale origin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kesavan, S.; Lee, S.; Polasky, M.E.

1991-01-01

This paper reports on shale oils obtained by nitrogen retorting of North Carolina, Cleveland, Ohio, Colorado, Rundle, Stuart, and Condor oil shales that have been chemically characterized by g.c.-m.s. techniques. After species identification, chemical compositions of the shale oils have been related to the geological origins of the parent shales. Based on the characteristics observed in the chromatograms, eight semi-quantitative parameters have been used to describe the chromatograms. Six of these parameters describe the chromatograms. Six of these parameters describe the relative abundance and distribution of straight chain alkanes and alkenes in the chromatograms. The other two parameters represent themore » abundance, relative to the total amount of volatiles in the oil, of alkylbenzenes and alkylphenols.« less

Evolution of mixed surfactant aggregates in solutions and at solid/solution interfaces

NASA Astrophysics Data System (ADS)

Zhang, Rui

Surfactant systems have been widely used in such as enhanced oil recovery, waste treatment and metallurgy, etc., in order to solve the problem of global energy crisis, to remove the pollutants and to generate novel energy resources. Almost all surfactant systems are invariably mixtures due to beneficial and economic considerations. The sizes and shapes of aggregates in solutions and at solid/solution interfaces become important, since the nanostructures of mixed aggregates determine solution and adsorption properties. A major hurdle in science is the lack of information on the type of complexes and aggregates formed by mixtures and the lack of techniques for deriving such information. Using techniques such as analytical ultracentrifuge, small angle neutron scattering, surface tension, fluorescence, cryo-TEM, light scattering and ultrafiltration, the nanostructures of aggregates of sugar based n-dodecyl-beta-D-maltoside (DM) and nonionic pentaethyleneglycol monododecyl ether or nonyl phenol ethoxylated decyl ether (NP-10) and their mixtures have been investigated to prove the hypothesis that the aggregation behavior is linked to packing of the surfactant governed by the molecular interactions as well as the molecular structures. The results from both sedimentation velocity and sedimentation equilibrium experiments suggest coexistence of two types of micelles in nonyl phenol ethoxylated decyl ether solutions and its mixtures with n-dodecyl-beta-D-maltoside while only one micellar species is present in n-dodecyl-beta-D-maltoside solutions, in good agreement with those from small angle neutron scattering, cryo-TEM, light scattering and ultrafiltration. Type I micelles were primary micelles at cmc while type II micelles were elongated micelles. On the other hand, the nanostructures of mixed surface aggregates have been quantitatively predicted for the first time using a modified packing index. As a continuation of the Somasundaran-Fuersteneau adsorption model, a

A novel fatty-acid-based in-tube dispersive liquid-liquid microextraction technique for the rapid determination of nonylphenol and 4-tert-octylphenol in aqueous samples using high-performance liquid chromatography-ultraviolet detection.

PubMed

Shih, Hou-Kuang; Shu, Ting-Yun; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2015-01-07

In this study, a novel fatty-acid-based in-tube dispersive liquid-liquid microextraction (FA-IT-DLLME) technique is proposed for the first time and is developed as a simple, rapid and eco-friendly sample extraction method for the determination of alkylphenols in aqueous samples using high-performance liquid chromatography-ultraviolet detection (HPLC-UV). In this extraction method, medium-chain saturated fatty acids were investigated as a pH-dependent phase because they acted as either anionic surfactants or neutral extraction solvents based on the acid-base reaction caused solely by the adjustment of the pH of the solution. A specially designed home-made glass extraction tube with a built-in scaled capillary tube was utilized as the phase-separation device for the FA-IT-DLLME to collect and measure the separated extractant phase for analysis. Nonylphenol (NP) and 4-tert-octylphenol (4-tOP) were chosen as model analytes. The parameters influencing the FA-IT-DLLME were thoroughly investigated and optimized. Under the optimal conditions, the detector responses of NP and 4-tOP were linear in the concentration ranges of 5-4000 μg L(-1), with correlation coefficients of 0.9990 and 0.9996 for NP and 4-tOP, respectively. The limits of detection based on a signal-to-noise ratio of 3 were 0.7 and 0.5 μg L(-1), and the enrichment factors were 195 and 143 for NP and 4-tOP, respectively. The applicability of the developed method was demonstrated for the analysis of alkylphenols in environmental wastewater samples, and the recoveries ranged from 92.9 to 107.1%. The extraction process required less than 4 min and utilized only acids, alkalis, and fatty acids to achieve the extraction. The results demonstrated that the presented FA-IT-DLLME approach is highly cost-effective, simple, rapid and environmentally friendly in its sample preparation. Copyright © 2014 Elsevier B.V. All rights reserved.

Monitoring Alkyl Phenol Ethoxylates And Degradation Products After Land Application Of Anaerobically Digested Biosolids

EPA Science Inventory

Annually, over 3 million dry tons of treated sewage sludge (or biosolids) are applied on agricultural lands in the U.S. In 2002, the National Research Council (NRC) recommended an examination of biosolids management practices including chemicals such as surfactants used in clean...

75 FR 22234 - Phosphate Ester, Tallowamine, Ethoxylated; Exemption from the Requirement of a Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2010-04-28

.../Developmental Toxicity Screening Test, clinical signs of toxicity (abnormal respiratory sounds, dyspnea... the AAPs are carcinogenic. The Agency used a qualitative structure activity relationship (QSAR... = 10x MOE = 300 in rats (MRID FQPA SF = 3x 47600707) (10% Dermal absorption; LOAEL = 200 mg/kg/day 100...

77 FR 75085 - Proposed Significant New Use Rule on Ethoxylated, Propoxylated Diamine Diaryl Substituted...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-12-19

... applications. Based on ecological structure activity relationship (EcoSAR) analysis of test data on analogous... significant regulatory action under Executive Order 12866. I. National Technology Transfer and Advancement Act Since this action does not involve any technical standards, section 12(d) of the National Technology...

Scaling up feasibility of the production of solid lipid nanoparticles (SLN).

PubMed

Gohla, S H; Dingler, A

2001-01-01

Solid lipid nanoparticles (SLN/Lipopearls) are widely discussed as colloidal drug carrier system. In contrast to polymeric systems, such as polylactic copolyol capsules, these systems show up with a good biocompatibility, if applied parenterally. The solid lipid matrices can be comprised of fats or waxes and allow protection of incorporated active ingredients against chemical and physical degradation. The SLN can either be produced by "hot homogenisation" of melted lipids at elevated temperatures or a "cold homogenization" process. This paper deals with production technologies for SLN formulations, based on non-ethoxylated fat components for topical application and high pressure homogenization (APV Deutschland GmbH, D-Lübeck). Based on the chosen fat components, a novel and easy manufacturing and scaling up method was developed to maintain chemical and physical integrity of encapsulated active and carrier.

Production of solid lipid nanoparticles (SLN): scaling up feasibilities.

PubMed

Dingler, A; Gohla, S

2002-01-01

Solid lipid nanoparticles (SLN/Lipopearls) are widely discussed as a new colloidal drug carrier system. In contrast to polymeric systems, such as Polylactic copolyol microcapsules, these systems show with a good biocompatibility, if applied parenterally. The solid lipid matrices can be comprised of fats or waxes, and allow protection of incorporated active ingredients against chemical and physical degradation. The SLN can either be produced by 'hot homogenization' of melted lipids at elevated temperatures or by a 'cold homogenization' process. This paper deals with production technologies for SLN formulations, based on non-ethoxylated fat components for topical application and high pressure homogenization. Based on the chosen fat components, a novel and easy manufacturing and scaling-up method was developed to maintain chemical and physical integrity of the encapsulated active ingredients in the carrier.

Colorimetric monitoring of solid-phase aldehydes using 2,4-dinitrophenylhydrazine.

PubMed

Shannon, Simon K; Barany, George

2004-01-01

A simple and rapid method to achieve colorimetric monitoring of resin-bound aldehydes, based on ambient temperature reaction with 2,4-dinitrophenylhydrazine (DNPH) in the presence of dilute acid, has been developed as an adjunct to solid-phase organic synthesis and combinatorial chemistry. By this test, the presence of aldehydes is indicated by a red to dark-orange appearance, within a minute. Alternatively, resins that are free of aldehydes or in which aldehyde functions have reacted completely retain their original color. The DNPH test was demonstrated for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethyl polystyrene (AMP), cross-linked ethoxylate acrylate resin (CLEAR), and acryloylated O,O'-bis(2-aminopropyl)poly(ethylene glycol) (PEGA) supports and gave results visible to the naked eye at levels as low as 18 micromol of aldehyde per gram of resin.

Food-grade microemulsions based on nonionic emulsifiers: media to enhance lycopene solubilization.

PubMed

Spernath, Aviram; Yaghmur, Anan; Aserin, Abraham; Hoffman, Roy E; Garti, Nissim

2002-11-06

Water-dilutable food-grade microemulsions consisting of ethoxylated sorbitan esters, and in some cases blended with other emulsifiers, water, (R)-(+)-limonene, ethanol, and propylene glycol, have been prepared. These microemulsions are of growing interest to the food industry as vehicles for delivering and enhancing solubilization of natural food supplements with nutritional and health benefits. Lycopene, an active natural lipophilic antioxidant from tomato, has solubilized in water-in-oil, bicontinuous, and oil-in-water types of microemulsions up to 10 times the oil [(R)-(+)-limonene] dissolution capacity. The effects of aqueous-phase dilution, nature of surfactant (hydrophilic-lypophilic balance), and mixed surfactant on solubilization capacity and solubilization efficiency were studied. Structural aspects studied by self-diffusion NMR were correlated to the solubilization capacity, and transformational structural changes were identified.

ILLUMINATING THE ROLE OF AGGLOMERATES ON CRITICAL PHYSICOCHEMICAL PROPERTIES OF AMORPHOUS CALCIUM PHOSPHATE COMPOSITES

PubMed Central

O’Donnell, J.N.R.; Antonucci, J.M.; Skrtic, D.

2009-01-01

Water sorption (WS), mechanical strength, and ion release of polymeric composites formulated with 40 % as-made or milled amorphous calcium phosphate (ACP) are compared after 1, 2 and 3 months of aqueous exposure. Ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate and methacryloxyethyl phthalate comprised the resin. The WS (mass %) peaked at 3 months. WS of as-made ACP composites was significantly higher than WS of milled ACP composites and copolymers. Both composite groups experienced decreases in biaxial flexural strength (BFS) with water aging, with milled ACP composites retaining a significantly higher BFS throughout immersion. Ion release was moderately reduced in milled ACP composites, though they remained superior to as-made ACP composites due to significantly lower WS and higher BFS after prolonged aqueous exposure. PMID:19774100

Temperature dependence of the vapour tension of methyl-substituted phenol derivatives

DOE Office of Scientific and Technical Information (OSTI.GOV)

S.G. Gagarin

2007-05-15

Notable among the coking products of coal are phenol and its derivatives, derived for the coal tar and water layer above ht tar. Given that phenol an its derivatives are mainly extracted from coal tar fractions by rectification, information on how the vapor tension of the individual components depends on the temperature is of great importance. For phenol and various substituted alkylphenols there are tabular data. In the pre-computer era these data were sufficient for the separation of phenol mixtures. However, the development and introduction of information technology in the coal industry and in the design process demands the mathematicalmore » description of the physicochemical processes of coking products. The temperature dependence of the saturated vapor pressure for organic compounds is commonly described by the Antoine equation.« less

Biodegradation and attenuation of steroidal hormones and alkylphenols by stream biofilms and sediments

USGS Publications Warehouse

Writer, Jeffrey; Barber, Larry B.; Ryan, Joseph N.; Bradley, Paul M.

2011-01-01

Biodegradation of select endocrine-disrupting compounds (17β-estradiol, estrone, 17α-ethynylestradiol, 4-nonylphenol, 4-nonylphenolmonoexthoylate, and 4-nonylphenoldiethoxylate) was evaluated in stream biofilm, sediment, and water matrices collected from locations upstream and downstream from a wastewater treatment plant effluent discharge. Both biologically mediated transformation to intermediate metabolites and biologically mediated mineralization were evaluated in separate time interval experiments. Initial time intervals (0–7 d) evaluated biodegradation by the microbial community dominant at the time of sampling. Later time intervals (70 and 185 d) evaluated the biodegradation potential as the microbial community adapted to the absence of outside energy sources. The sediment matrix was more effective than the biofilm and water matrices at biodegrading 4-nonylphenol and 17β-estradiol. Biodegradation by the sediment matrix of 17α-ethynylestradiol occurred at later time intervals (70 and 185 d) and was not observed in the biofilm or water matrices. Stream biofilms play an important role in the attenuation of endocrine-disrupting compounds in surface waters due to both biodegradation and sorption processes. Because sorption to stream biofilms and bed sediments occurs on a faster temporal scale (<1 h) than the potential to biodegrade the target compounds (50% mineralization at >185 d), these compounds can accumulate in stream biofilms and sediments.

A novel polydentate ligand chromophore for simultaneously colorimetric detection of trace Ag + and Fe3 +

NASA Astrophysics Data System (ADS)

Yan, Zhengquan; Zhao, Qi; Wen, Meijun; Hu, Lei; Zhang, Xuezhong; You, Jinmao

2017-11-01

A novel polydentate ligand chromophore, 3,6-di-(N-ethyl-N-ethoxyl phenylazo) acridine (EEPA), was identified and synthesized. After its structure was characterized by FTIR, 1H NMR, mass spectra and element analyses, it was noted to find that there was a simultaneously colorimetric response to Ag+ and Fe3 + accompanying with different color changes, i.e., from brown to light purple for Ag+ and further to purple-red for Fe3 +, respectively. Their different action mechanisms, a 1:2 complex mode for EEPA-Ag+ and 1:1 for EEPA-Fe3 +, were investigated and confirmed by means of Job's plot and theoretical calculation. EEPA would be a potential colorimetric chemo-dosimeter for simultaneous detection of Ag+ and Fe3 + with the detection limits of 1.6 nmol·L- 1 and 69 nmol·L- 1, respectively.

Atmospheric concentrations and air-sea exchanges of nonylphenol, tertiary octylphenol and nonylphenol monoethoxylate in the North Sea.

PubMed

Xie, Zhiyong; Lakaschus, Soenke; Ebinghaus, Ralf; Caba, Armando; Ruck, Wolfgang

2006-07-01

Concentrations of nonylphenol isomers (NP), tertiary octylphenol (t-OP) and nonylphenol monoethoxylate isomers (NP1EO) have been simultaneously determined in the sea water and atmosphere of the North Sea. A decreasing concentration profile appeared following the distance increasing from the coast to the central part of the North Sea. Air-sea exchanges of t-OP and NP were estimated using the two-film resistance model based upon relative air-water concentrations and experimentally derived Henry's law constant. The average of air-sea exchange fluxes was -12+/-6 ng m(-2)day(-1) for t-OP and -39+/-19 ng m(-2)day(-1) for NP, which indicates a net deposition is occurring. These results suggest that the air-sea vapour exchange is an important process that intervenes in the mass balance of alkylphenols in the North Sea.

In vitro evaluation of the disinfection efficacy on Eimeria tenella unsporulated oocysts isolated from broilers.

PubMed

Guimarães, José S; Bogado, Alexey L Gomel; da Cunha, Thiago Cezar B; Garcia, João Luis

2007-01-01

The objective of this study was to evaluate in vitro the action of eight chemical principles by disinfection efficacy (DE) of Eimeria tenella oocysts. Disinfection efficacy was evaluated by either destruction or sporulation inhibition of the oocysts. Eight treatments were performed: T1 (Glutaraldehyde 42.5 g + Benzalkonium Chloride 7.5 g); T2 (Benzalkonium chloride + quaternary ammonium salt); T3 (formol 37% + Sodium Dodecylbenzene Sulfonate 12%); T4 (sodium hypochlorite 2%); T5 (Orthodichlorobenzene 60% + Xylene 30%); T6 (Polyoctyl polyamino ethyl glycine + Polyoxyethylene alkylphenol ether + Sodium Chloride); T7 (Chloramine T) and finally T8 (free iodine 2.25% + Phosphoric acid 15 g). The control test was carried out with distilled water (T9). The best DE were observed, respectively, in T3 (79.49%), T5 (75.60%) and T4 (65.56%) treatments.

SOLUBILIZATION OF DODECANE, TETRACHLOROETHYLENE, AND 1,2-DICHLOROBENZENE IN MICELLAR SOLUTIONS OF ETHOXYLATED NONIONIC SURFACTANTS

EPA Science Inventory

Although surfactants have received considerable attention as a potential means for enhancing the recovery of organic compounds from the subsurface, only limited information is available regarding the micellar solubilization of common groundwater contaminants by nonionic surfactan...

Adsorption of ethoxylated styrene oxide and polyacrylic acid and mixtures there of on organic pigment.

PubMed

Wijting, W K; Laven, J; van Benthem, R A T M; de With, G

2008-11-01

The adsorption of two polymeric surfactants on an organic pigment was investigated. As surfactants the anionic polyacrylic acid sodium salt (PANa, M(W)=15,000) and a non-ionic block copolymer surfactant based on styrene oxide (SO) and ethylene oxide (EO) (M(W)=1500) were used. The adsorption behavior was analyzed by size exclusion chromatography of the supernatant after centrifugation of the pigment dispersions. It was found that PANa has no affinity to the pigment, whereas SO-EO has a strong affinity to the pigment surface. Competitive adsorption of PANa and SO-EO was not observed. Addition of SO-EO yields stable dispersions.

Monitoring of selected non-ionic surfactants in river water by liquid chromatography-tandem mass spectrometry.

PubMed

Zembrzuska, Joanna; Budnik, Irena; Lukaszewski, Zenon

2016-03-15

Alcohol ethoxylates (AEs) are a significant component of the non-ionic surfactant (NS) flux discharged into surface water. Due to the polydispersity of the majority of NS, they are easily recognizable by their 'fingerprints', i.e. a series of mass peaks which differ by m/z = 44, namely the m/z of a single oxyethylene subunit. Dodecanol ethoxylates (C12EOx) represent AEs from both renewable and petrochemical sources. Therefore, C12Ex are suitable fingerprints of NS in the aquatic environment. The aim of this work was to develop an LC-MS/MS method suitable for AE monitoring in river water. River water samples taken from the River Warta in Poznan (Poland) were extracted with ethyl acetate, evaporated, reconstituted in the mobile phase and processed by the LC - Multistage MS procedure (LC-MS/MS) using optimum multiple reaction monitoring (MRM). The method of multiple standard additions was used for the evaluation of each AE fingerprint concentration. The concentration of C12EOx having 2-9 oxyethylene subunits was determined. Standards for higher C12EOx are not yet available. The developed method offers an LOD of between 1 and 9 ng L(-1), and is suitable for the monitoring of NS fingerprints in river water. The range of C12EO2-9 concentrations determined in the River Warta varied within two orders of magnitude in all cases. The lowest determined concentration was 17 ± 1 ng L(-1), while the highest was 2.6 ± 0.14 μg L(-1). The total concentration of C12EO2-C12EO9 homologues varied between 1.4 and 11.2 μg L(-1). A relatively high concentration of short-chained homologues (2-5 oxyethylene subunits) was observed in the investigated river water. This provides evidence of a biodegradation pathway involving the gradual shortening of the AE oxyethylene chain. Distinct evidence was also obtained of unregulated NS discharges into the river. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ FTIR and flash pyrolysis/GC-MS characterization of Protosalvinia (Upper Devonian, Kentucky, USA): Implications for maceral classification

USGS Publications Warehouse

Mastalerz, Maria; Hower, J.C.; Carmo, A.

1998-01-01

Protosalvinia from Devonian rocks in Kentucky has been analyzed using petrographic and in situ FTIR and flash pyrolysis/GC-MS techniques in order to discuss its origin and placement in organic matter classification. In reflected light, Protosalvinia resembles cutinite in shape, color and reflectance, whereas in fluorescent mode it reveals yellow-green fluorescence, reminiscent of alginite. Alkylbenzenes, alkylnaphthalenes, and n-alkanes are the principal compounds in the pyrolyzates, whereas alkylphenols and n-alk-l-enes are present in minor concentrations. FTIR results show that aliphatic bands (both in stretching and bending modes) are prominent. Protosalvinia also reveals well developed aromatic bands in the out-of-plane region. Such a mixture of aliphatic and aromatic components is not known in documented organic matter types of either marine or terrestrial origin. It is suggested that Protosalvinia might belong to rare marine organisms that yield aromatic pyrolyzates. Based on morphological features and optical properties Protosalvinia should be classified as a maceral of the liptinite group. It does not, however, fit precisely within any of the established categories of the liptinite macerals.Protosalvinia from Devonian rocks in Kentucky has been analyzed using petrographic and in situ FTIR and flash pyrolysis/GC-MS techniques in order to discuss its origin and placement in organic matter classification. In reflected light, Protosalvinia resembles cutinite in shape, color and reflectance, whereas in fluorescent mode it reveals yellow-green fluorescence, reminiscent of alginite. Alkylbenzenes, alkylnaphthalenes, and n-alkanes are the principal compounds in the pyrolyzates, whereas alkylphenols and n-alk-l-enes are present in minor concentrations. FTIR results show that aliphatic bands (both in stretching and bending modes) are prominent. Protosalvinia also reveals well developed aromatic bands in the out-of-plane region. Such a mixture of aliphatic and

Impact of endocrine disrupting compounds in sewage impacted coastal area on seabream.

PubMed

Al-Jandal, Noura; Saeed, Talat; Azad, Ismail; Al-Subiai, Sherain; Al-Zekri, Waleed; Hussain, Sumaiah; Al-Hasan, Enas

2018-04-15

The pollution of coastal regions worldwide has been of a great concern due to the presence of endocrine disrupting chemicals (EDCs). These chemicals find their way to the marine environment via the sewage treatment plants (STPs). Hence, this study was designed to investigate the status and sources of EDCs and their effect on fish in Kuwait's coastal areas, from the chemical and biological perspectives. The assessment of three STPs indicated the presence of significant levels of phthalates (19 and 31µg/l), alkylphenols (85 and 159ng/l), and estrogens (30 and 368ng/l) in both inflow and outflow samples. The analysis of samples from field exposure sites revealed significant levels of EDCs in seawater (phthalates: 2.1-4.6µg/l; alkylphenols: 1.2-16.4ng/l; estrogens: 0-36.2ng/l) and sediment (phthalates: 2.1-15.7mg/kg dry wt; alkyphenols: 2.5-15.1µg/kg dry wt.; estrogens: 4.1-214.2µg/kg dry wt.) samples. The biological perspective investigated through the exposure of fish to sewage outlets at five sites. The hepatosomatic index (HSI) revealed a higher level in winter samples 0.48-0.79%) in comparison to summer samples 1-1.5%). Histological observation of hepatic tissue of fish exposed during winter months in all sites, showed much less necrotic changes and hepatic vacuolation in the hepatic tissue of summer exposed fish. Imunnohistochemistry evidences revealed a significant level of positive signals and Vtg localization in the hepatic tissue as the results support the histopathological alterations observed. Results of enzyme-linked immunosorbent assay (ELISA) showed no significant difference between the plasma protein content of winter and summer samples. Overall, the study suggest that there is possible local source or a chronic input of untreated and/or partially treated water due to the significant levels of phthalates, alkyphenols, and estrogens detected in the Kuwait Bay. These levels were enough to initiate alteration in the hepatic tissue of fish exposed to

Crystallization and X-ray analysis of the salmon-egg lectin SEL24K.

PubMed

Murata, Kenji; Fisher, Andrew J; Hedrick, Jerry L

2007-05-01

The 24 kDa egg lectin of Chinook salmon (Oncorhynchus tshawytscha) is released from the egg during the cortical reaction. The lectin functions in blocking polyspermy during the fertilization process. The egg lectin was purified by affinity chromatography from salmon eggs and crystallized by the hanging-drop vapor-diffusion method using 15/4 EO/OH (pentaerythritol ethoxylate) as a precipitant. The crystal diffracted synchrotron-radiation X-rays to 1.63 A resolution. The crystal belongs to the monoclinic space group P2(1), with unit-cell parameters a = 93.0, b = 73.6, c = 113.6 A, alpha = 90, beta = 92.82, gamma = 90 degrees. The crystal is likely to contain eight molecules in the asymmetric unit (V(M) = 2.3 A3 Da(-1)), corresponding to a solvent content of 45.5%. A self-rotation function suggests an arrangement with 222 point symmetry within the asymmetric unit.

Simultaneous quantification of poly-dispersed anionic, amphoteric and nonionic surfactants in simulated wastewater samples using C18 high-performance liquid chromatography-quadrupole ion-trap mass spectrometry

NASA Technical Reports Server (NTRS)

Levine, Lanfang H.; Garland, Jay L.; Johnson, Jodie V.

2005-01-01

This paper describes the development of a guantitative method for direct and simultaneous determination of three frequently encountered surfactants, amphoteric (cocoamphoacetate, CAA), anionic (sodium laureth sulfate, SLES), and nonionic (alcohol ethoxylate, AE) using a reversed-phase C18 HPLC coupled with an ESI ion-trap mass spectrometer (MS). Chemical composition, ionization characteristics and fragmentation pathways of the surfactants are presented. Positive ESI was effective for all three surfactants in agueous methanol buffered with ammonium acetate. The method enables rapid determinations in small sample volumes containing inorganic salts (up to 3.5 g L(-1)) and multiple classes of surfactants with high specificity by applying surfactant specific tandem mass spectrometric strategies. It has dynamic linear ranges of 2-60, 1.5-40, 0.8-56 mg L(-1) with R2 egual or greater than 0.999, 0.98 and 0.999 (10 microL injection) for CAA, SLES, and AE, respectively.

Analytical study of endocrine-disrupting chemicals in leachate treatment process of municipal solid waste (MSW) landfill sites.

PubMed

Asakura, Hiroshi; Matsuto, Toshihiko; Tanaka, Nobutoshi

2007-01-01

Influent and processed water were sampled at different points in the leachate treatment facilities of five municipal solid waste (MSW) landfill sites. Then, the concentrations of endocrine-disrupting chemicals (EDCs), namely, alkylphenols (APs), bisphenol A (BPA), phthalic acid esters (PAEs) and organotin compounds (OTs), in the treated leachate samples were determined and the behavior of the EDCs in the treatment processes was discussed. The concentrations of APs were as low as those in surface waters, and no OTs were detected (detection limit: 0.01 microg/L). Meanwhile, diethylhexyl phthalate (DEHP), which was the most abundant of the four substances measured as PAEs, and BPA were found in all of the influent samples. BPA was considerably degraded by aeration, except when the water temperature was low and the total organic carbon (TOC) was high. By contrast, aeration, biological treatment, and coagulation/sedimentation removed only a small amount of DEHP.

Identification of a p-cresol degradation pathway by a GFP-based transposon in Pseudomonas and its dominant expression in colonies.

PubMed

Cho, Ah Ra; Lim, Eun Jin; Veeranagouda, Yaligara; Lee, Kyoung

2011-11-01

In this study, the chromosome-encoded pcuRCAXB genes that are required for p-cresol degradation have been identified by using a newly constructed green fluorescent protein (GFP)-based promoter probe transposon in the long-chain alkylphenol degrader Pseudomonas alkylphenolia. The deduced amino acid sequences of the genes showed the highest identities at the levels of 65-93% compared with those in the databases. The transposon was identified to be inserted in the pcuA gene, with the promoterless gfp gene being under the control of the pcu catabolic gene promoter. The expression of GFP was positively induced by p-cresol and was about 10 times higher by cells grown on agar than those in liquid culture. In addition, phydroxybenzoic acid was detected during p-cresol degradation. These results indicate that P. alkylphenolia additionally possesses a protocatechuate ortho-cleavage route for pcresol degradation that is dominantly expressed in colonies.

Oxygen compounds in the Irati Shale oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alfonso, J.C.; Schmal, M.; Cardoso, J.N.

1992-04-01

This paper reports the principal alkylphenols (4 wt %) and carboxylic acids (1.2 wt %) present in the Irati Shale oil S[tilde a]o Mateus do Sul, Paran acute (a) by means of a combination of gas chromatography-mass spectrometry (GC-MS) and retention time-data of standard compounds. it appears that the phenols are essentially monocyclic in nature with methyl groups as the main substituents. Carboxylic acids are principally linear and predominantly of the range C[sub 14]--C[sub 20]. After catalytic hydrotreatment (400 [degrees]C, 125 atm) high hydrodeoxygenation levels were obtained (87 wt %) for phenols and carboxylic acids, although the relative distribution ofmore » the various compounds was not significantly changed. Oxygen is present in the carbonaceous residue as several functionalities xanthenes, phenols, aryl ethers, carbonyl compounds, and furanic structures. The remaining acidic compounds may cause instability of the treated shale oil.« less

Ecotoxicity by the biodegradation of alkylphenol polyethoxylates depends on the effect of trace elements.

PubMed

Hotta, Yudai; Hosoda, Akifumi; Sano, Fumihiko; Wakayama, Manabu; Niwa, Katsuki; Yoshikawa, Hiromichi; Tamura, Hiroto

2010-01-27

The bacteria Sphingomonas sp. strain BSN22, isolated from bean fields, degraded octylphenol polyethoxylates (OPEO(n)) to octylphenol (OP) under aerobic conditions. This biodegradation mechanism proceeded by the following two-step degradation process: (1) degradation of OPEO(n) to octylphenol triethoxylate (OPEO(3)), (2) degradation from OPEO(3) to OP via octylphenoxy acetic acid (OPEC(1)). The chemical structure of OPEC(1) was confirmed by analysis using (18)O-labeled water. Quantitative studies revealed that magnesium (Mg(2+)) and calcium (Ca(2+)) ions were essential for the biodegradation of OPEO(n). Furthermore, the rate of biodegradation was especially accelerated by ferric ions (Fe(3+)), and the accumulated amounts of endocrine active chemicals, such as OP, OPEO(1), and OPEC(1), significantly increased to the concentration of 22.8, 221.7, and 961.1 microM in the presence of 37.0 microM Fe(3+), respectively. This suggests that environmental elements significantly influence the resultant ecotoxicity as well as the rate of their biodegradation in the environment. This study on the mechanism of OPEO(n) biodegradation may play an important role in understanding and managing environmental safety, including drinking water safety.

Effects of solvent composition in the normal-phase liquid chromatography of alkylphenols and naphthols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hurtubise, R.J.; Hussain, A.; Silver, H.F.

1981-11-01

The normal-phase liquid chromatographic models of Scott, Snyder, and Soczewinski were considered for a ..mu..-Bondapak NH/sub 2/ stationary phase. n-Heptane:2-propanol and n-heptane:ethyl acetate mobile phases of different compositions were used. Linear relationships were obtained from graphs of log K' vs. log mole fraction of the strong solvent for both n-heptane:2-propanol and n-heptane:ethyl acetate mobile phases. A linear relationship was obtained between the reciprocal of corrected retention volume and % wt/v of 2-propanol but not between the reciprocal of corrected retention volume and % wt/v of ethyl acetate. The slopes and intercept terms from the Snyder and Soczewinski models were foundmore » to approximately describe interactions with ..mu..-Bondapak NH/sub 2/. Capacity factors can be predicted for the compounds by using the equations obtained from mobile phase composition variation experiments.« less

Dermal in vitro penetration of methiocarb, paclobutrazol, and pirimicarb: effect of nonylphenolethoxylate and protective gloves.

PubMed Central

Nielsen, J B; Andersen, H R

2001-01-01

Dermal exposure has become the major route of human occupational exposure to pesticides. Detergents are used as part of formulated pesticide products and are known to change the barrier properties of human skin in vitro. However, studies on the influence of detergents as well as protective glove materials on dermal penetration of pesticides are scarce. In an experiment using in vitro static diffusion cells mounted with human skin, we evaluated the effect of nonylphenol-ethoxylate on dermal penetration of three extensively used pesticides--methiocarb, paclobutrazol, and pirimicarb--and the protection against dermal penetration offered by protective gloves made of latex or nitrile. There was a general tendency, though not statistically significant for all pesticides, for nonylphenolethoxylate to decrease the percutaneous penetration of the three pesticides. The nitrile generally offered better protection against percutaneous penetration of pesticides than did latex, but the degree of protection decreased over time and depended on the pesticides used. PMID:11266321

Mineralization of Surfactants by Microbiota of Aquatic Plants.

PubMed

Federle, Thomas W; Schwab, Burney S

1989-08-01

The biodegradation of linear alkylbenzene sulfonate (LAS) and linear alcohol ethoxylate (LAE) by the microbiota associated with duckweed (Lemna minor) and the roots of cattail (Typha latifolia) was investigated. Plants were obtained from a pristine pond and a pond receiving wastewater from a rural laundromat. Cattail roots and duckweed plants were incubated in vessels containing sterile water amended with [C]LAS, [C]LAE, or C-labeled mixed amino acids (MAA). Evolution of CO(2) was determined over time. The microbiota of cattail roots from both ponds mineralized LAS, LAE, and MAA without lag periods, and the rates and extents of mineralization were not significantly affected by the source of the plants. Mineralization of LAS and LAE was more rapid in the rhizosphere than in nearby root-free sediments, which exhibited differences as a function of pond. The microbiota of duckweed readily mineralized LAE and MAA but not LAS. The rate and extent of mineralization were not affected by the source of the duckweed.

Highly Efficient and Fully Solution-Processed Inverted Light-Emitting Diodes with Charge Control Interlayers.

PubMed

Fu, Yan; Jiang, Wei; Kim, Daekyoung; Lee, Woosuk; Chae, Heeyeop

2018-05-23

In this work, we developed a charge control sandwich structure around QD layers for the inverted QLEDs, the performance of which is shown to exceed that of the conventional QLEDs in terms of the external quantum efficiency (EQE) and the current efficiency (CE). The QD light-emitting layer (EML) is sandwiched with two ultrathin interfacial layers: one is a poly(9-vinlycarbazole) (PVK) layer to prevent excess electrons, and the other is a polyethylenimine ethoxylated (PEIE) layer to reduce the hole injection barrier. The sandwich structure resolves the imbalance between injected holes and electrons and brings the level of balanced charge carriers to a maximum. We demonstrated the highly improved performance of 89.8 cd/A of current efficiency, 22.4% of external quantum efficiency, and 72 814 cd m -2 of maximum brightness with the solution-processed inverted QLED. This sandwich structure (PVK/QD/PEIE), as a framework, can be applied to various QLED devices for enhancing performance.

The influence of detergents and active components of detergent on bioproduction of organic matters and enzymatic activity of some species of fungi.

PubMed

Stojanović, Jelica; Stojanović, Marina; Iles, Deana; Mijusković, Zoran

2004-01-01

Detergent (Merix, "Merima " Krusevac) applied in concentration of 1% vol. showed specific influence on the bioproduction of some 15 different amino acids and on the enzyme activity of the species of fungi A. niger, A. alternata and T. roseum. Detergent has significantly stimulated the production of 15 analyzed amino acids of the fungi species A. niger. The same applied concentration of detergent has decreased or considerably decreased the production of some 14 of totally 15 analyzed amino acids of investigated fungi species A. alternata and T. roseum. The enzyme activity of the fungi A. niger was more intensive in relation to the species A. alternata and T. roseum during the experimental period or in some phases of the experimental period. The detergent component, ethoxyled oleyl-cetyl alcohol, in concentration of 0.01%, 0.1% and 1% showed an inhibitory effect, or significant inhibitory effect on the enzyme activity of the examined species of fungi (A. niger, A. alternata and T. roseum).

Determination of 4-nonylphenol and 4-octylphenol in human blood samples by high-performance liquid chromatography with multi-electrode electrochemical coulometric-array detection.

PubMed

Inoue, K; Yoshimura, Y; Makino, T; Nakazawa, H

2000-11-01

Alkylphenols can affect human health because they disrupt the endocrine system. In this study, an analytical method for determining trace amounts of 4-nonylphenol (NP) and 4-octylphenol (OP) in human blood samples was developed. Reversed-phase HPLC with multi-electrode electrochemical coulometric-array detection was used for the determination of NP and OP in plasma and serum samples prepared with a solid-phase extraction method. The separation was achieved using an isocratic mobile phase of 0.7% phosphoric acid-acetonitrile with a C18 reversed phase column. The detection limits of NP and OP were 1.0 and 0.5 ng ml-1, respectively. The recoveries of NP and OP added to human plasma samples were above 70.0% with a relative standard deviation of less than 15.5%. The method was found to be applicable to the determination of NP and OP in various human blood samples such as serum and plasma.

Cross-linked cyclodextrin-based material for treatment of metals and organic substances present in industrial discharge waters

PubMed Central

Euvrard, Élise; Morin-Crini, Nadia; Druart, Coline; Bugnet, Justine; Martel, Bernard; Cosentino, Cesare; Moutarlier, Virginie

2016-01-01

Summary In this study, a polymer, prepared by crosslinking cyclodextrin (CD) by means of a polycarboxylic acid, was used for the removal of pollutants from spiked solutions and discharge waters from the surface treatment industry. In spiked solutions containing five metals, sixteen polycyclic aromatic hydrocarbons (PAH) and three alkylphenols (AP), the material exhibited high adsorption capacities: >99% of Co2+, Ni2+ and Zn2+ were removed, between 65 and 82% of the PAHs, as well as 69 to 90% of the APs. Due to the structure of the polymer and its specific characteristics, such as the presence of carboxylic groups and CD cavities, the adsorption mechanism involves four main interactions: ion exchange, electrostatic interactions and precipitation for metal removal, and inclusion complexes for organics removal. In industrial discharge waters, competition effects appeared, especially because of the presence of calcium at high concentrations, which competed with other pollutants for the adsorption sites of the adsorbent. PMID:27829889

Endocrine disrupting chemicals in the atmosphere: Their effects on humans and wildlife.

PubMed

Annamalai, Jayshree; Namasivayam, Vasudevan

2015-03-01

Endocrine disrupting chemicals (EDCs) are exogenous agents that interfere or disrupt the normal synthesis, secretion, transportation, binding and metabolism of natural hormones; eventually dysregulating homeostatic mechanisms, reproduction and development. They are emitted into the atmosphere during anthropogenic activities and physicochemical reactions in nature. Inhalation of these EDCs as particulate and gaseous vapors triggers their interaction with endocrine glands and exerts agonist or antagonists actions at hormone receptors. The endocrine disruption at nanogram levels of EDC's has gained concern in the last decade, due to infertility among men and women, early puberty, obesity, diabetes and cancer. Thus, the review explores the literature that addresses the major occurring EDCs in the atmosphere including phthalates, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), brominated flame retardants (BFRs), dioxins, alkylphenols (APs) and perfluorinated chemicals (PFCs). Sources, fate, half-life, mechanism, measured concentrations in air, bioaccumulation in tissues, laboratory exposures correlating to toxicological effects of these EDCs in humans and wildlife are discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Phenolic profile and fermentation patterns of different commercial gluten-free pasta during in vitro large intestine fermentation.

PubMed

Rocchetti, Gabriele; Lucini, Luigi; Chiodelli, Giulia; Giuberti, Gianluca; Gallo, Antonio; Masoero, Francesco; Trevisan, Marco

2017-07-01

The fate of phenolic compounds, along with short-chain fatty acids (SCFAs) production kinetics, was evaluated on six different commercial gluten-free (GF) pasta samples varying in ingredient compositions, focussing on the in vitro faecal fermentation after the gastrointestinal digestion. A general reduction of both total phenolics and reducing power was observed in all samples, together with a substantial change in phenolic profile over 24h of faecal fermentation, with differences among GF pasta samples. Flavonoids, hydroxycinnamics and lignans degraded over time, with a concurrent increase in low-molecular-weight phenolic acids (hydroxybenzoic acids), alkylphenols, hydroxybenzoketones and tyrosols. Interestingly, discriminant analysis also identified several alkyl derivatives of resorcinol as markers of the changes in phenolic profile during in vitro fermentation. Furthermore, degradation pathways of phenolics by intestinal microbiota have been proposed. Considering the total SCFAs and butyrate production during the in vitro fermentation, different fermentation kinetics were observed among GF pasta post-hydrolysis residues. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic micropollutants in marine plastics debris from the open ocean and remote and urban beaches.

PubMed

Hirai, Hisashi; Takada, Hideshige; Ogata, Yuko; Yamashita, Rei; Mizukawa, Kaoruko; Saha, Mahua; Kwan, Charita; Moore, Charles; Gray, Holly; Laursen, Duane; Zettler, Erik R; Farrington, John W; Reddy, Christopher M; Peacock, Emily E; Ward, Marc W

2011-08-01

To understand the spatial variation in concentrations and compositions of organic micropollutants in marine plastic debris and their sources, we analyzed plastic fragments (∼10 mm) from the open ocean and from remote and urban beaches. Polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), dichloro-diphenyl-trichloroethane and its metabolites (DDTs), polybrominated diphenyl ethers (PBDEs), alkylphenols and bisphenol A were detected in the fragments at concentrations from 1 to 10,000 ng/g. Concentrations showed large piece-to-piece variability. Hydrophobic organic compounds such as PCBs and PAHs were sorbed from seawater to the plastic fragments. PCBs are most probably derived from legacy pollution. PAHs showed a petrogenic signature, suggesting the sorption of PAHs from oil slicks. Nonylphenol, bisphenol A, and PBDEs came mainly from additives and were detected at high concentrations in some fragments both from remote and urban beaches and the open ocean. Copyright © 2011 Elsevier Ltd. All rights reserved.

Catalytic Mechanism of Short Ethoxy Chain Nonylphenol Dehydrogenase Belonging to a Polyethylene Glycol Dehydrogenase Group in the GMC Oxidoreductase Family

PubMed Central

Liu, Xin; Ohta, Takeshi; Kawabata, Takeshi; Kawai, Fusako

2013-01-01

Ethoxy (EO) chain nonylphenol dehydrogenase (NPEO-DH) from Ensifer sp. AS08 and EO chain octylphenol dehydrogenase from Pseudomonas putida share common molecular characteristics with polyethylene glycol (PEG) dehydrogenases (PEG-DH) and comprise a PEG-DH subgroup in the family of glucose-methanol-choline (GMC) oxidoreductases that includes glucose/alcohol oxidase and glucose/choline dehydrogenase. Three-dimensional (3D) molecular modeling suggested that differences in the size, secondary structure and hydropathy in the active site caused differences in their substrate specificities toward EO chain alkylphenols and free PEGs. Based on 3D molecular modeling, site-directed mutagenesis was utilized to introduce mutations into potential catalytic residues of NPEO-DH. From steady state and rapid kinetic characterization of wild type and mutant NPEO-DHs, we can conclude that His465 and Asn507 are directly involved in the catalysis. Asn507 mediates the transfer of proton from a substrate to FAD and His465 transfers the same proton from the reduced flavin to an electron acceptor. PMID:23306149

Catalytic mechanism of short ethoxy chain nonylphenol dehydrogenase belonging to a polyethylene glycol dehydrogenase group in the GMC oxidoreductase family.

PubMed

Liu, Xin; Ohta, Takeshi; Kawabata, Takeshi; Kawai, Fusako

2013-01-10

Ethoxy (EO) chain nonylphenol dehydrogenase (NPEO-DH) from Ensifer sp. AS08 and EO chain octylphenol dehydrogenase from Pseudomonas putida share common molecular characteristics with polyethylene glycol (PEG) dehydrogenases (PEG-DH) and comprise a PEG-DH subgroup in the family of glucose-methanol-choline (GMC) oxidoreductases that includes glucose/alcohol oxidase and glucose/choline dehydrogenase. Three-dimensional (3D) molecular modeling suggested that differences in the size, secondary structure and hydropathy in the active site caused differences in their substrate specificities toward EO chain alkylphenols and free PEGs. Based on 3D molecular modeling, site-directed mutagenesis was utilized to introduce mutations into potential catalytic residues of NPEO-DH. From steady state and rapid kinetic characterization of wild type and mutant NPEO-DHs, we can conclude that His465 and Asn507 are directly involved in the catalysis. Asn507 mediates the transfer of proton from a substrate to FAD and His465 transfers the same proton from the reduced flavin to an electron acceptor.

Behavior of Selected Endocrine Disrupting Chemicals in Sewage Treatment Plant

NASA Astrophysics Data System (ADS)

Wang, Xinze; Lu, Jiaming; Ollivier, Natacha; Saturnino, Anais; Gomez, Elena; Casellas, Claude; Picot, Bernadette

2010-11-01

The behavior of endocrine disrupting chemicals in sewage treatment plant affects their final fate in water environment. We selected six endocrine disrupting chemicals: 4 alkylphenols (4-tert-octylphenol, octylphenol, 4-nonylphenol, bisphenol A) and 2 steroids (17α-ethinylestradiol and estriol) as targets, their removal and transformation in wastewater treatment plant were studied. Five mixed liquors were sampled respectively from different stages of Minhang wastewater treatment plant in Shanghai. EDCs concentration were analyzed with GC-MS. The main removal pathways of EDCs include initial adsorption by suspended solids and following biodegradation in biological sludge. The removal efficiency of six targets was more than 86%. The concentration of OP and 4-n-NP in water significantly increased in anoxic stage, the reason may be the releases of EDCs from sludge to water on the condition of low DO. And it was also found that the EDCs could be released to water phase in the secondary clarifier, which may cause potential risk of EDCs entering the environment with discharge.

Utilization of coal as a source of chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Demirbas, A.

Coal consists carbon-based substances can be used as a source of specialty aromatic chemicals and aliphatic chemicals. Four widespread processes allow for making chemicals from coals: gasification, liquefaction, direct conversion, and co-production of chemicals and fuels along with electricity. Coal is gasified to produce synthesis gas (syngas) with a gasifier which is then converted to paraffinic liquid fuels and chemicals by Fischer-Tropsch synthesis. Liquid product from coal gasification mainly contains benzene, toluene, xylene (BTX), phenols, alkylphenols, and cresol. Methanol is made using coal or syngas with hydrogen and carbon monoxide in a 2 to 1 ratio. Coal-derived methanol has manymore » preferable properties as it is free of sulfur and other impurities. Syngas from coal can be reformed to hydrogen. Ammonium sulfate from coal tar by pyrolysis can be converted to ammonia. The humus substances can be recovered from brown coal by alkali extraction.« less

A role for calcium hydroxide and dolomite in water: acceleration of the reaction under ultraviolet light.

PubMed

Nagase, Hiroyasu; Tsujino, Hidekazu; Kurihara, Daisuke; Saito, Hiroshi; Kawase, Masaya

2014-04-01

Organic environmental pollutants are now being detected with remarkably high frequency in the aquatic environment. Photodegradation by ultraviolet light is sometimes used as a method for removing organic chemicals from water; however, this method is relatively inefficient because of the low degradation rates involved, and more efficient methods are under development. Here we show that the removal of various organic pollutants can be assisted by calcined dolomite in aqueous solution under irradiation with ultraviolet light. It was possible to achieve substantial removal of bisphenol A, chlorophenols, alkylphenols, 1-naphthol and 17β-estradiol. The major component of dolomite responsible for the removal was calcium hydroxide. Our results demonstrate that the use of calcium hydroxide with ultraviolet light irradiation can be a very effective method of rapidly removing organic environmental pollutants from water. This is a new role for calcium hydroxide and dolomite in water treatment. Copyright © 2013 Elsevier Ltd. All rights reserved.

End-group-functionalized poly(N,N-diethylacrylamide) via free-radical chain transfer polymerization: Influence of sulfur oxidation and cyclodextrin on self-organization and cloud points in water

PubMed Central

Reinelt, Sebastian; Steinke, Daniel

2014-01-01

Summary In this work we report the synthesis of thermo-, oxidation- and cyclodextrin- (CD) responsive end-group-functionalized polymers, based on N,N-diethylacrylamide (DEAAm). In a classical free-radical chain transfer polymerization, using thiol-functionalized 4-alkylphenols, namely 3-(4-(1,1-dimethylethan-1-yl)phenoxy)propane-1-thiol and 3-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propane-1-thiol, poly(N,N-diethylacrylamide) (PDEAAm) with well-defined hydrophobic end-groups is obtained. These end-group-functionalized polymers show different cloud point values, depending on the degree of polymerization and the presence of randomly methylated β-cyclodextrin (RAMEB-CD). Additionally, the influence of the oxidation of the incorporated thioether linkages on the cloud point is investigated. The resulting hydrophilic sulfoxides show higher cloud point values for the lower critical solution temperature (LCST). A high degree of functionalization is supported by 1H NMR-, SEC-, FTIR- and MALDI–TOF measurements. PMID:24778720

Assessment of biological effects of environmental pollution in Mersin Bay (Turkey, northeastern Mediterranean Sea) using Mullus barbatus and Liza ramada as target organisms.

PubMed

Yılmaz, Doruk; Kalay, Mustafa; Dönmez, Erdem; Yılmaz, Nejat

2016-01-01

The increasing emphasis on the assessment and monitoring of marine ecosystems has revealed the need to use appropriate biological indicators for these areas. Enzyme activities and histopathology are increasingly being used as indicators of environmental stress since they provide a definite biological end-point of pollutant exposure. As part of an ecotoxicological assessment of Mersin Bay, EROD enzyme activity and histopathological response in selected organs and tissues of two species of fish, Mullus barbatus (red mullet) and Liza ramada (thinlip grey mullet), captured from area were examined. Pollutant (Organochlorines (OC), alkylphenols (APs) and BPA) levels and biomarker responses in tissue samples were evaluated together for their potential to alter the metabolism and cellular aspects in liver and gonad. Elevated induction of EROD activity and histopathological alterations in contaminated samples from Mersin Bay was observed compared to reference site indicating the exposure to potential pollutants. Copyright © 2015 Elsevier Ltd. All rights reserved.

Occurrence and transport of pesticides and alkylphenols in water samples along the Ebro River Basin

NASA Astrophysics Data System (ADS)

Navarro, Alícia; Tauler, Romà; Lacorte, Sílvia; Barceló, Damià

2010-03-01

SummaryWe report the temporal and geographical variations of a set of 30 pesticides (including triazines, organophosphorus and acetanilides) and industrial compounds in surface waters along the Ebro River during the period 2004-2006. Using descriptive statistics we found that the compounds with industrial origin (tributylphosphate, octylphenol and nonylphenol) appeared in over 60% of the samples analyzed and at very high concentrations, while pesticides had a point source origin in the Ebro delta area and overall low-levels, between 0.005 and 2.575 μg L -1. Correlations among pollutants and their distributions were studied using Principal Component Analysis (PCA), a multivariate exploratory data analysis technique which permitted us to discern between agricultural and industrial source contamination. Over a 3 years period a seasonal trend revealed highest concentrations of pesticides over the spring-summer period following pesticide application.

Schistosomicidal Activity of Alkyl-phenols from the Cashew Anacardium occidentale against Schistosoma mansoni Adult Worms.

PubMed

Alvarenga, Tavane A; de Oliveira, Pollyanna F; de Souza, Julia M; Tavares, Denise C; Andrade E Silva, Márcio L; Cunha, Wilson R; Groppo, Milton; Januário, Ana H; Magalhães, Lizandra G; Pauletti, Patrícia M

2016-11-23

Bioassay-guided study of the ethanol extract from the cashew Anacardium occidentale furnished cardol triene (1), cardol diene (2), anacardic acid triene (3), cardol monoene (4), anacardic acid diene (5), 2-methylcardol triene (6), and 2-methylcardol diene (7). 1D- and 2D-NMR experiments and HRMS analysis confirmed the structures of compounds 1-7. Compounds 2 and 7 were active against Schistosoma mansoni adult worms in vitro, with LC 50 values of 32.2 and 14.5 μM and selectivity indices of 6.1 and 21.2, respectively. Scanning electron microscopy of the tegument of male worms in the presence of compound 7 at 25 μM after 24 h of incubation showed severe damage as well as peeling and reduction in the number of spine tubercles. Transmission electron microscopy analyses revealed swollen mitochondrial membrane, vacuoles, and altered tegument in worms incubated with compound 2 (25 μM after 24 h). Worms incubated with compound 7 (25 μM after 24 h) had lysed interstitial tissue, degenerated mitochondria, and drastically altered tegument. Together, the results indicated that compound 7 presents promising in vitro schistosomicidal activity.

Bisphenol A and alkylphenols concentrations in selected mariculture fish species from Pulau Kukup, Johor, Malaysia.

PubMed

Ismail, Nur Afifah Hanun; Wee, Sze Yee; Aris, Ahmad Zaharin

2018-02-01

Endocrine disrupting compound (EDC) contamination in food is a global concern. Concerning potential environmental and human health exposed to EDCs via food intake, an experiment was conducted on the selected EDCs concentration in the mariculture fish, Trachinotus blochii (golden pomfret), Lutjanus campechanus (snapper), and Lates calcarifer (sea bass) at Pulau Kukup, Johor. Mariculture activity at Pulau Kukup involves active export of fishes to Singapore and Indonesia. The recovery of BPA (bisphenol A), 4OP (4-octylphenol), and 4NP (4-nonylphenol) were 61.54%-93.00%, 16.79%-17.13%, and 61.24%-71.49%, respectively. Relatively high concentration of BPA was recorded in T. blochii (0.322ng/g), followed by L. calcarifer (0.124ng/g) and L. campechanus (0.023ng/g). Furthermore, 4OP and 4NP were detected only in T. blochii at concentrations of 0.084ng/g and 0.078ng/g, respectively. The results of the present study provide insights on monitoring and managing mariculture activity in relation to environmental protection and food safety. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reaction of alkylphenols with acetals. II. Reaction of 4methyl-2-tert-butylphenol with dimethoxymethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Starikova, O.F.; Gurvich, Y.A.; Kumok, S.T.

1985-12-20

The authors explain how di(hydroxydialkylaryl) derivatives of methane play an important role in the inhibition of oxidation processes in polymers, oils, fuels, and other organic materials. They investigate the reaction of 4-methyl-2-tert-butylphenol with dimethoxymethane, and established that the reaction mass contained 2-methoxymethyl-4-6-tert-butylphenol. The formation and the transformations of 2-methoxymethyl-4-methyl-6-tert-butylphenol do not have a significant effect on the synthesis of di(2-hydroxy-5-methyl-3-tert-butylphenyl) methane from 4-methyl-2-tert-butyl-phenol and dimethoxymethane.

Biodegradation in seawater of PAH and alkylphenols from produced water of a North Sea platform.

PubMed

Lofthus, Synnøve; Almås, Inger K; Evans, Peter; Pelz, Oliver; Brakstad, Odd Gunnar

2018-09-01

Operational planned discharges of produced water (PW) to the marine environment from offshore oil production installations, contain low concentrations of dispersed oil compounds, like polycyclic aromatic hydrocarbons (PAHs) and alkylated phenols (APs). Biotransformation in natural seawater (SW) of naphthalenes/PAHs and phenol/APs in field-collected PW from a North Sea platform was investigated in this biodegradation study. The PW was diluted in SW from a Norwegian fjord, and the biodegradation study was performed in slowly rotating carousels at 13 °C over a period of 62 days. Naphthalenes/PAHs and phenol/APs biotransformation was determined by first-order rate kinetics, after normalization against the recalcitrant biomarker 17α(H),21β(H)-Hopane. The results from this study showed total biotransformation half-lives ranging from 10 to 19 days for groups of naphthalenes and PAHs, while half-lives for APs (C0- to C9-alkylated) were 10-14 days. Biotransformation half-lives of single compounds ranged from 8 to >100 days for naphthalenes and PAHs (median 16 days), and from 5 to 70 days (median 15 days) for phenols and APs. Four of the tested PAHs (chrysene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(g,h,i)perylene) and one AP (4-tert-butylphenol) showed biotransformation half-lives >50 days. This is one of a few studies that has investigated the potential for biodegradation of PW in natural SW. Methods and data from this study may be used as a part of Risk Based Approaches (RBA) for assessments of environmental fate of PW released to the marine environment and as part of the persistence related to risk. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.

Clam bioaccumulation of Alkylphenols and Polyciclic aromatic hydrocarbons in the Venice lagoon under different pressures.

PubMed

Ademollo, N; Patrolecco, L; Matozzo, V; Marin, M G; Valsecchi, S; Polesello, S

2017-11-15

Biota-Sediment Accumulation Factors (BSAFs) of nonylphenols (NPs) and polycyclic aromatic hydrocarbons (PAHs) in Ruditapes philippinarum from the Venice Lagoon (Italy) were determined with the aim to verify whether the routine biomonitoring studies are reliable in contaminated sites. Clams and sediments were collected in field campaigns (October 2003 to June 2004) in three sites of the Venice Lagoon. Results showed that Marghera and Campalto sediments were more contaminated by NPs and PAHs than Poveglia. Different trends were observed in the contamination of clams with the highest BSAFs found at Poveglia. BSAF trend appeared to be inversely related to the contaminant pressure on the sites. These results suggest that clam bioaccumulation is not always representative of the chemical pressure on aquatic biota. The direct correlation between sediment and biota concentrations in contaminated sites can be lost as a function of the site-specific conditions such as sediment toxicity and food availability. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of nonylphenol ethoxylate metabolites in vegetables and crops by high performance liquid chromatography-tandem mass spectrometry.

PubMed

She, Yongxin; Wang, Jing; Zheng, Yongquan; Cao, Weiqiang; Wang, Rongyan; Dong, Fengshou; Liu, Xingang; Qian, Mingrong; Zhang, Hu; Wu, Liqing

2012-05-01

A method has been developed for the simultaneous determination of the concentration of nonylphenol (4-NP), nonylphenol monoethoxylates (NP1EO) and nonylphenol diethoxylates (NP2EO) in vegetables and crops by liquid chromatography-tandem quadrupole mass spectrometry (HPLC-MS/MS). These target compounds were extracted from vegetable and crop samples with acetonitrile, and then the extracts were cleaned using solid phase extraction with graphitised carbon black tandem primary secondary amine (PSA) cartridges. The MS method enabled highly reliable identification by monitoring the corresponding ammonium adduct [M+NH4](+) in the positive mode for NP1EO and NP2EO, and the deprotonated molecule [M-H](-) in the negative mode for 4-NP. Recoveries for the spiked samples ranged from 65% to 118%. The limit of detection (LOD) of 4-NP, NP1EO and NP2EO was 3, 5 and 0.1μgkg(-1), respectively. This method would be useful for the quick and routine detection of the residues of 4-NP, NP1EO and NP2EO in vegetables and crops. Copyright © 2011 Elsevier Ltd. All rights reserved.

Occurrence and risk assessment of nonylphenol and nonylphenol ethoxylates in sewage sludge from different conventional treatment processes.

PubMed

González, M M; Martín, J; Santos, J L; Aparicio, I; Alonso, E

2010-01-01

In the present work, the concentrations of the organic pollutants nonylphenol (NP) and nonylphenol mono- and diethoxylates (NP1EO and NP2EO, respectively) in primary, secondary, mixed, aerobically-digested, anaerobically-digested, dehydrated, compost and lagoon sludge samples from different sludge treatments have been evaluated. Toxicological risk assessment of these compounds in sludge and sludge-amended soil has also been reported. NP, NP1EO and NP2EO were monitored in sludge samples obtained from treatment plants located in Andalusia (south of Spain) based on anaerobic treatments (11 anaerobic-digestion wastewater treatment plants and 3 anaerobic wastewater stabilization ponds) or on aerobic treatments (3 aerobic-digestion wastewater treatment plants, 1 dehydration treatment plant and 2 composting plants). The sum of NP, NP1EO and NP2EO (NPE) concentrations has been evaluated in relation to the limit value of 50 mg/kg set by the European Union Sludge Directive draft published in April 2000 (Working Document on Sludge). In most of the samples, NP was present at higher concentration levels (mean value 88.0 mg/kg dm) than NP1EO (mean value 33.8 mg/kg dm) and NP2EO (mean value 14.0 mg/kg dm). The most contaminated samples were compost, anaerobically-digested sludge, lagoon sludge and aerobically-digested sludge samples, which contained NPE concentrations in the ranges 44-962 mg/kg dm, 8-669 mg/kg dm, 27-319 mg/kg dm and 61-282 mg/kg dm, respectively. Risk quotients, expressed as the ratios between environmental concentrations and the predicted no-effect concentrations, were higher than 1 for NP, NP1EO and NP2EO in the 99%, 92% and 36% of the studied samples, respectively; and higher than 1 in the 86%, 6% and 2%, respectively, after sludge application to soil, leading to a significant ecotoxicological risk mainly due to the presence of NP.

Transitional phase inversion of emulsions monitored by in situ near-infrared spectroscopy.

PubMed

Charin, R M; Nele, M; Tavares, F W

2013-05-21

Water-heptane/toluene model emulsions were prepared to study emulsion transitional phase inversion by in situ near-infrared spectroscopy (NIR). The first emulsion contained a small amount of ionic surfactant (0.27 wt % of sodium dodecyl sulfate) and n-pentanol as a cosurfactant. In this emulsion, the study was guided by an inversion coordinate route based on a phase behavior study previously performed. The morphology changes were induced by rising aqueous phase salinity in a "steady-state" inversion protocol. The second emulsion contained a nonionic surfactant (ethoxylated nonylphenol) at a concentration of 3 wt %. A continuous temperature change induced two distinct transitional phase inversions: one occurred during the heating of the system and another during the cooling. NIR spectroscopy was able to detect phase inversion in these emulsions due to differences between light scattered/absorbed by water in oil (W/O) and oil in water (O/W) morphologies. It was observed that the two model emulsions exhibit different inversion mechanisms closely related to different quantities of the middle phases formed during the three-phase behavior of Winsor type III.

Adsorption of Anionic, Cationic and Nonionic Surfactants on Carbonate Rock in Presence of ZrO 2 Nanoparticles

NASA Astrophysics Data System (ADS)

Esmaeilzadeh, Pouriya; Bahramian, Alireza; Fakhroueian, Zahra

The adsorption of surfactants at the solid-water interface is important for the control of wetting, lubrication, detergency and in mineral flotation.We have studied the adsorptions of different types of surfactants, cationic (Dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS) and non-anionic (lauryl alcohol-7 mole ethoxylate, LA7) on carbonate rock in presence of zirconium oxide spherical nanoparticles (17-19 nm). ZrO2 nanoparticles with tetrahedral structure have significant effect on adsorption of surfactants on the carbonate rock. We have used the measured conductivities to determine the rate of adsorption of surfactants at rock-water interfaces. The conductivity of DTAB in aqueous solutions containing calcite powder decreases more than the other surfactants in contact with ZrO2 nanoparticles. We have also investigated the adsorption of surfactants at the air-water interface. The presence of nanoparticles, as demonstrated by our experiments, enhances the surface activity and surface adsorption of the surfactants through electrostatic forces or formation of nanostructures. Dynamic light structuring data shows similar aggregation number of nanoparticles in presence of nanoparticles.

Mineralization of surfactants by microbiota of aquatic plants. [Lemna minor, Typha latifolia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Federle, T.W.; Schwab, B.S.

1989-08-01

The biodegradation of linear alkylbenzene sulfonate (LAS) and linear alcohol ethoxylate (LAE) by the microbiota associated with duckweed (Lemna minor) and the roots of cattail (Typha latifolia) was investigated. Plants were obtained from a pristine pond and a pond receiving wastewater from a rural laundromat. Cattail roots and duckweed plants were incubated in vessels containing sterile water amended with ({sup 14}C)LAS, ({sup 14}C)LAE, or {sup 14}C-labeled mixed amino acids (MAA). Evolution of {sup 14}CO{sub 2} was determined over time. The microbiota of cattail roots from both ponds mineralized LAS, LAE, and MAA without lag periods, and the rates and extentsmore » of mineralization were not significantly affected by the source of the plants. Mineralization of LAS and LAE was more rapid in the rhizosphere than in nearby root-free sediments, which exhibited differences as a function of pond. The microbiota of duckweed readily mineralized LAE and MAA but not LAS. The rate and extent of mineralization were not affected by the source of the duckweed.« less

Polymer Film Dewetting by Water/Surfactant/Good-Solvent Mixtures: A Mechanistic Insight and Its Implications for the Conservation of Cultural Heritage.

PubMed

Baglioni, Michele; Montis, Costanza; Chelazzi, David; Giorgi, Rodorico; Berti, Debora; Baglioni, Piero

2018-06-18

Aqueous nanostructured fluids (NSFs) have been proposed to remove polymer coatings from the surface of works of art; this process usually involves film dewetting. The NSF cleaning mechanism was studied using several techniques that were employed to obtain mechanistic insight on the interaction of a methacrylic/acrylic copolymer (Paraloid B72) film laid on glass surfaces and several NSFs, based on two solvents and two surfactants. The experimental results provide a detailed picture of the dewetting process. The gyration radius and the reduction of the T g of Paraloid B72 fully swollen in the two solvents is larger for propylene carbonate than for methyl ethyl ketone, suggesting higher mobility of polymer chains for the former, while a nonionic alcohol ethoxylate surfactant was more effective than sodium dodecylsulfate in favoring the dewetting process. FTIR 2D imaging showed that the dewetting patterns observed on model samples are also present on polymer-coated mortar tiles when exposed to NSFs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flexible inverted polymer solar cells fabricated in air at low temperatures

NASA Astrophysics Data System (ADS)

Kuwabara, Takayuki; Wang, Xiaofan; Kusumi, Takuji; Yamaguchi, Takahiro; Taima, Tetsuya; Takahashi, Kohshin

2016-08-01

A series of modified indium tin oxide (ITO) materials, including sol-gel zinc-oxide-coated ITO (ITO/ZnO), ZnO nanoparticle-coated ITO (ITO/ZnO-NP), 1,4-bis(3-aminopropyl)piperazine (BAP)-modified ITO, and polyethylenimine ethoxylated (PEIE)-modified ITO, were used for electron-collection electrodes in inverted polymer solar cells (PSCs). The modified ITO electrodes were prepared in air at temperatures below 100 °C, using various ITO films on flexible poly(ethylene terephthalate) substrates (PET-ITO) with sheet resistances ranging from 12 to 60 Ω sq-1. The PET-ITO (12 Ω sq-1)/ZnO-NP PSC exhibited an improved power conversion efficiency (PCE) (2.93%), and this PCE was ˜90% of that observed for a cell using glass-ITO/ZnO-NP (sheet resistance = 10 Ω sq-1 PCE = 3.28%). Additionally, we fabricated a flexible inverted ZnO-NP PSC using an indene-C60 bisadduct (ICBA) as the acceptor material in place of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and obtained a PCE of 4.18%.

Aqueous solution-chemical derived Nisbnd Al2O3 solar selective absorbing coatings. 2. Wetting agents and spreading of aqueous solutions on aluminum substrate

NASA Astrophysics Data System (ADS)

Li, Zhenxiang; Zhao, Jianxi

2013-03-01

Wettability of aluminum substrate by the aqueous solutions containing ethoxylated alcohol nonionic surfactants C12En- or Triton X-series was studied using dynamic contact angle measurements. The efficiency of wetting was found to strongly depend on the length of polyoxyethylene (POE) chain of C12En- or Triton X surfactants. For C12E4 that has a very short POE chain, it hardly made the aqueous solution spreading over aluminum. The others with a long POE chain were indeed very efficient in promoting the solution spreading. Moreover, all the spreading process could be completed within 10 s. The single-layer Nisbnd Al2O3 coatings were fabricated from the precursor solutions containing C12En- or Triton X surfactants and the reflectance spectra were measured by a UV/vis spectrophotometer equipped with an integrating sphere. The results indicated that the precursor solution with a long POE chain surfactant as wetting agent favored to fabricate a uniform film on the aluminum substrate and therefore to get a high solar absorptance.

Mineralization of Surfactants by Microbiota of Aquatic Plants

PubMed Central

Federle, Thomas W.; Schwab, Burney S.

1989-01-01

The biodegradation of linear alkylbenzene sulfonate (LAS) and linear alcohol ethoxylate (LAE) by the microbiota associated with duckweed (Lemna minor) and the roots of cattail (Typha latifolia) was investigated. Plants were obtained from a pristine pond and a pond receiving wastewater from a rural laundromat. Cattail roots and duckweed plants were incubated in vessels containing sterile water amended with [14C]LAS, [14C]LAE, or 14C-labeled mixed amino acids (MAA). Evolution of 14CO2 was determined over time. The microbiota of cattail roots from both ponds mineralized LAS, LAE, and MAA without lag periods, and the rates and extents of mineralization were not significantly affected by the source of the plants. Mineralization of LAS and LAE was more rapid in the rhizosphere than in nearby root-free sediments, which exhibited differences as a function of pond. The microbiota of duckweed readily mineralized LAE and MAA but not LAS. The rate and extent of mineralization were not affected by the source of the duckweed. PMID:16347999

Environmental concentration of nonylphenol alters the development of urogenital and visceral organs in avian model.

PubMed

Roig, Benoit; Cadiere, Axelle; Bressieux, Stephanie; Biau, Sandrine; Faure, Sandrine; de Santa Barbara, Pascal

2014-01-01

Nonylphenol (NP) is an endocrine disruptor with harmful effects including feminization and carcinogenesis on various organisms. This substance is a degradation product of nonylphenol ethoxylates (NPEO) that is used in several industrial and agricultural processes. In this paper, we examined the assessment of NP exposure on chick embryo development, using a concentration consistent with the environmental concentrations of NP. With this aim, NP (between 0.1 and 50 μg/egg) was injected into the yolk of egg through a small needle hole in the shell. We report the effect of NP on chick reproductive system development although the effect we observed is lower than those observed by exposition to other endocrine disruptors. However, histological analysis highlighted a decrease of intraluminal seminiferous surface area in 64.12% of case (P=0.0086) and an heterogeneous organization of the renal tubules when 10 μg/egg were injected. Moreover, an impairment of liver development with an abnormal bile spillage was observed when higher concentration of NP was injected (50 μg/egg). © 2013.

Simultaneous Measurement of Fluorescence, Conversion and Physical/mechanical Properties for Monitoring Bulk and Localized Photopolymerization Reactions in Heterogeneous Systems

PubMed Central

Medel, S.; Bosch, P.; Grabchev, I.; Shah, P. K.; Liu, J.; Aguirre-Soto, A.; Stansbury, J. W.

2016-01-01

An FT-NIR spectrometer, rheometer and fluorescence spectrophotometer were coupled for the real-time monitoring of polymerization reactions, allowing the simultaneous tracking of polymerization kinetics, storage modulus as well as fluorescence. In this study, a methacrylate functionalized dansyl chromophore (DANSMA) was synthesized and two different nanogels were made from urethane dimethacrylate and isobornyl methacrylate. Two series of resin formulations were prepared using the DANSMA probe, ethoxylated bisphenol A dimethacrylate as the matrix monomer, Irgacure® 651 as the initiator and the dispersed, monomer-swollen nanogels to give clear UV-curable resins. Placement of the fluorescent probe either throughout the resin or linked into the nanogel before its dispersion in the matrix provides a tool to study how the nanogel structure affects local network development by means of fluorescence from the DANSMA probe. We demonstrate the potential of this new technique using a composite as the two phase system (resin and polymerizable nanogel) including a dansyl derivative as a polymerizable probe to follow the reactions that are taking places in both phases. PMID:27213038

The interface modification for GNWs/Si Schottky junction with PEI/PEIE interlayers

NASA Astrophysics Data System (ADS)

Zhou, Quan; Liu, Xiangzhi; Luo, Wei; Shen, Jun; Wang, Yuefeng; Wei, Dapeng

2018-03-01

Polyethylenimine ethoxylated (PEIE) and polyethyl-enimine (PEI), the two kinds of interface buffer layer, are widely used in the organic light-emitting diodes and solar cells for band alignment adjustment. In this report, we carefully studied the influence of the inserting organic layer on the graphene nanowalls(GNWS)/Si junction quality and the photoresponse of the Schottky devices. We found that thinner layers of PEI could decrease the dark current and improve the photo-to-dark ratio to 105 for n-Si devices. The s-kink effect and degradation of open circuit voltage could be observed for thicker thickness and excessive doping. Relatively, PEIE with stable thin layer not only improve the rectifying characteristics of p-Si devices but also the incident photon conversion efficiency. The maximus IPCE could reach 44% and be adjusted to zero by the reverse bias. The tunneling inhibition for electrons can be alleviated by increasing the barrier height. Our results provide an attractive method to improve the efficiency of pristine GNWs/Si junction with interface doping and passivation.

Development of a Freeze-Dried Fungal Wettable Powder Preparation Able to Biodegrade Chlorpyrifos on Vegetables

PubMed Central

Chen, Shaohua; Xiao, Ying; Hu, Meiying; Zhong, Guohua

2014-01-01

Continuous use of the pesticide chlorpyrifos has resulted in harmful contaminations in environment and species. Based on a chlorpyrifos-degrading fungus Cladosporium cladosporioides strain Hu-01 (collection number: CCTCC M 20711), a fungal wettable powder preparation was developed aiming to efficiently remove chlorpyrifos residues from vegetables. The formula was determined to be 11.0% of carboxymethyl cellulose-Na, 9.0% of polyethylene glycol 6000, 5.0% of primary alcohol ethoxylate, 2.5% of glycine, 5.0% of fucose, 27.5% of kaolin and 40% of freeze dried fungi by response surface methodology (RSM). The results of quality inspection indicated that the fungal preparation could reach manufacturing standards. Finally, the degradation of chlorpyrifos by this fungal preparation was determined on pre-harvest cabbage. Compared to the controls without fungal preparation, the degradation of chlorpyrifos on cabbages, which was sprayed with the fungal preparation, was up to 91% after 7 d. These results suggested this freeze-dried fungal wettable powder may possess potential for biodegradation of chlorpyrifos residues on vegetables and provide a potential strategy for food and environment safety against pesticide residues. PMID:25061758

Development of a freeze-dried fungal wettable powder preparation able to biodegrade chlorpyrifos on vegetables.

PubMed

Liu, Jie; He, Yue; Chen, Shaohua; Xiao, Ying; Hu, Meiying; Zhong, Guohua

2014-01-01

Continuous use of the pesticide chlorpyrifos has resulted in harmful contaminations in environment and species. Based on a chlorpyrifos-degrading fungus Cladosporium cladosporioides strain Hu-01 (collection number: CCTCC M 20711), a fungal wettable powder preparation was developed aiming to efficiently remove chlorpyrifos residues from vegetables. The formula was determined to be 11.0% of carboxymethyl cellulose-Na, 9.0% of polyethylene glycol 6000, 5.0% of primary alcohol ethoxylate, 2.5% of glycine, 5.0% of fucose, 27.5% of kaolin and 40% of freeze dried fungi by response surface methodology (RSM). The results of quality inspection indicated that the fungal preparation could reach manufacturing standards. Finally, the degradation of chlorpyrifos by this fungal preparation was determined on pre-harvest cabbage. Compared to the controls without fungal preparation, the degradation of chlorpyrifos on cabbages, which was sprayed with the fungal preparation, was up to 91% after 7 d. These results suggested this freeze-dried fungal wettable powder may possess potential for biodegradation of chlorpyrifos residues on vegetables and provide a potential strategy for food and environment safety against pesticide residues.

Search for the source of an apparent interfacial resistance to mass transfer of CnEm surfactants to the water/oil interface.

PubMed

Huston, Kyle J; Kiemen, Ashley; Larson, Ronald G

2018-06-12

Experiments have shown that relaxation of oil/water interfacial tension by adsorption of alkyl ethoxylate surfactants from water onto an oil droplet is delayed relative to diffusion-controlled adsorption. We examine possible causes of this delay, and we show that several are implausible. We find that re-dissolution of the surfactant in the oil droplet cannot explain the apparent interfacial resistance at short times, because the interface will preferentially fill before any such re-dissolution occurs. We also perform umbrella sampling with molecular dynamics simulation and do not find any evidence of a free energy barrier or low-diffusivity zone near the interface. Nor do we find evidence from simulation that pre-micellar aggregation slows diffusion enough to cause the observed resistance to interfacial adsorption. We are therefore unable to pinpoint the cause of the resistance, but we suggest that "dead time" associated with the experimental method could be responsible - specifically a local depletion of surfactant by the ejected droplet when creating the fresh interface between the oil and water.

Efficiency of solution-processed multilayer polymer light-emitting diodes using charge blocking layers

NASA Astrophysics Data System (ADS)

Kasparek, Christian; Rörich, Irina; Blom, Paul W. M.; Wetzelaer, Gert-Jan A. H.

2018-01-01

By blending semiconducting polymers with the cross-linkable matrix ethoxylated-(4)-bisphenol-a-dimethacrylate (SR540), an insoluble layer is acquired after UV-illumination. Following this approach, a trilayer polymer light-emitting diode (PLED) consisting of a blend of poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] (poly-TPD) and SR540 as an electron-blocking layer, Super Yellow-Poly(p-phenylene vinylene) (SY-PPV) blended with SR540 as an emissive layer, and poly(9,9-di-n-octylfluorenyl-2,7-diyl) as a hole-blocking layer is fabricated from solution. The trilayer PLED shows a 23% increase in efficiency at low voltage as compared to a single layer SY-PPV PLED. However, at higher voltage, the advantage in current efficiency gradually decreases. A combined experimental and modelling study shows that the increased efficiency is not only due to the elimination of exciton quenching at the electrodes but also due to suppressed nonradiative trap-assisted recombination due to carrier confinement. At high voltages, holes can overcome the hole-blocking barrier, which explains the efficiency roll-off.

Design and synthesis of oxymatrine analogues overcoming drug resistance in hepatitis B virus through targeting host heat stress cognate 70.

PubMed

Gao, Li-Mei; Han, Yan-Xing; Wang, Yu-Ping; Li, Yu-Huan; Shan, Yong-Qiang; Li, Xin; Peng, Zong-Gen; Bi, Chong-Wen; Zhang, Tian; Du, Na-Na; Jiang, Jian-Dong; Song, Dan-Qing

2011-02-10

Heat-stress cognate 70 (Hsc70) is a host protein required for hepatitis B virus (HBV) replication, and oxymatrine (1) suppresses Hsc70 expression. Taking Hsc70 as a target against HBV, 22 analogues of 1 defined with substituents at position 1, 13, or 14 were synthesized and evaluated for their activity on Hsc70 mRNA expression. The SAR revealed that (i) the oxygen atom at the 1-position was not essential, (ii) increasing electron density on the ring D reduced the activity, and (iii) introducing a proper substituent at the 13- and/or 14-position(s), especially electron-withdrawing groups, might enhance the activity. Among the analogues, 6b possessing 13-ethoxyl afforded an increased activity in respect to 1. Importantly, it was active for either wild-type or lamivudine-resistant HBV, as its target is host Hsc70 but not viral enzymes. LD(50) of 6b in mice was over 750 mg/kg in oral route. We consider compound 6b promising for further investigation.

EMBRYO TOXICITY OF THE ALKYLPHENOL DEGREDATION PRODUCT 4-NONYLPHENOL TO THE CRUSTACEAN DAPHNIA MAGNA. (R826129)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Toxicological properties of thio- and alkylphenols causing flavor tainting in fish from the upper Wisconsin River

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heil, T.P.; Lindsay, R.C.

1989-08-01

EC50 Microtox (5 min, 25 degrees C) assay values for 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2,4-diisopropylphenol, 2,5-diisopropylphenol 2,6-diisopropylphenol, 3,5-diisopropylphenol, carvacrol, thymol, thiophenol, and thiocresol ranged from 2 x 10(-2) mM for thymol (least toxic) to 2 x 10(-4) mM for 2,4-diisopropylphenol and 4-isopropylphenol (most toxic).

Estrogenic alkylphenols in fish tissues, sediments, and waters from the U.K. Tyne and Tees estuaries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lye, C.M.; Frid, C.L.J.; Gill, M.E.

1999-04-01

Nonylphenols and related compounds are common products of biodegradation of a large group of nonionic surfactants, the nonylphenol polyethoxylates. Many of these compounds are known to be environmentally persistent and to elicit estrogenic response in both mammals and fish. In this study, nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and octylphenol (OP) were found in tissues of mature male flounder, Platichthys flesus, and in tissues of juvenile flounder. These fish also showed detectable levels of the yolk protein vitellogenin in their plasma, indicative of estrogenic exposure. The compounds were also found in discharges from a major sewage treatment works and in sedimentsmore » from two estuaries in north-east England; the highest levels from the highly industrialized Tees and lower levels from the industrialized/urbanized Tyne estuary. The implications of these findings for fish populations are discussed.« less

Lignin Depolymerisation and Lignocellulose Fractionation by Solvated Electrons in Liquid Ammonia.

PubMed

Prinsen, Pepijn; Narani, Anand; Rothenberg, Gadi

2017-03-09

We explored the depolymerisation of several lignins in liquid ammonia at relatively high temperatures and pressures (120 °C and 88 bar). Five different lignins were tested: Indulin AT kraft, Protobind 1000 soda, wheat straw organosolv, poplar organosolv and elephant grass-milled wood lignin (EG MWL). In pure liquid ammonia, all lignins underwent slow incorporation of nitrogen into their structure, resulting in higher molecular weight and polydispersity index. Subsequently, we show a reductive depolymerisation by solvated electrons at room temperature by adding sodium metal to the liquid ammonia without any external hydrogen donor. The netto yields of bio-oil are low for technical lignins (10-23 %), but with higher yields of alkylphenols. In the case of native EG MWL, netto yields of 40 % bio-oil were achieved. Finally, when the room temperature method was applied to poplar wood fibre, we observe improved delignification upon the addition of sodium compared to poplar wood fractionation in pure liquid ammonia. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnCl 2 induced catalytic conversion of softwood lignin to aromatics and hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongliang; Zhang, Libing; Deng, Tiansheng

2016-01-01

Selective cleavage of C-O-C bonds in lignin without disrupting C-C linkages can result in releasing aromatic monomers and dimers that can be subsequently converted into chemicals and fuels. Results showed that both biomass-derived lignin and lignin model compounds were depolymerized in a highly concentrated ZnCl2 solution. Zn2+ ions in highly concentrated ZnCl2 solutions appeared to selectively coordinate with C-O-C bonds to cause key linkages of lignin much easier to cleave. In 63 wt.% ZnCl2 solution at 200 °C for 6 h, nearly half of the softwood technical lignin was converted to liquid products, of which the majority was alkylphenols. Resultsmore » indicated that most β-O-4 and Cmethyl-OAr bonds of model compounds were cleaved undersame conditions, providing a foundation towards understanding lignin depolymerization in a concentrated ZnCl2 solution. The phenolic products were further converted into cyclic hydrocarbons via hydrodeoxygenation and coupling reactions by co-catalyst Ru/C.« less

Methods development for separation of inorganic anions, organic acids and bases, and neutral organic compounds by ion chromatography and capillary electrophoresis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jie

1999-04-01

A novel anion-exchange resin containing three amine groups was prepared by reaction of a chloromethylated polystyrene-divinylbenzene (PS-DVB) resin with diethylenetriamine. After being protonated by contact with an aqueous acid, this resin can be used for ion chromatographic separation of anions. The charge on the resins can be varied from +1 to +3 by changing the mobile phase pH. The selectivity of the new ion exchangers for various inorganic anions was quite different from that of conventional anion exchangers. The performance of this new anion exchanger was studied by changing the pH and the concentration of the eluent, and several differentmore » eluents were used with some common anions as testing analytes. Conductivity detection and UV-visible detection were applied to detect the anions after separation. The new resin can also be used for HPLC separation of neutral organic compounds. Alkylphenols and alkylbenzenes were separated with this new polymeric resin, and excellent separations were obtained under simple conditions. This report contains Chapter 1: General introduction and Chapter 6: General conclusions.« less

Microwave-assisted acid pretreatment of alkali lignin: Effect on characteristics and pyrolysis behavior.

PubMed

Duan, Dengle; Ruan, Roger; Wang, Yunpu; Liu, Yuhuan; Dai, Leilei; Zhao, Yunfeng; Zhou, Yue; Wu, Qiuhao

2018-03-01

This study performed microwave-assisted acid pretreatment on pure lignin. The effects of microwave temperature, microwave time, and hydrochloric acid concentration on characteristics and pyrolysis behavior of lignin were examined. Results of ultimate analysis revealed better properties of all pretreated samples than those of raw lignin. Fourier transform infrared spectroscopy analysis showed breakage of βO4 bond and aliphatic side chain, decrease in OH groups, and formation of CO groups in pretreatment. Microwave temperature exerted more significant influence on lignin structure. Thermal stability of treated lignin was improved and insensitive to short microwave time and acid concentration under mild conditions. Resulting from improved alkyl-phenols and decreased alkoxy-phenols, microwave-assisted acid pretreatment of lignin yielded bio-oil with excellent quality. Total yield of phenols in pyrolysis vapors (200 °C) improved to 14.15%, whereas that of guaiacols decreased to 22.36%. This study shows that microwave-assisted acid pretreatment is a promising technology for lignin conversion. Copyright © 2017 Elsevier Ltd. All rights reserved.

MICROBIAL METABOLISM OF AROMATIC COMPOUNDS I.

PubMed Central

Tabak, Henry H.; Chambers, Cecil W.; Kabler, Paul W.

1964-01-01

Tabak, Henry H. (Robert A. Taft Sanitary Engineering Center, Cincinnati, Ohio), Cecil W. Chambers, and Paul W. Kabler. Microbial metabolism of aromatic carbon compounds. I. Decomposition of phenolic compounds and aromatic hydrocarbons by phenol-adapted bacteria. J. Bacteriol. 87:910–919. 1964.—Bacteria from soil and related environments were selected or adapted to metabolize phenol, hydroxy phenols, nitrophenols, chlorophenols, methylphenols, alkylphenols, and arylphenols when cultured in mineral salts media with the specific substrate as the sole source of carbon. A phenol-adapted culture (substrate-induced enzyme synthesis proven) was challenged in respirometric tests with 104 related compounds; probable significant oxidative activity occurred with 65. Dihydric phenols were generally oxidized; trihydric phenols were not. Cresols and dimethylphenols were oxidized; adding a chloro group increased resistance. Benzoic and hydroxybenzoic acids were oxidized; sulfonated, methoxylated, nitro, and chlorobenzoic acids were not; m-toluic acid was utilized but not the o- and p-isomers. Benzaldehyde and p-hydroxybenzaldehyde were oxidized. In general, nitro- and chloro-substituted compounds and the benzenes were difficult to oxidize. PMID:14137630

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

PubMed

Gao, Dawen; Li, Zhe; Guan, Junxue; Liang, Hong

2017-04-01

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, NP1EO and NP2EO 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 NPnEO compounds were most abundant in winter, with the total concentrations of influent NP, NP1EO and NP2EO ranging from 3900 to 7000ng/L, 4000 to 4800ng/L and 5200 to 7200ng/L, respectively. Regarding the total removal efficiencies of the three types of short-chain NPnEO 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; NP2EO concentrations decreased as follows: summer>autumn>winter>spring, while NP1EO 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 NPnEOs from the wastewater. Copyright © 2016. Published by Elsevier B.V.

Solvent Extraction of Sodium Hydroxide Using Alkylphenols and Fluorinated Alcohols: Understanding the Extraction Mechanism by Equilibrium Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Hyun-Ah; Engle, Nancy L.; Bonnesen Peter V.

2004-03-29

In the present work, it has been the aim to examine extraction efficiencies of nine proton-ionizable alcohols (HAs) in 1-octanol and to identify both the controlling equilibria and predominant species involved in the extraction process within a thermochemical model. Distribution ratios for sodium (DNa) extraction were measured as a function of organic-phase HA and aqueous-phase NaOH molarity at 25 °C. Extraction efficiency follows the expected order of acidity of the HAs, 4-(tert-octyl) phenol (HA 1a) and 4-noctyl- a,a-bis-(trifluoromethyl)benzyl alcohol (HA 2a) being the most efficient extractants among the compounds tested. By use of the equilibrium-modeling program SXLSQI, a model formore » the extraction of NaOH has been advanced based on an ion-pair extraction by the diluent to give organic-phase Na+OH- and corresponding free ions and cation exchange by the weak acids to form monomeric organic-phase Na+A- and corresponding free organic-phase ions.« less

Development of molecularly imprinted polymer in porous film format for binding of phenol and alkylphenols from water.

PubMed

Gryshchenko, Andriy O; Bottaro, Christina S

2014-01-20

Molecularly imprinted polymers (MIPs) were fabricated on glass slides with a "sandwich" technique giving ~20 µm thick films. Methanol/water as a solvent, and polyethyleneglycol and polyvinylacetate as solvent modifiers, were used to give a porous morphology, which was studied with scanning electron microscopy and gravimetric analysis. Various MIPs were synthesized through non-covalent imprinting with phenol as the template; itaconic acid, 4-vinylpyridine, and styrene as monomers; ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and pentaerythritol triacrylate (PETA) as cross-linkers. Binding and imprinting properties of the MIPs were evaluated based on phenol adsorption isotherms. Since phenol has only one weakly acidic hydroxyl group and lacks unique structural characteristics necessary for binding specificity, the preparation of selective MIPs was challenging. The recognition of phenol via hydrogen bonding is suppressed in water, while hydrophobic interactions, though promoted, are not specific enough for highly-selective phenol recognition. Nevertheless, the styrene-PETA MIP gave modest imprinting effects, which were higher at lower concentrations (Imprinting Factor (IF) = 1.16 at 0.5 mg·L(-1)). The isotherm was of a Freundlich type over 0.1-40 mg·L(-1) and there was broad cross-reactivity towards other structurally similar phenols. This shows that phenol MIPs or simple adsorbents can be developed based on styrene for hydrophobic binding, and PETA to form a tighter, hydrophilic network.

DETERMINATION OF SEX HORMONES AND NONYLPHENOL ETHOXYLATES IN THE AQUEOUS MATRIXES OF TWO PILOT-SCALE MUNICIPAL WASTEWATER TREATMENT PLANTS

EPA Science Inventory

Two analytical methods were developed and refined for the detection and quantitation of two groups of endocrine-disrupting chemicals (EDCs) in the liquid matrixes of two pilot-scale municipal wastewater treatment plants. The targeted compounds are seven sex hormones (estradiol, ...

Impact of non-ionic surfactant on the long-term development of lab-scale-activated sludge bacterial communities.

PubMed

Lozada, Mariana; Basile, Laura; Erijman, Leonardo

2007-01-01

The development of bacterial communities in replicate lab-scale-activated sludge reactors degrading a non-ionic surfactant was evaluated by statistical analysis of denaturing gradient gel electrophoresis (DGGE) fingerprints. Four sequential batch reactors were fed with synthetic sewage, two of which received, in addition, 0.01% of nonylphenol ethoxylates (NPE). The dynamic character of bacterial community structure was confirmed by the differences in species composition among replicate reactors. Measurement of similarities between reactors was obtained by pairwise similarity analysis using the Bray Curtis coefficient. The group of NPE-amended reactors exhibited the highest similarity values (Sjk=0.53+/-0.03), indicating that the bacterial community structure of NPE-amended reactors was better replicated than control reactors (Sjk=0.36+/-0.04). Replicate NPE-amended reactors taken at different times of operation clustered together, whereas analogous relations within the control reactor cluster were not observed. The DGGE pattern of isolates grown in conditioned media prepared with media taken at the end of the aeration cycle grouped separately from other conditioned and synthetic media regardless of the carbon source amendment, suggesting that NPE degradation residuals could have a role in the shaping of the community structure.