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Sample records for alkylphenol ethoxylates apeos

  1. Alkylphenols and their ethoxylates in seafood from the Tyrrhenian Sea.

    PubMed

    Ferrara, Fulvio; Ademollo, Nicoletta; Delise, Mirella; Fabietti, Fabio; Funari, Enzo

    2008-07-01

    The present study reports the results of an investigation on occurrence of octylphenols (OPs), nonylphenols (NPs) and their respective ethoxylates (with 1-6 ethoxylic group) in aquatic species of commercial interest from the Tyrrhenian Sea. Samples were collected at Livorno, Fiumicino and Salerno commercial harbors, during September-October 2003. The data obtained showed that almost all of the tested compounds were found in all the samples. NP was generally detected at the highest concentrations. Among the tested species common to the three sampling sites, mullets and seabreams generally showed high values of total alkylphenols (APs) and alkylphenol ethoxylates (APEOs) (44-55 ng g(-1) and 27-525 ng g(-1) fw), yet, the maximum concentrations were found in shrimps from Fiumicino (1255 ng g(-1) fw). On the contrary, the lowest concentrations were observed in hakes and anchovies (34-36 ng g(-1) and 6-37 ng g(-1) fw). Tuna, exhibited very high concentrations of total alkylphenolic compounds (APEs) (889 ng g(-1) fw). Seafood from Fiumicino fishing area, which is under the influence of the River Tiber, showed a degree of contamination of at least one order of magnitude higher than the other two sites. On the basis of the results of this study, the corresponding daily intakes of NPs are much lower than the TDI proposed by the Danish Environmental Agency.

  2. The replacement of alkyl-phenol ethoxylates to improve the environment acceptability of drilling fluid additives

    SciTech Connect

    Getliff, J.M.; James, S.G.

    1996-12-31

    Alkyl-phenol ethoxylates (APEO) are a class of surfactants which have been used widely in the drilling fluid industry. The popularity of these surfactants is based on their cost effectiveness, availability and the range of hydrophilic-lipophilic balance values obtainable. Studies have shown that APEOs exhibit oestrogenic effects, and can cause sterility in some male aquatic species. This may have subsequent human consequences and such problems have lead to a banning of their use in some countries and agreements to phase out their use e.g. PARCOM recommendation 92/8. The use of APEOs as additives in detergents, lubricants and stuck-pipe release agents for drilling fluid applications is discussed. The effectiveness of products formulated with APEOs are directly compared with alternative products which are non-persistent and less damaging to aquatic species. Lubricity measurements using standard and in-house designed equipment and washing tests to compare the efficiency of surfactants are explained and product performance results presented. The results show that alternatives to products containing APEOs are available and that in some cases they show a better technical performance. In addition to the improved environmental acceptability of the base chemicals, the better performance enables lower concentrations to be used, hence reducing the environmental impact even further.

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

    PubMed

    Zoller, Uri

    2006-02-01

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

  4. Quantitative determination of octylphenol, nonylphenol, alkylphenol ethoxylates and alcohol ethoxylates by pressurized liquid extraction and liquid chromatography-mass spectrometry in soils treated with sewage sludges.

    PubMed

    Andreu, Vicente; Ferrer, Emilia; Rubio, José Luís; Font, Guillermina; Picó, Yolanda

    2007-05-25

    Surfactants have one of the highest production rates of all organic chemicals. Non-ionic surfactants, especially alkylphenol ethoxylates, received most attention as precursors of estrogenic metabolic products generated during wastewater treatment. Alkylphenols (octyl and nonylphenol), alkylphenol polyethoxylates (APEOs), and alcohol ethoxylates (AEOs) have been determined in a Mediterranean forest soil (Mediterranean Rendzic Leptosol) amended with sludges from six waste water treatment plants (WWTPs) located in the Valencian Community. These compounds were isolated from soil by pressurized liquid extraction (PLE) using a mixture acetone-hexane (50:50 v/v), the extracts were cleaned up by solid-phase extraction (SPE) with C(18), and determined by liquid chromatography atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) using analytical standards for quantification. The method enabled high-reliable identification by monitoring the corresponding ammonium adduct [M+NH(3)](+) for AEOs and APEOs, and the deprotonated molecule [M-H](-) for octyl and nonylphenol. Recoveries, determined spiking soil samples at different concentrations, ranged from 89 to 94%, with limits of quantification from 1 to 100 microg kg(-1). Data obtained from a soil sample mixed with biosolids in the laboratory showed that these compounds are present at concentrations ranging from 0.02 to 5 mg kg(-1). According to these concentrations, levels of possible risk can be concluded for the presence of non-ionic surfactants in soil. However, further assessment will be necessary to establish the relationship between exposure and effect findings.

  5. METHODS FOR THE ANALYSIS OF ALKYLPHENOL ETHOXYLATES AND DERIVATIVES

    EPA Science Inventory

    Alkylphenol ethoxylates and their derivatives are well known for their harmful impact in wildlife. These compounds are being phased-out and banned in most European Countries. Their use has increased in the U.S. resulting in their addition to the Priority Testing List, TSCA (1...

  6. Selecting Surrogates for an Alkylphenol Ethoxylate Analytical Method in Sewage and Soil Matrices

    EPA Science Inventory

    Alkylphenol ethoxylates (APEs) are nonionic surfactants commonly used in industrial detergents. These products contain complex mixtures of branched and linear chains. APEs and their degradation products, alkylphenols, are highly toxic to aquatic organisms, potentially estrogeni...

  7. 40 CFR 721.10443 - Ethoxylated alkylphenol sulfate, ammonium salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., ammonium salt (generic). 721.10443 Section 721.10443 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10443 Ethoxylated alkylphenol sulfate, ammonium salt... identified generically as ethoxylated alkylphenol sulfate, ammonium salt (PMN P-01-470) is subject...

  8. 40 CFR 721.10443 - Ethoxylated alkylphenol sulfate, ammonium salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., ammonium salt (generic). 721.10443 Section 721.10443 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10443 Ethoxylated alkylphenol sulfate, ammonium salt... identified generically as ethoxylated alkylphenol sulfate, ammonium salt (PMN P-01-470) is subject...

  9. 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...

  10. ITC-CMA partnership and data needs for alkylphenols and ethoxylates

    USGS Publications Warehouse

    Rattner, B.A.; Rice, C.P.; Walker, J.D.

    1996-01-01

    The ITC has been an independent advisory committee to the EPA Administrator since enactment of the Toxics Substances Control Act (TSCA) in 1976. The ITC identifies and coordinates U.S. Government data needs for TSCA-regulable chemicals, and makes recommendations to the Administrator for priority testing consideration. Chemicals recommended by the ITC are added to the TSCA Priority Testing List that is revised semi-annually in Reports to the Administrator. In recent Reports, the ITC added alkylphenols (APs) and ethoxylates to the Priority Testing List. About 500 million pounds are produced annually for industrial processing, cleaning and personal care products. APs have been detected in the tissues of fish from the Great Lakes, and one AP (nonylphenol) causes vitellogenin gene expression in trout hepatocytes. Numerous APs and ethoxylates were recommended by the ITC because data are needed on: (1) chemical composition, (2) environmental fate of parent chemicals and impurities, and (3) health and ecological effects (including toxicokinetics and endocrine-modulating effects). In response to the ITC's recommendations, two activities have ensued. First, the EPA promulgated rules requiring manufacturers, importers and processors of APs and ethoxylates to submit production and exposure reports, and unpublished health and safety studies, for review. Second, the Alkylphenols and Ethoxylates Panel of Chemical Manufacturers Association (CMA) and the ITC formed a Dialogue Group to discuss the data needs. Data needs and activities initiated by the Dialogue Group will be presented.

  11. Octyl- and Nonylphenol Ethoxylates and Their Transformation Products in the Back River, Maryland

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Back River is a sub-estuary of the Chesapeake Bay that receives effluent from a wastewater treatment plant (WWTP) and urban runoff from the metropolitan area of Baltimore, MD. In order to study the fate of the alkylphenol ethoxylates (APEOs) and their transformation products, including those th...

  12. Fate and Distribution of the Octyl- and Nonylphenol Ethoxylates and Some Carboxylated Transformation Products in the Back River, Maryland

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Back River is a sub-estuary of the Chesapeake Bay that receives effluent from a wastewater treatment plant (WWTP) and urban runoff from the metropolitan area of Baltimore, MD. In order to study the fate of the alkylphenol ethoxylates (APEOs) and their transformation products, including those th...

  13. Pressurized liquid extraction followed by liquid chromatography-mass spectrometry for the determination of alkylphenolic compounds in river sediment.

    PubMed

    Petrovic, Mira; Lacorte, Silvia; Viana, Paula; Barceló, Damia

    2002-06-14

    A new methodology based on pressurized liquid extraction (PLE) followed by LC-MS is presented for the simultaneous and unequivocal determination of alkylphenol ethoxylates (APEOs) and their degradation products, alkylphenols (APs) and alkylphenoxy carboxylates (APECs), in sediment samples. The protocol, applicable to a full range of APEO oligomers and degradation products, permits the sensitive and selective determination of APEOs (nEO = 1-15), APECs (nEO = 0-1) and APs at low ppb levels (LODs = 1-5 microg/kg) in sediment samples. Optimization of the operational parameters of PLE clearly demonstrates that significant thermal losses of APs occur during extraction at elevated temperatures. The loss of octylphenol (OP) at 100 degrees C was 61.2% and of nonylphenol (NP) 40.0%, whereas other compounds were completely recovered. Thus, to avoid losses due to the volatility of alkylphenols, a low extraction temperature should be applied. The conditions that gave the best results for all target compounds were as follows: extraction solvent mixture, methanol-acetone (1:1, v/v); temperature, 50 degrees C; pressure, 1500 p.s.i.; two static cycles. Using PLE and a subsequent clean-up with solid-phase extraction (SPE), the simultaneous extraction of APEOs, APs and APECs from sediment samples was achieved yielding recoveries >70% and producing low MS background noise. The developed methodology was applied on a routine basis to the analysis of alkylphenolic compounds in sediment samples. APEOs and their persistent degradation products were detected in significant concentrations in sediments from Portuguese rivers, especially at sites situated in the proximity of industrial plants (mainly the textile industry). The total concentration of alkylphenolic compounds (APEOs+APs+APECs) ranged from 155 to 2400 microg/kg. Of all the alkylphenolic compounds, NP comprised 40 to 50% with concentrations up to 1172 microg/kg.

  14. Effects of nonionic surfactants on the microbial mineralization of phenanthrene in soil-water systems. [Surfactants used: alkylethoxylate and alkylphenol ethoxylate

    SciTech Connect

    Laha, S.; Luthy, R.G.

    1992-01-01

    The purpose of the work reported in this paper was to determine whether the inhibitory effect on microbial degradation of phenanthrene was specific to the nonionic surfactants used previously, i.e., the alkylethoxylate and alkylphenol ethoxylate surfactants. Thus, a number of nonionic surfactants of varying structures and properties were selected for further investigation. In addition, several tests were performed to verify results from earlier experiments.

  15. 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).

  16. Identification of alkylphenols and other estrogenic compounds in wastewater, septage, and groundwater on Cape Cod, Massachusetts

    USGS Publications Warehouse

    Rudel, Ruthann A.; Melly, Steven J.; Geno, Paul W.; Sun, Gang; Brody , Julia G.

    1998-01-01

    As part of a larger effort to characterize the impacts to Cape Cod drinking water supplies from on-site wastewater disposal, we developed two analytical methods using HPLC and GC/MS for a range of compounds identified as endocrine-disrupting chemicals (EDCs), including the nonionic surfactants alkylphenol polyethoxylates (APEOs) and their degradation products. We analyzed samples for nonylphenol, octylphenol, and their ethoxylates up to the hexaethoxylate using an HPLC method, with detection limits ranging from 2 to 6 μg/L. A set of phenolic compounds including bisphenol A and nonylphenol were derivatized and analyzed by GC/MS with detection limits from 0.001 to 0.02 μg/L. Total APEOs in untreated wastewater and septage samples ranged from 1350 to 11 000 μg/L by the HPLC method. Nonylphenol was detected in all septage samples at concentrations above 1000 μg/L. Phenylphenol and bisphenol A were detected in septage and wastewater at about 1 μg/L. In groundwater downgradient of an infiltration bed for secondary treated effluent, nonyl/octylphenol and ethoxylates were present at about 30 μg/L. Bisphenol A, nonylphenol monoethoxycarboxylate, and nonyl/octylphenol tetraethoxylate were detected in some drinking water wells at concentrations ranging from below the quantitation limit to 32.9 μg/L. Results suggest that septic systems may be a significant source of APEOs to groundwater.

  17. Improved derivatization protocol for simultaneous determination of alkylphenol ethoxylates and brominated flame retardants followed by gas chromatography-mass spectrometry analyses.

    PubMed

    Chokwe, T B; Okonkwo, J O; Sibali, L L; Ncube, E J

    2014-01-01

    An improved derivatization protocol for the simultaneous determination of alkylphenol ethoxylates and brominated flame retardants with heptafluorobutyric anhydride under triethylamine amine base was investigated. The derivatization reaction was completed in 30 min at 50 °C using hexane as solvent. Under these conditions, it was observed that alkylphenol ethoxylates and tetrabromobisphenol A were derivatized successfully in the presence of hexabromocyclododecane, lower congeners of polybrominated biphenyls and polybrominated diphenyl ethers. The improved protocol was applied to the recover of the analytes of interest from a simulated water sample after solid phase extraction. The recoveries achieved were above 60%. The limit of detection and limit of quantification ranged from 0.01-0.20 and 0.05-0.66 μg L(-1), respectively. The improved derivatization procedure was also successfully applied to determine trace amounts of these compounds in environmental water samples. The concentrations of the targeted analytes from the environmental samples were determined from limit of quantification. The levels of the targeted compounds in the environmental samples ranged from nd-7.63 ±2.83 μg L(-1).

  18. A robust method for determining water-extractable alkylphenol polyethoxylates in textile products by reaction-based headspace gas chromatography.

    PubMed

    Zhang, Shu-Xin; Chai, Xin-Sheng; Huang, Bo-Xi; Mai, Xiao-Xia

    2015-08-07

    Alkylphenol polyethoxylates (APEO), surfactants used in the production of textiles, have the potential to move from the fabric to the skin of the person wearing the clothes, posing an inherent risk of adverse health consequences. Therefore, the textile industry needs a fast, robust method for determining aqueous extractable APEO in fabrics. The currently-favored HPLC methods are limited by the presence of a mixture of analytes (due to the molecular weight distribution) and a lack of analytical standards for quantifying results. As a result, it has not been possible to reach consensus on a standard method for the determination of APEO in textiles. This paper addresses these limitations through the use of reaction-based head space-gas chromatography (HS-GC). Specifically, water is used to simulate body sweat and extract APEO. HI is then used to react the ethoxylate chains to depolymerize the chains into iodoethane that is quantified through HS-GC, providing an estimate of the average amount of APEO in the clothing. Data are presented to justify the optimal operating conditions; i.e., water extraction at 60°C for 1h and reaction with a specified amount of HI in the headspace vial at 135°C for 4h. The results show that the HS-GC method has good precision (RSD<10%) and good accuracy (recoveries from 95 to 106%) for the quantification of APEO content in textile and related materials. As such, the method should be a strong candidate to become a standard method for such determinations.

  19. 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?

  20. Use of oleic-acid functionalized nanoparticles for the magnetic solid-phase microextraction of alkylphenols in fruit juices using liquid chromatography-tandem mass spectrometry.

    PubMed

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

    2016-05-01

    Magnetic nanoparticles of cobalt ferrite with oleic acid as the surfactant (CoFe2O4/oleic acid) were used as sorbent material for the determination of alkylphenols in fruit juices. High sensitivity and specificity were achieved by liquid chromatography and detection using both diode-array (DAD) and electrospray-ion trap-tandem mass spectrometry (ESI-IT-MS/MS) in the selected reaction monitoring (SRM) mode of the negative fragment ions for alkylphenols (APs) and in positive mode for ethoxylate APs (APEOs). The optimized conditions for the different variables influencing the magnetic separation procedure were: mass of magnetic nanoparticles, 50mg, juice volume, 10mL diluted to 25mL with water, pH 6, stirring for 10min at room temperature, separation with an external neodymium magnet, desorption with 3mL of methanol and orbital shaking for 5min. The enriched organic phase was evaporated and reconstituted with 100µL acetonitrile before injecting 30µL into a liquid chromatograph with a mobile phase composed of acetonitrile/0.1% (v/v) formic acid under gradient elution. Quantification limits were in the range 3.6 to 125ngmL(-1). The recoveries obtained were in the 91-119% range, with RSDs lower than 14%. The ESI-MS/MS spectra permitted the correct identification of both APs and APEOs in the fruit juice samples.

  1. Aquatic toxicity of nine aircraft deicer and anti-icer formulations and relative toxicity of additive package ingredients alkylphenol ethoxylates and 4,5-methyl-1H-benzotriazoles

    USGS Publications Warehouse

    Corsi, S.R.; Geis, S.W.; Loyo-Rosales, J. E.; Rice, C.P.

    2006-01-01

    Characterization of the effects of aircraft deicer and anti-icer fluid (ADAF) runoff on aquatic organisms in receiving streams is a complex issue because the identities of numerous toxic additives are proprietary and not publicly available. Most potentially toxic and endocrine disrupting effects caused by ADAF are due to the numerous additive package ingredients which vary among manufacturers and types of ADAF formulation. Toxicity investigations of nine ADAF formulations indicate that endpoint concentrations for formulations of different manufacturers are widely variable. Type IV ADAF (anti-icers) are more toxic than Type I (deicers) for the four organisms tested (Vibrio fischeri, Pimephales promelas, Ceriodaphnia dubia, and Selenastrum capricornutum). Acute toxicity endpoint concentrations ranged from 347 to 7700 mg/L as ADAF for Type IV and from 1550 to 45 100 mg/L for Type I formulations. Chronic endpoint concentrations ranged from 70 to 1300 mg/L for Type IV and from 37 to 18 400 mg/L for Type I formulations. Alkylphenol ethoxylates and tolyltriazoles are two known classes of additives. Nonylphenol, nonylphenol ethoxylates, octylphenol, octylphenol ethoxylates, and 4,5-methyl-1H-benzotriazoles were quantified in the nine ADAF formulations, and toxicity tests were conducted with nonylphenol ethoxylates and 4,5-methyl-1H-benzotriazoles. Toxicity units computed for glycol and these additives, with respect to toxicity of the ADAF formulations, indicate that a portion of ADAF toxicity can be explained by the known additives and glycols, but much of the toxicity is due to unidentified additives. ?? 2006 American Chemical Society.

  2. LC-MS-MS analysis and occurrence of octyl- and nonylphenol, their ethoxylates and their carboxylates in Belgian and Italian textile industry, waste water treatment plant effluents and surface waters.

    PubMed

    Loos, Robert; Hanke, Georg; Umlauf, Gunther; Eisenreich, Steven J

    2007-01-01

    Alkylphenols (APs), alkylphenol ethoxylates (APEOs), ethoxycarboxylate metabolites (APECs) and bisphenol A were determined in surface water using solid-phase extraction (SPE) followed by triple-quadrupole LC-MS-MS. APs were separated by LC from APECs using an acetonitrile-water-gradient without the addition of any buffer. Nonylphenol ethoxycarboxylates (NPECs) interfere in the detection of nonylphenols (NPs) when using an acidic mobile phase, because they produce the same MS-MS fragment ions (219>133 and 147). 4n-NP shows the characteristic transition 219>106; it is well suited as internal standard. Nonylphenol ethoxylates NPE(n)Os (n=1-17) were analysed separately in a second run by positive ionization using an ammonium acetate mobile phase. Textile industry discharges, the corresponding wastewater treatment plant (WWTP) effluents and the receiving rivers in Belgium and Italy were analysed. Among the substances investigated, NPE1C and NPE2O exhibited the highest concentrations in the water samples, up to 4.5 microg l(-1) NPE1C in a WWTP effluent and 3.6 microg l(-1) NPE2O in a river. The highest NP levels were found in the receiving rivers (max. 2.5 microg l(-1)). The predicted no-effect concentration (PNEC) for NP of 0.33 microg l(-1) for water species was frequently exceeded in the surface waters investigated, suggesting potential adverse effects to the aquatic environment.

  3. The environmental occurrence and effect of alkylphenol polyethoxylates and their metabolites in Taiwan

    NASA Astrophysics Data System (ADS)

    Ding, W.

    2009-12-01

    Alkylphenol polyethoxylates (APEOs) are widely used nonionic surfactants in domestic, agricultural and household applications, which have been commonly found in wastewater discharges and in sewage treatment plant effluents. Degradation of APEOs in wastewater or in the environment generates more persistent pollutants, including alkylphenols (APs, such as 4-nonylphenol isomers (4-NPs) and 4-t-octylphenol (4-t-OP)) and shortened ethoxy chain APEO residues (such as AP1~3EO). These metabolites of APEOs are of interest in the field of environmental monitoring because of the volume of these substances used and their activity as either endocrine disruptors or as persistent pollutants. APEOs are mass-produced and used widely in Taiwan. Large quantities of these metabolites in wastewater are discharged into the rivers directly because Taiwan’s municipal and industrial wastewater treatment facilities are deficient. However, the occurrence and fate of these metabolites are unclear and can potentially affect the aquatic environment and public health in Taiwan. Determination of APEOs and their metabolites have been performed for household detergents, various surface water, soil, sediments, biota, foodstuffs and even in breast milk. APEOs and their metabolites were detected in all media analyzed and in all environmental samples. The relatively high concentrations detected in oysters and snails provide evidence for bioaccumulation of APs. The presence of APs in breast milk implies that APs enter the food chain in local biota after long chain APEOs were biodegraded. There are also some indications that the plastic wrappings and containers for foodstuffs sold in Taiwan may contain NP or tris(nonylphenol) phosphate (TNPP) used as plasticizers or antioxidants. In addition, possible sources of APs may come from the extensive use of pesticides containing APEO as emulsifiers in agriculture.

  4. Simultaneous determination of linear alkylbenzenesulfonates, alkylphenol polyethoxylates, and nonylphenol by high-performance liquid chromatography

    SciTech Connect

    Marcomini, A.; Giger, W.

    1987-07-01

    Linear 4-alkylbenzenesulfonates (LAS), 4-alkylphenol polyethoxylates (APEO) (i.e., 4-octylphenol polyethoxylates (OPEO) and 4-nonylphenol polyethoxylates (NPEO), and 4-nonylphenol (NP) are simultaneously determined by reversed-phase high-performance liquid chromatography (HPLC) using octylsilica columns and water/acetonitrile gradient elution. LAS are separated according to their alkyl chain lengths and coelution of NPEO and NP is observed in contrast to the separation of OPEO and NPEO. The determination of oligomer distributions of APEO and quantitation of NP,NP1EO, and NP2EO require additional information attainable by normal-phase HPLC. Recoveries of 85-100% were found for LAS, APEO, and NP isolated by Soxhlet extraction under basic conditions from laundry detergent powders, sewage sludges, sludge-amended soils, and river sediments. Relative standard deviations for all analytes in the different matrices did not exceed 6%. Detection limits with UV fluorescence detection are 95 ng for NP, 80 ng for LAS, and 65 ng for NPEO with respect to injected amounts.

  5. Identification and quantitation method for nonylphenol and lower oligomer nonylphenol ethoxylates in fish tissues.

    PubMed

    Snyder, S A; Keith, T L; Naylor, C G; Staples, C A; Giesy, J P

    2001-09-01

    Substantial research is currently focused on the toxicological effects of alkylphenol ethoxylates (APEs) and alkylphenols (APs) on aquatic animals. Considerable data are available on the concentrations of APEs and APs in river systems in the United States; however, few if any data are available on the tissue concentrations of fish living in these rivers. A reliable method for the analysis of nonylphenol (NP) and lower oligomer nonylphenol ethoxylates (NPE1-3) in fish tissues has been developed. Nonylphenol and NPE1-3 were extracted from fish tissues using extractive steam distillation. Normal phase high-performance liquid chromatography (HLPC) was used as a cleanup step prior to analysis by gas chromatography with mass selective detection (GC/MSD) using selected ion monitoring. Optimization of this technique resulted in consistent recoveries in excess of 70%, with the exception of NPE3 (17%). Method detection limits (MDLs) and limits of quantitation using the technique range from 3 to 20 and 5 to 29 ng/g wet weight, respectively. Nonylphenol and NPE1 were detected in subsamples (n = 6) of a single common carp captured in the Las Vegas Bay of Lake Mead (NV, USA) at average concentrations of 184+/-4 ng/g and 242+/-9 wet weight, respectively. Nonylphenol ethoxylates were not detected in the carp collected at Lake Mead.

  6. 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.

  7. 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.

  8. 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.

  9. Toxicity on crustaceans and endocrine disrupting activity on Saccharomyces cerevisiae of eight alkylphenols.

    PubMed

    Isidori, Marina; Lavorgna, Margherita; Nardelli, Angela; Parrella, Alfredo

    2006-06-01

    In the last few years many concerns have been raised regarding the environmental safety of alkylphenol polyethoxylate surfactants (APnEOs). They are widely used in detergents, paints, herbicides and many other formulated products. It has been estimated that 60% of APnEOs end up in the aquatic environment; they are biodegradable and transformed into alkylphenols, such as nonylphenol and octylphenol that are hydrophobic and tend to accumulate. In the present study, acute and chronic aquatic toxicity and the estrogenic activity of the following eight alkylphenols were assessed: 4-nonylphenol, 4-octylphenol, 4-nonylphenol-10-ethoxylate, 4-tert-octylphenol, POE (1 to 2)-nonylphenol, POE (6)-nonylphenol, POE (3)-tert-octylphenol and POE (9 to 10)-tert-octylphenol. The toxic potential was measured on the crustaceans Daphnia magna and Ceriodaphnia dubia, while the estrogenic activity was determined by using the YES-test with the strain Saccharomyces cerevisiae RMY326. The results showed that the exposure of crustaceans to the eight xenoestrogens investigated caused both acute and chronic effects. The EC50 values found for C. dubia at 48 h were compared to D. magna at 24h and, gave a first indication about the toxic activity of the compounds investigated, that is better expressed in the long-term. In fact, chronic data showed a strong increase in toxicity with EC50 values one or two orders of magnitude lower than the acute values. The results of the YES-test showed that nonylphenol, octylphenol and 4-tert-octylphenol were the most estrogenic and the bioassay was able to detect their estrogenicity at very low concentrations (ng-microg/l).

  10. Fate of the Alkylphenol Ethoxylate Components of ADAF in Airport Runoff

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aircraft deicing and anti-icing fluids (ADAF) contain toxic compounds that are often released without treatment and in relatively high concentrations to water bodies. The main components in ADAF, propylene glycol and ethylene glycol, are toxic; but in some instances, other constituents, such as alk...

  11. 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...

  12. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

  13. 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...

  14. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  15. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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...

  16. 40 CFR 721.4365 - Substituted ethoxylated hydrocarbon (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  17. 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...

  18. 40 CFR 721.4365 - Substituted ethoxylated hydrocarbon (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

  19. 40 CFR 721.4365 - Substituted ethoxylated hydrocarbon (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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...

  20. 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...

  1. 75 FR 40751 - Castor Oil, Ethoxylated, Oleate; Tolerance Exemption

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-14

    ... AGENCY 40 CFR Part 180 Castor Oil, Ethoxylated, Oleate; Tolerance Exemption AGENCY: Environmental... requirement of a tolerance for residues of castor oil, ethoxylated, oleate (CAS Reg. No. 220037-02-5) with a... residues of castor oil, ethoxylated, oleate on food or feed commodities. DATES: This regulation...

  2. 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.

  3. 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...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  5. 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

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  12. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  13. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  14. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  15. 40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... compound. 721.655 Section 721.655 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical... as an ethoxylated alkyl quaternary ammonium compound (PMN P-96-573) is subject to reporting...

  16. 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,...

  17. 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,...

  18. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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,...

  19. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 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,...

  20. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 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,...

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

    SciTech Connect

    Beck, B.D.; Toole, A.P.; Callahan, B.G.; Siddhanti, S.K. )

    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 aromatic 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.

  2. 40 CFR 721.10309 - Ethoxylated, propoxylated diamine diaryl substituted phenylmethane ester with alkenylsuccinate...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... diaryl substituted phenylmethane ester with alkenylsuccinate (generic). 721.10309 Section 721.10309... Ethoxylated, propoxylated diamine diaryl substituted phenylmethane ester with alkenylsuccinate (generic). (a... generically as ethoxylated, propoxylated diamine diaryl substituted phenylmethane ester with...

  3. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with ethoxylated fatty alcohols. 721.6475 Section 721.6475 Protection of Environment ENVIRONMENTAL... ethoxylated fatty alcohols. (a) Chemical substance and significant new uses subject to reporting. (1) The... generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols (PMN...

  4. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... with ethoxylated fatty alcohols. 721.6475 Section 721.6475 Protection of Environment ENVIRONMENTAL... ethoxylated fatty alcohols. (a) Chemical substance and significant new uses subject to reporting. (1) The... generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols (PMN...

  5. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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...

  6. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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...

  7. 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...

  8. 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...

  9. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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...

  10. 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...

  11. 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...

  12. 77 FR 65834 - Residues of Fatty Acids, Tall-Oil, Ethoxylated Propoxylated; Tolerance Exemption

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-10-31

    ... AGENCY 40 CFR Part 180 Residues of Fatty Acids, Tall-Oil, Ethoxylated Propoxylated; Tolerance Exemption... an exemption from the requirement of a tolerance for residues of fatty acids, tall-oil, ethoxylated... residues of fatty ] acids, tall-oil, ethoxylated propoxylated on food or feed commodities. DATES:...

  13. 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...

  14. 40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... salt. 721.643 Section 721.643 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

  15. 40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... salt. 721.643 Section 721.643 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

  16. 40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... salt. 721.643 Section 721.643 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

  17. 40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... salt. 721.643 Section 721.643 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

  18. 40 CFR 721.643 - Ethoxylated alcohol, phosphated, amine salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... salt. 721.643 Section 721.643 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... 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...

  19. Chromium(VI) oxide oxidation of non-ethoxylated and ethoxylated alcohols for determination by electrospray ionization mass spectrometry.

    PubMed

    Beneito-Cambra, Miriam; Bernabé-Zafón, Virginia; Simó-Alfonso, Ernesto F; Ramis-Ramos, Guillermo

    2010-07-30

    A new derivatization procedure to increase the sensitivity of electrospray ionization mass spectrometry (ESI-MS) to non-ethoxylated and ethoxylated alcohols was investigated. The analytes were oxidized with chromium(VI) oxide and the resulting carboxylic and ethoxy-carboxylic acids were isolated by extraction with ethyl acetate; the extracts were alkalinized and infused into the ESI-MS system working in the negative-ion mode. The yields of the combined oxidation-extraction were ca. 100% for non-ethoxylated fatty alcohols dissolved in acetone and they decreased moderately in samples containing increasing amounts of water (e.g., a 75% yield was obtained with 50% water). Ethoxylated alcohols with more than two ethylene oxide units resulted in yields of ca. 60%. Low limits of detection (LODs) were obtained when the procedure was applied to the analysis of body-care products and cosmetics containing fatty alcohols, e.g., in a varicose-vein cream, the LODs were 25 microg cetyl alcohol and 7.5 microg stearyl alcohol (detected as palmitic acid and stearic acid, respectively) per gram of sample. High molecular mass alcohols were also detected in seawater after pre-concentration by solid-phase extraction. Thus, the proposed method is particularly valuable for use in industrial samples having complex matrices and in environmental samples and it is competitive with other methods for the analysis of trace amounts of fatty alcohols.

  20. 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

  1. Development of an electrochemical biosensor for alkylphenol detection.

    PubMed

    Belkhamssa, Najet; da Costa, João P; Justino, Celine I L; Santos, Patrícia S M; Cardoso, Susana; Duarte, Armando C; Rocha-Santos, Teresa; Ksibi, Mohamed

    2016-09-01

    In this work, electrochemical biosensors based on field effect transistors (FET) with single-walled carbon nanotubes (SWCNT) were constructed as disposable analytical devices to detect alkylphenols through immunoreaction using 4-nonylphenol (NP) as model analyte, and validated by comparison with enzyme-linked immunosorbent assay (ELISA). The calibration curve displays a working range with five concentrations between 5 and 500µgL(-1), and for each concentration, five biosensors were analysed for reproducibility estimation and two analytical measurements were performed for each biosensor for repeatability estimation. The accuracy of the biosensors was validated by analyzing NP contents in ten spiked artificial seawater samples and comparing these results to those obtained with the traditional ELISA methodology. Excellent analytical performance was obtained with reproducibility of 0.56±0.08%, repeatability of 0.5±0.2%, limit of detection for NP as low as 5µgL(-1), and average recovery between 97.8% and 104.6%. This work demonstrates that simple biosensors can be used to detect hazardous priority substances in seawater samples, even at low concentrations.

  2. 40 CFR 721.10245 - Branched and linear fatty alcohol ethoxylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Branched and linear fatty alcohol... Specific Chemical Substances § 721.10245 Branched and linear fatty alcohol ethoxylate (generic). (a... generically as branched and linear fatty alcohol ethoxylate (PMN P-09-207) is subject to reporting under...

  3. 40 CFR 721.10007 - Alcohols, C12-14-secondary, ethoxylated propoxylated.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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)...

  4. 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)...

  5. 40 CFR 721.10245 - Branched and linear fatty alcohol ethoxylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Branched and linear fatty alcohol... Specific Chemical Substances § 721.10245 Branched and linear fatty alcohol ethoxylate (generic). (a... generically as branched and linear fatty alcohol ethoxylate (PMN P-09-207) is subject to reporting under...

  6. 40 CFR 721.10007 - Alcohols, C12-14-secondary, ethoxylated propoxylated.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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)...

  7. 40 CFR 721.10245 - Branched and linear fatty alcohol ethoxylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Branched and linear fatty alcohol... Specific Chemical Substances § 721.10245 Branched and linear fatty alcohol ethoxylate (generic). (a... generically as branched and linear fatty alcohol ethoxylate (PMN P-09-207) is subject to reporting under...

  8. 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.

  9. Alkylphenolic contaminants in the diet: Sparus aurata juveniles hepatic response.

    PubMed

    Traversi, I; Gioacchini, G; Scorolli, A; Mita, D G; Carnevali, O; Mandich, A

    2014-09-01

    A wide range of endocrine disrupter chemicals can mimic steroid hormones causing adverse health effects. Nonylphenol (NP) and t-octhylphenol (t-OP) are man-made alkylphenolic environmental contaminants possessing controversial endocrine disruption properties. This study has investigated the effects of NP and t-OP enriched diets on hepatic tissue and biotransformation activities in the liver. To this aim, sea bream juveniles were fed with commercial diet enriched with three different doses of NP (NP1: 5mg/kg bw, NP2: 50mg/kg bw and NP3: 100mg/kg bw) or t-OP (t-OP1: 5mg/kg bw, t-OP2: 50mg/kg bw and t-OP3: 100mg/kg bw) for 21 days. A significant increase of the hepatosomatic index was observed in NP1 and t-OP1. Alteration of liver morphology was observed in both NP and t-OP exposed juveniles although the most altered endpoints were observed in t-OP2 with 100% of tissue degeneration. Ethoxyresorufin-O-deethylase activity was significantly inhibited by NP and t-OP (p<0.05), while catalase activity was significantly induced, at both doses. A different pattern of protein expression of different isoforms of both vitellogenin and zona radiata protein was evidenced within the treatments. In addition, a significant increase in the abundance of the stress induced heat shock protein 70 gene in the liver of t-OP2 fish and a significant increase in the abundance of the estrogen induced cathepsin D gene in the liver of NP1 and t-OP2 fish, were observed. Finally, estradiol-17β (E2) and testosterone (T) plasma levels and E2/T showed significantly different patterns in NP and t-OP exposed against control fish.

  10. 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.

  11. 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.

  12. Effects of North Sea oil and alkylphenols on biomarker responses in juvenile Atlantic cod (Gadus morhua).

    PubMed

    Sturve, Joachim; Hasselberg, Linda; Fälth, Herman; Celander, Malin; Förlin, Lars

    2006-06-01

    A consequence of oil drilling at sea is the release of produced water contaminated with e.g. polycyclic aromatic hydrocarbons (PAH) and alkylphenols. In the present study, juvenile Atlantic cod were exposed to North Sea oil, nonylphenol and a combination of the North Sea oil and an alkylphenol mixture in a flow-through system. A suite of hepatic biomarkers were analysed. Exposure to North Sea oil resulted in strong induction of CYP1A protein levels and EROD activities. Exposure to nonylphenol, on the other hand, resulted in decreased CYP1A levels and EROD activities. Thus, nonylphenol appears to down-regulate CYP1A expression in Atlantic cod. Combined exposure to North Sea oil with an alkylphenol mixture resulted in lower EROD induction, compared to that in fish exposed to North Sea oil alone. This difference was not statistically significant, but still we believe that the alkylphenols have inhibited CYP1A activities in the fish which may have compromised CYP1A mediated metabolism of other xenobiotics, including PAH. CYP3A protein levels were lower, compared to controls, in fish exposed to nonylphenol and the combination of North Sea oil and alkylphenol mixture. In contrast, the oil alone had no effect on CYP3A protein content. North Sea oil exposure, alone or in combination with alkylphenols, caused oxidative stress observed as elevated levels of GSSG content and GR and CAT activities. Interestingly, exposure to nonylphenol resulted in a marked depletion of total glutathione levels. This apparent depletion may be a consequence of increased conjugation of glutathione to nonylphenol followed by excretion. An increase in conjugation enzyme GST activity was observed in the nonylphenol exposed group, although the difference was not significant. No sign of oxidative damage, measured as lipid peroxidation, was observed in any of the exposures experiments. This study suggests that North Sea oil may lead to oxidative stress and altered CYP1A and CYP3A expression

  13. 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.

  14. 40 CFR 180.1288 - Tristyrylphenol ethoxylates; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... FOOD Exemptions From Tolerances § 180.1288 Tristyrylphenol ethoxylates; exemption from the requirement...-hydroxy-, (CAS Reg. No. 99734-09-5) on citrus crops, group 10, when used as inert ingredients under...

  15. Toxicity of nonylphenol and nonylphenol ethoxylates to Ceriodaphnia

    SciTech Connect

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

    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 Ceriodaphnia are much less sensitive to these chemicals than are other aquatic organisms.

  16. 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.

  17. The effect of liquid crystalline structures on antiseizure properties of aqueous solutions of ethoxylated alcohols.

    PubMed

    Sulek, Marian Wlodzimierz; Bak, Anna

    2010-01-12

    Aqueous solutions of ethoxylated alcohols which form lyotropic liquid crystals at high concentrations (40-80%) were selected as model lubricating substances. Microscopic studies under polarized light and viscosity measurements were carried out in order to confirm the presence of liquid crystalline structures in the case of alcohol solutions with ethoxylation degrees of 3, 5, 7 and 10. Microscopic images and viscosity coefficient values characteristic of various mesophases were obtained. As expected, the viscosity of LLCs decreases considerably with an increase in shearing rate which is characteristic of liquid crystals being non-Newtonian liquids. Antiseizure properties were determined by means of a four-ball machine (T-02 Tester) and characterized by scuffing load (P(t)), seizure load (P(oz)) and limiting pressure of seizure (p(oz)). Alcohol ethoxylates forming mesophases in aqueous solutions have the strongest effect on the P(t) values which are several times higher than those measured in the presence of water. Ethoxylates with higher degrees of ethoxylation exhibit higher values of scuffing load. Those changes have been interpreted as a result of higher cloud points at which those compounds lose their amphiphilic properties. In general, the presence of mesophases in the bulk phase and particularly in the surface phase may lead to the formation of a lubricant film which separates the frictionally cooperating elements of a friction pair. The antiseizure efficiency of alcohol solutions is highest up to the load value which does not exceed the scuffing load value.

  18. Biodegradation of polyalcohol ethoxylate by a wastewater microbial consortium.

    PubMed

    Sharvelle, Sybil E; Garland, Jay; Banks, M K

    2008-04-01

    Polyalcohol ethoxylate (PAE), an anionic surfactant, is the primary component in most laundry and dish wash detergents and is therefore highly loaded in domestic wastewater. Its biodegradation results in the formation of several metabolites and the fate of these metabolites through wastewater treatment plants, graywater recycling processes, and in the environment must be clearly understood. Biodegradation pathways for PAE were investigated in this project with a municipal wastewater microbial consortium. A microtiter-based oxygen sensor system was utilized to determine the preferential use of potential biodegradation products. Results show that while polyethylene glycols (PEGs) were readily degraded by PAE acclimated microorganisms, most of the carboxylic acids tested were not degraded. Biodegradation of PEGs suggests that hydrophobe-hydrophile scission was the dominant pathway for PAE biodegradation in this wastewater community. Ethylene glycol (EG) and diethylene glycol (DEG) were not utilized by microbial populations capable of degrading higher molecular weight EGs. It is possible that EG and DEG may accumulate. The microtiter-based oxygen sensor system was successfully utilized to elucidate information on PAE biodegradation pathways and could be applied to study biodegradation pathways for other important contaminants.

  19. Alkylphenols and polycyclic aromatic hydrocarbons in eastern Mediterranean Spanish coastal marine bivalves.

    PubMed

    Bouzas, Alberto; Aguado, Daniel; Martí, Nuria; Pastor, José Manuel; Herráez, Rosa; Campins, Pilar; Seco, Aurora

    2011-05-01

    This paper reports the first results on alkylphenol pollution in edible bivalves from the Spanish coast. Two sampling campaigns (July 2006 and July 2007) were carried out to determine the concentration of nonylphenol (NP), octylphenol (OP), and eight polycyclic aromatic hydrocarbons (PAHs) in wild mussels (Mytilus galloprovincialys) and clams (Donax trunculus) at 14 sampling sites along the eastern Mediterranean Spanish coast. The results show that NP is the predominant alkylphenol, being the port of Valencia the most polluted area (up to 147 μg/kg wet weight in clams). Moving away from the ports the concentration of NP in bivalves decreased. OP concentration was below its detection limit in most of the studied areas and its maximum concentration (6 μg/kg w/w) was measured in clams from the port of Sagunto. The presence of low levels of PAHs was observed in most of the studied areas. The total PAHs concentration (i.e., sum of the eight measured PAHs) achieved a maximum value of 10.09 μg/kg w/w in the north coast of Valencia city. The distribution pattern of the individual PAHs showed that both pollution sources petrogenic and pyrolytic were present in the sampled areas. Fluoranthene was the most abundant PAH in mussels while benzo(b)fluoranthene in clams. The maximum concentration of 10 μg/kg w/w for benzo(a)pyrene established by the European Commission was never reached, indeed sampled bivalves showed concentrations 10 times lower than this reference value. Thus, they can be considered safe for human consumption. Despite the low contamination levels, the results show an overall pollution of bivalves by alkylphenol and PAHs as well as an increment in the number of polluted areas from 2006 to 2007. Thus, periodical sampling campaigns should be carried out to monitor the long-term tendency of these toxic and persistent pollutants.

  20. 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.

  1. Partition behaviour of alkylphenols in crude oil/brine systems under subsurface conditions

    NASA Astrophysics Data System (ADS)

    Bennett, B.; Larter, S. R.

    1997-10-01

    Partition of organic solutes between oils and water in the subsurface is an important geochemical process occurring during petroleum migration and reservoiring, during water washing, and during petroleum production. Currently no data exists on the quantitative aspects of the partition process at subsurface conditions for solutes such as phenols and aromatic hydrocarbons which are major components of both oils and waters. We have constructed an equilibration device for oils and waters based on flow injection analysis principles to measure partition coefficients of alkylphenols in crude oil/brine systems under reservoir conditions. Concentrations of C 0C 2 alkylphenols in waters and solid phase extracts of crude oils produced in the device were determined by reverse phase high performance liquid chromatography with electrochemical detection (RP-HPLC-ED), partition coefficients being measured as a function of pressure (25-340 bar), temperature (25-150°C), and water salinity (0-100,000 mg/L sodium chloride) for a variety of oils. Partition coefficients for all compounds decreased with increasing temperature, increased with water salinity and crude oil bulk NSO content, and showed little change with varying pressure. These laboratory measurements, determined under conditions close to those typically encountered in petroleum reservoirs, suggest temperature, water salinity, and crude oil bulk NSO content will have important influence on oil-water partition processes in the subsurface during migration and water washing.

  2. 40 CFR 721.10027 - Ethoxylated alkylsulfate, substituted alkylamine salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... alkylamine salt (generic). 721.10027 Section 721.10027 Protection of Environment ENVIRONMENTAL PROTECTION... salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as ethoxylated alkylsulfate, substituted alkylamine salt (PMN P-01-862)...

  3. 40 CFR 721.10027 - Ethoxylated alkylsulfate, substituted alkylamine salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... alkylamine salt (generic). 721.10027 Section 721.10027 Protection of Environment ENVIRONMENTAL PROTECTION... salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as ethoxylated alkylsulfate, substituted alkylamine salt (PMN P-01-862)...

  4. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  5. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  6. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  7. 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 ...

  8. 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...

  9. 40 CFR 721.10027 - Ethoxylated alkylsulfate, substituted alkylamine salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... alkylamine salt (generic). 721.10027 Section 721.10027 Protection of Environment ENVIRONMENTAL PROTECTION... salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as ethoxylated alkylsulfate, substituted alkylamine salt (PMN P-01-862)...

  10. 40 CFR 721.10027 - Ethoxylated alkylsulfate, substituted alkylamine salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... alkylamine salt (generic). 721.10027 Section 721.10027 Protection of Environment ENVIRONMENTAL PROTECTION... salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as ethoxylated alkylsulfate, substituted alkylamine salt (PMN P-01-862)...

  11. 40 CFR 721.10027 - Ethoxylated alkylsulfate, substituted alkylamine salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... alkylamine salt (generic). 721.10027 Section 721.10027 Protection of Environment ENVIRONMENTAL PROTECTION... salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as ethoxylated alkylsulfate, substituted alkylamine salt (PMN P-01-862)...

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. 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.

  17. Determination of alkylphenolic residues in fresh fruits and vegetables by extractive steam distillation and gas chromatography-mass spectrometry.

    PubMed

    Yang, Deng-Kai; Ding, Wang-Hsien

    2005-09-23

    This study describes a simple and sensitive method for determining the alkylphenolic compounds, 4-tert-octylphenol (4-t-OP), 4-nonylphenol isomers (4-NPs), and their monoethoxylates (4-t-OP1EO and 4-NP1EOs), in fresh fruits and vegetables. The method involves extracting a sample by a modified Nielson-Kryger steam distillation extraction using n-hexane for 1 h. The alkylphenolic compounds were identified and quantitated by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. Various pH values and amounts of NaCl added to the sample solution were evaluated as extraction conditions. The quantitation limit of this method was less than 0.2 ng/g in 10 g (fresh weight) of sample. Recovery of alkylphenolic compounds in spiked samples exceeded 64% while R.S.D. ranged from 1.0 to 9.8%. Alkylphenolic residues were detected in fresh fruits and vegetables at concentrations of 4-NPs and 4-t-OP from n.d. to 16 ng/g and from n.d. to 4.8 ng/g (fresh weight), respectively. NP1EO and OP1EO were always below the quantitation limit.

  18. 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

  19. Kinetics of ethoxylation and propoxylation of 1- and 2-octanol catalyzed by KOH

    SciTech Connect

    Di Serio, M.; Vairo, G.; Iengo, P.; Santacesaria, E.; Felippone, F.

    1996-11-01

    Ethoxylation and propoxylation reactions are often performed together or in alternation to obtain surfactants with particular properties or random and block copolymers. Both reactions are normally performed in the same reactor, in the presence of an alkaline catalyst, at relatively low temperature, 120--130 C, to avoid the intervention of the side reactions that are typical of the propoxylation. The propoxylation of a primary fatty alcohol is slower than the corresponding ethoxylation and gives place to a secondary hydroxyl terminal group that is still less reactive. on the contrary, ethoxylation restores more reactive primary hydroxyl terminal groups. Therefore, it is important for optimizing the described industrial operations to know the reactivity of ethylene and propylene oxide with, respectively, primary and secondary hydroxyls, in the presence of the most used KOH catalyst. In this paper, the kinetics of both the ethoxylation and propoxylation of 1- and 2-octanol catalyzed by KOH have been studied for this purpose. The authors show, first of all, that propylene oxide ring opening occurs selectively giving only secondary hydroxyls as terminal groups. The ratio of addition rate of ethylene oxide to primary and secondary alcohol with respect to that of propylene oxide is always greater than 1. Kinetic data collected have been interpreted by using a kinetic model able to simulate during the time the consumption of both the octanol and the alkoxide and the evolution of the oligomer distributions. The kinetic model and related parameters can be easily extrapolated to different industrial situations in which ethoxylation and propoxylation occur together or in alternation.

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

    SciTech Connect

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

    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 oxidation resistance, anticorrosion properties, and detergency-dispersancy of the DS-11 diesel oil.

  1. Sites and Functional Consequence of Alkylphenol Anesthetic Binding to Kv1.2 Channels.

    PubMed

    Bu, Weiming; Liang, Qiansheng; Zhi, Lianteng; Maciunas, Lina; Loll, Patrick J; Eckenhoff, Roderic G; Covarrubias, Manuel

    2017-02-15

    Inhalational general anesthetics, such as sevoflurane and isoflurane, modulate a subset of brain Kv1 potassium channels. However, the Kv1.2 channel is resistant to propofol, a commonly used intravenous alkylphenol anesthetic. We hypothesize that propofol binds to a presumed pocket involving the channel's S4-S5 linker, but functional transduction is poor and, therefore, propofol efficacy is low. To test this hypothesis, we used a photoactive propofol analog (meta-aziPropofol = AziPm) to directly probe binding and electrophysiological and mutational analyses in Xenopus oocytes to probe function. We find that AziPm photolabels L321 in the S4-S5 linker of both the wild-type Kv1.2 and a mutant Kv1.2 (G329 T) with a novel gating phenotype. Furthermore, whereas propofol does not significantly modulate Kv1.2 WT but robustly potentiates Kv1.2 G329T, AziPm inhibits Kv1.2 WT and also potentiates Kv1.2 G329T. Kv1.2 modulation by AziPm was abolished by two mutations that decreased hydrophobicity at L321 (L321A and L321F), confirming the specific significance of the S4-S5 linker in the mechanism of general anesthetic modulation. Since AziPm binds to Kv1.2 G329T and shares the propofol ability to potentiate this mutant, the parent propofol likely also binds to the Kv1.2 channel. However, binding and alkylphenol-induced transduction are seemingly sensitive to the conformation of the S4-S5 linker site (altered by G329T) and subtle differences in the chemical structures of propofol and AziPm. Overall, the results are consistent with a mechanism of general anesthetic modulation that depends on the complementarity of necessary ligand binding and permissive ion channel conformations that dictate modulation and efficacy.

  2. Detailed molecular characterization of castor oil ethoxylates by liquid chromatography multistage mass spectrometry.

    PubMed

    Nasioudis, Andreas; van Velde, Jan W; Heeren, Ron M A; van den Brink, Oscar F

    2011-10-07

    The molecular characterization of castor oil ethoxylates (CASEOs) was studied by reverse-phase liquid chromatography (RPLC) mass spectrometry (MS) and multistage mass spectrometry (MS(n)). The developed RPLC method allowed the separation of the various CASEO components, and especially, the baseline separation of multiple nominal isobars (same nominal mass) and isomers (same exact mass). MS and MS(n) were used for the determination and structure elucidation of various structures and for the discrimination of the isobars and isomers. Different ionization techniques and adduct ions were also tested for optimization of the MS detection and the MS(n) fragmentation. A unique fragmentation pathway of ricinoleic acid is proposed, which can be used as a marker of the polymerization process and the topology of ethoxylation in the CASEO. In addition, characteristic neutral losses of ricinoleic acid reveal its (terminal or internal) position in the molecule.

  3. Oxidation of polyvinylpyrrolidone and an ethoxylate surfactant in phase-inversion wastewater.

    PubMed

    Loraine, Gregory A

    2008-04-01

    In this paper, components of an industrial wastewater that cause operational problems during biological treatment were oxidized by UV light and hydrogen peroxide (UV/H202). Preoxidation of wastewater was shown to remove polyvinylpyrrolidone (PVP) and ethoxylate surfactant and increase overall biodegradability. Several UV intensities and hydrogen peroxide concentrations were tested to find optimal conditions for the complete depolymerization of PVP in a synthetic wastewater composed of high concentrations of hydroxyl radical scavengers. To compare treatment options, absorption isotherms for PVP on granular activated carbon (GAC) in water and in the synthetic phase-inversion wastewater matrix were determined. The data were extrapolated to estimate the cost of using UV/H2O2, GAC, or off-site treatment. It was found that UV/H2O2 pretreatment was economically viable. Incomplete oxidation of an ethoxylate surfactant increased foaming tendency and foam stability; however, extended oxidation (> 90 minutes) destroyed the foam.

  4. Modeling nonlinear sorption of alcohol ethoxylates to sediment: the influence of molecular structure and sediment properties.

    PubMed

    Droge, Steven T J; Yarza-Irusta, Leire; Hermens, Joop L M

    2009-08-01

    The nonlinear sorption of individual alcohol ethoxylate (AE) homologues was studied as a function of the chemical structure of AE and properties of six marine sediments and three clay minerals. All sorption data for both sediments and clays are well described by a dual-mode model, combining a Langmuir and linear sorption term. The nonlinear isotherms of a single homologue on different substrates almost overlap when sorbed concentrations are expressed per specific surface area. Below and above the Langmuir maximum capacity, isotherms approach linearity. Accordingly, it is demonstrated for nine individual AE that the two linear sorption coefficients for the clay mineral illite are predictive within a factor of two for a North Sea sediment. The linear sorption term at high concentrations is likely related to bilayer formation on the mineral surfaces, for both clays and sediments. Adsorption and bilayer formation to mineral surfaces dominate the sorption behavior of most AE homologues to the tested marine sediments. The two fitted sorption coefficients correlate well with the polar and nonpolar chain lengths of the AE. The enhanced nonlinearity of isotherms for AE with longer ethoxylate chains is explained by both an increasing adsorption coefficient and a decreasing bilayer formation affinity with additional ethoxylate units.

  5. 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.

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

    SciTech Connect

    Khim, J.S.; Villeneuve, D.L.; Kannan, K.; Lee, K.T.; Snyder, S.A.; Koh, C.H.; Giesy, J.P.

    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. 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.

  7. Bacterial strains isolated from river water having the ability to split alcohol ethoxylates by central fission.

    PubMed

    Budnik, Irena; Zembrzuska, Joanna; Lukaszewski, Zenon

    2016-07-01

    Alcohol ethoxylates (AE) are a major component of the surfactant stream discharged into surface water. The "central fission" of AE with the formation of poly(ethylene glycols) (PEG) is considered to be the dominant biodegradation pathway. However, information as to which bacterial strains are able to perform this reaction is very limited. The aim of this work was to establish whether such an ability is unique or common, and which bacterial strains are able to split AE used as a sole source of organic carbon. Four bacterial strains were isolated from river water and were identified on the basis of phylogenetic trees as Enterobacter strain Z2, Enterobacter strain Z3, Citrobacter freundii strain Z4, and Stenotrophomonas strain Z5. Sterilized river water and "artificial sewage" were used for augmentation of the isolated bacteria. The test was performed in bottles filled with a mineral salt medium spiked with surfactant C12E10 (10 mg L(-1)) and an inoculating suspension of the investigated bacterial strain. Sequential extraction of the tested samples by ethyl acetate and chloroform was used for separation of PEG from the water matrix. LC-MS was used for PEG determination on the basis of single-ion chromatograms. All four selected and investigated bacterial strains exhibit the ability to split fatty alcohol ethoxylates with the production of PEG, which is evidence that this property is a common one rather than specific to certain bacterial strains. However, this ability increases in the sequence: Stenotrophomonas strain Z5 < Enterobacter strain Z2 < Enterobacter strain Z3 = Citrobacter freundii strain Z4. Graphical Abstract Biodegradation by central fission of alcohol ethoxylates by bacterial strains isolated from river water.

  8. Formation of middle-phase microemulsions using surfactants derived from a renewable resource: ethoxylated tall oils

    SciTech Connect

    Magid, L.J.

    1982-06-01

    The range of salinities over which a large number of multicomponent systems containing ethoxylated tall oils or tall-oil derivatives form middle-phase microemulsions was determined. n-Octane and n-decane were used as the hydrocarbons; 2 methyl-1-propanol and 2-butanol as the cosurfactants. It is possible, with an appropriate choice of surfactant, to produce systems with optimal salinities from 0 to ca. 17 wt% NaCl. Phase volume diagrams are presented for 24 of the systems investigated; interfacial tension measurements for selected systems show tensions in the millidyn/cm range at the optimal salinities.

  9. Formation of middle-phase microemulsions in multicomponent systems containing petrostep-465 and ethoxylated tall oils

    SciTech Connect

    Magid, L.J.

    1982-06-01

    The range of salinities over which certain Petrostep-465/ethoxylated tall oil/cosurfactant/hydrocarbon/brine systems form middle-phase microemulsions was determined. The presence of the nonionic surfactant, in cases where n-decane is the hydrocarbon and 2-butanol is the cosurfactant, increases the optimal salinity of the system. Some broadening of the salinity range over which low interfacial tensions are observed is also found. Phase behavior for systems containing P-465 as the only surfactant shows order of mixing effects.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Comparison of mass spectrometric techniques for generating molecular weight information on a class of ethoxylated oligomers.

    PubMed

    Parees, D M; Hanton, S D; Clark, P A; Willcox, D A

    1998-04-01

    The results of fast atom bombardment (FAB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), matrix-assisted laser desorption/ionization (MALD/I), electrospray ionization (ESI), and field desorption (FD) analyses of ethoxylated oligomers of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfynol(®) 104) were compared.Each of these desorption mass spectrometry (MS) techniques can produce spectra of unfragmented cationized oligomers. From the observed ion series we calculate average molecular weight information. We have compared the results of mass spectrometric analyses of a series of ethoxylated Surfynol surfactants. Our data indicate that FAB, ToF-SIMS, MALDI/I, and ESI produce similar results for the lower molecular weight species, but that as the average molecular weight increases FAB and SIMS produce slightly lower results than MALD/I and FD. This could be due to increased fragmentation. ESI produced a result similar to FAB and SIMS for the highest average molecular weight material. Further experiments compare the mass spectral results with gas chromatographic quantitative data. Although gas chromatography is not expected to accurately analyze the higher mass oligomers, we observe significant differences in intensities of the short-chain oligomers (especially the 0- and 1-mers) when compared to the desorption mass spectrometer results. These differences may reflect poor cationization efficiency for very short oligomer chains in the mass spectrometric analyses.

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. Partitioning behavior of an acid-cleavable, 1,3-dioxolane alkyl ethoxylate, surfactant in single and binary surfactant mixtures for 2- and 3-phase microemulsion systems according to ethoxylate head group size.

    PubMed

    Gomez del Rio, Javier; Hayes, Douglas G; Urban, Volker S

    2010-12-15

    Partition coefficients for a pH-degradable 1,3-dioxolane alkyl ethoxylate surfactant, 4-CH(3)O (CH(2)CH(2)O)(5.6)-CH(2), 2,2-(CH(2))(12)CH(3), 2-(CH(2)) CH(3), 1,3-dioxolane or "cyclic ketal" surfactant, CK-2,13-E(5.6,ave), between isooctane- and water-rich phases of 2- and 3-phase microemulsion systems (K(n)) were determined as functions of the ethoxylate size, n, and temperature for the neat surfactant and its binary surfactant mixtures, to understand the partitioning of alkyl ethoxylates possessing a broad distribution of ethoxylate size and to determine conditions required for formation of 3-phase microemulsion systems at an optimal temperature where phase separation occurs rapidly, important for protein purification via proteins' selective partitioning to the middle phase, driven by affinity to the second surfactant of the binary mixture. A semi-empirical thermodynamic mathematical model described the partitioning data well, provided optimal temperature values consistent with phase diagrams and theory, and demonstrated that the tail region of CK-2,13-E(5.6,ave) is more polar than the hydrophobes of fatty alcohol ethoxylates. The addition of Aerosol-OT (AOT) removed the temperature sensitivity of CK-2,13-E(5.6,ave)s partitioning, producing 3-phase microemulsion systems between 20 °C and 40 °C. Analysis of the bottom phases of the 2- and 3-phase microemulsion systems formed by CK-2,13-E(5.6,ave) via small-angle neutron scattering demonstrated the presence of spherical, monodisperse oil-in-water microemulsions.

  1. Partitioning behavior of an acid-cleavable, 1,3-dioxolane alkyl ethoxylate, surfactant in single and binary surfactant mixtures for 2- and 3-phase microemulsion systems according to ethoxylate head group size

    SciTech Connect

    Gomez Del Rio, Javier A; Hayes, Douglas G; Urban, Volker S

    2010-01-01

    Partition coefficients for a pH-degradable 1,3-dioxolane alkyl ethoxylate surfactant, 4-CH{sub 3}O (CH{sub 2}CH{sub 2}O){sub 5.6}-CH{sub 2}, 2,2-(CH{sub 2}){sub 12}CH{sub 3}, 2-(CH{sub 2}) CH{sub 3}, 1,3-dioxolane or ''cyclic ketal'' surfactant, CK-2,13-E{sub 5.6,ave}, between isooctane- and water-rich phases of 2- and 3-phase microemulsion systems (K{sub n}) were determined as functions of the ethoxylate size, n, and temperature for the neat surfactant and its binary surfactant mixtures, to understand the partitioning of alkyl ethoxylates possessing a broad distribution of ethoxylate size and to determine conditions required for formation of 3-phase microemulsion systems at an optimal temperature where phase separation occurs rapidly, important for protein purification via proteins selective partitioning to the middle phase, driven by affinity to the second surfactant of the binary mixture. A semi-empirical thermodynamic mathematical model described the partitioning data well, provided optimal temperature values consistent with phase diagrams and theory, and demonstrated that the tail region of CK-2,13-E{sub 5.6,ave} is more polar than the hydrophobes of fatty alcohol ethoxylates. The addition of Aerosol-OT (AOT) removed the temperature sensitivity of CK-2,13-E{sub 5.6,ave}s partitioning, producing 3-phase microemulsion systems between 20 C and 40 C. Analysis of the bottom phases of the 2- and 3-phase microemulsion systems formed by CK-2,13-E{sub 5.6,ave} via small-angle neutron scattering demonstrated the presence of spherical, monodisperse oil-in-water microemulsions.

  2. 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.

  3. Anaerobic nonylphenol ethoxylate degradation coupled to nitrate reduction in a modified biodegradability batch test.

    PubMed

    Luppi, Lorena I; Hardmeier, Ivo; Babay, Paola A; Itria, Raúl F; Erijman, Leonardo

    2007-08-01

    The aim of this work was to elucidate the role of nitrate as a terminal electron acceptor on the biodegradation of NPEO. We have characterized the products of NPEO degradation by mixed microbial communities in anaerobic batch tests by means of HPLC, (1)H NMR and GC-MS. Anaerobic degradation of NPEO was strictly dependent on the presence of nitrate. Within seven days of anoxic incubation, NP2EO appeared as the major degradation product. After 21 days, NP was the main species detected, and was not degraded further even after 35 days. Nitrate concentration decreased in parallel with NPEO de-ethoxylation. A transient accumulation of nitrite was observed within the time period in which NP formation reached its maximum production. The observed generation of nonylphenol coupled to nitrate reduction suggests that the microbial consortium possessed an alternate pathway for the degradation of NPEO, which was not accessible under aerobic conditions.

  4. The hydroxyl radical scavenging effect of textile preparation auxiliaries on the photochemical treatment of nonylphenol ethoxylate.

    PubMed

    Arslan-Alaton, Idil; Shayin, Sarina; Olmez-Hanci, Tugba

    2012-01-01

    The present paper deals with the effects of frequently used textile preparation chemicals and common ions on the H2O2/UV-C treatment of a commercially important and slowly biodegradable nonionic surfactant, namely a nonylphenol bearing 10 ethoxylated chains. For this purpose, the effect of soda ash carbonate (0-5.0 g L(-1)), two phosphonic acid-based organic sequestering agents (0-2.5 g L(-1)) and chloride (0-3.0 g L(-1)) at two different pH values (3.5 and 10.5) as hydroxyl radical scavengers was experimentally investigated. Among the studied textile preparation chemicals and hydroxyl radical scavengers, the decreasing order of hydroxyl radical scavenging capacity was established as diethylene triamine pentamethylene phosphonic acid > 1-hydroxy ethylidene-1,1-diphosphonic acid > soda ash carbonate at pH 10.5 > chloride at pH 3.5 > chloride at pH 10.5.

  5. Electronic structure and mesoscopic simulations of nonylphenol ethoxylate surfactants. a combined DFT and DPD study.

    PubMed

    Valencia, Diego; Aburto, Jorge; García-Cruz, Isidoro

    2013-08-07

    The aim of this work was to gain insight into the effect of ethylene oxide (EO) chains on the properties of a series of nonylphenol ethoxylate (NPE) surfactants. We performed a theoretical study of NPE surfactants by means of density functional theory (DFT) and dissipative particle dynamics (DPD). Both approximations were used separately to obtain different properties. Four NPEs were selected for this purpose (EO = 4, 7, 11 and 15 length chains). DFT methods provided some electronic properties that are related to the EO units. One of them is the solvation Gibbs energy, which exhibited a linear trend with EO chain length. DPD calculations allow us to observe the dynamic behavior in water of the NPE surfactants. We propose a coarse-grained model which properly simulates the mesophases of each surfactant. This model can be used in other NPEs applications.

  6. Assessment of alcohol ethoxylate surfactants and fatty alcohols mixtures in river sediments and prospective risk assessment.

    PubMed

    Dyer, Scott D; Sanderson, Hans; Waite, Scott W; Van Compernolle, Remi; Price, Bradford; Nielsen, Allen M; Evans, Alex; Decarvalho, Alvaro J; Hooton, Dennis J; Sherren, Andrew J

    2006-09-01

    A feasible and relatively readily available analytical method was adapted for the assessment of alcohol ethoxylates (AE) and fatty alcohols (FA) in sediments. This study illustrates the simultaneous measurement of 38 of 114 possible alcohol ethoxylate ethoxymers (AE) and fatty alcohols (FA) found in commercially important AE products. We predicted toxicity for all identified fractions, as well as the total mixture toxicity, relative to three exposure scenarios via sewage treatment plants (STP) for these widely used chemicals in consumer products and hence generate a preliminary environmental risk screening for AE and FA in sediments. The method is based on derivatization of solvent or solid-phase extracts with 2-fluoro-N-methylpyridinium p-toluenesulfonate (Pyr+). The derivatized extracts were analyzed with liquid chromatography/mass spectrometry (LC/MS) operating in the positive ion electrospray mode. The extraction efficiency of AE and FA in three different sediments of varying composition was evaluated with spike-recovery studies, ranging from 64% to 80%. The detection limits for individual ethoxymers typically ranged from 1 to 5 ngg(-1)on a dry weight basis. The mean limit of detection (LOD) was 6 ngg(-1)and the median LOD was 3 ngg(-1). AE and FA in sediments were found to be stable for two weeks if preserved with 3% (v/v) formalin and stored at 4-6( composite function)C. Based on equilibrium partitioning, background concentrations of AE and FA were predicted to be below concentrations known to elicit chronically toxic effects. Total worst case mixture toxicities for all AE ethoxymers combined with FA were predicted to result in a risk quotient less than 0.6. Activated sludge treatment (STP) significantly reduced the release of total AE and FA by four-fold, suggesting that the total mixture risk quotient would be < 0.15 for sediment dependent organisms.

  7. Metabolites and biodegradation pathways of fatty alcohol ethoxylates in microbial biocenoses of sewage treatment plants.

    PubMed Central

    Steber, J; Wierich, P

    1985-01-01

    The biodegradation of fatty alcohol polyglycol ethers was studied by analyzing the 14C-labeled intermediates isolated from the effluent of a model continuous-flow sewage treatment plant after dosage of either alkyl- or heptaglycol-labeled stearyl alcohol ethoxylate (SA-7EO). In each case, uncharged and carboxylated (mainly dicarboxylated) polyethylene glycols constituted the most prominent metabolites. The results indicate that there is a faster degradation of the alkyl than the polyethylene glycol moiety and that there are two distinct primary degradation mechanisms acting simultaneously in microbial biocenoses: intramolecular scission of the surfactant as well as omega- and beta-oxidation of the alkyl chain. Characterization of the bulk of 14C-labeled metabolites as a homologous series of neutral and acidic polyglycol units and identification of several C2-fragments accounted for the depolymerization of the hydrophilic part of the surfactant by stepwise cleavage of ether-bound EO units; from additional degradation studies employing either neutral or carboxylated 14C-labeled polyethylene glycols as model metabolites, it was concluded that hydrolytic as well as oxidative cleavage of C2-units is involved. Most of the identified low-molecular-weight 14C-labeled acids suggest an ultimate degradation of EO monomers by the oxidative dicarbonic acid cycle or the glycerate pathway or both. In addition, the finding of considerable amounts of oxalic and formic acids allow consideration of an additional mineralization route via glyoxylic, oxalic, and formic acids. The simultaneous action of different degradation mechanisms indicates the involvement of several distinct bacterial groups in the biodegradation of fatty alcohol ethoxylates under environmental conditions. PMID:3994363

  8. Field comparison of passive sampling and biological approaches for measuring exposure to PAH and alkylphenols from offshore produced water discharges.

    PubMed

    Harman, Christopher; Brooks, Steven; Sundt, Rolf C; Meier, Sonnich; Grung, Merete

    2011-01-01

    Polycyclic aromatic hydrocarbons (PAH) and alkylphenols (AP) that are present in routine discharges of produced water (PW) from the offshore industry continue to cause concern. The suitability of biological methods and chemical based passive samplers to determine exposure to these compounds was tested by deploying them around an oil installation and at reference locations in the North Sea. PAH and AP were analysed either as parent compounds in passive samplers and mussel tissue or as metabolites in fish bile. Generally the pattern of exposure relative to proximity to the discharge was represented by mussels, SPMDs and fish for PAH. Fish and SPMDs showed good correlation for PAH accumulations, whereas some differences were apparent between mussels and SPMDs. POCIS was the only technique tested that could accurately measure the most abundant AP in PW. The advantages of biologically independent measures of exposure for inclusion in discharge monitoring studies are outlined.

  9. 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.

  10. Final report of the amended safety assessment of sodium laureth sulfate and related salts of sulfated ethoxylated alcohols.

    PubMed

    Robinson, Valerie C; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Alan Andersen, F

    2010-07-01

    Sodium laureth sulfate is a member of a group of salts of sulfated ethoxylated alcohols, the safety of which was evaluated by the Cosmetic Ingredient Review (CIR) Expert Panel for use in cosmetics. Sodium and ammonium laureth sulfate have not evoked adverse responses in any toxicological testing. Sodium laureth sulfate was demonstrated to be a dermal and ocular irritant but not a sensitizer. The Expert Panel recognized that there are data gaps regarding use and concentration of these ingredients. However, the overall information available on the types of products in which these ingredients are used and at what concentrations indicates a pattern of use. The potential to produce irritation exists with these salts of sulfated ethoxylated alcohols, but in practice they are not regularly seen to be irritating because of the formulations in which they are used. These ingredients should be used only when they can be formulated to be nonirritating.

  11. Occurrence and risk screening of alcohol ethoxylate surfactants in three U.S. river sediments associated with wastewater treatment plants.

    PubMed

    Sanderson, Hans; van Compernolle, Remi; Dyer, Scott D; Price, Bradford B; Nielsen, Allen M; Selby, Martin; Ferrer, Darci; Stanton, Kathleen

    2013-10-01

    Alcohol ethoxylates (AE) are high production volume (HPV) chemicals globally used in detergent and personal care products and are truly a work-horse for the household and personal care industries. Commercial AE generally consist of a mixture of several homologues of varying carbon chain length and degree of ethoxylation. Homologues that are not ethoxylated are also known as aliphatic alcohols or simply fatty alcohols (FA). This group of homologues represents a special interest in the context of environmental risk, as these are also abundant and ubiquitous naturally occurring compounds (e.g. animal fats and in human feces). Hence, in a risk assessment one needs to distinguish between the natural (background) concentrations and the added contribution from anthropogenic activities. We conducted a weight-of-evidence risk assessment in three streams, documenting the exposure and predicted risk, and compared these to the habitat and in situ biota. We found that the parameters (e.g., habitat quality and total perturbations hereunder total suspended solids (TSS) and other abiotic and biotic stressors) contributed to the abundance of biota rather than the predicted risk from AE and FA. Moreover, the documented natural de novo synthesis and rapid degradation of FA highlight the need to carefully consider the procedures for environmental risk assessment of naturally occurring compounds such as FA, e.g. in line with the added risk concept known from metal risk assessment.

  12. Biodegradation of low-ethoxylated nonylphenols in a bioreactor packed with a new ceramic support (Vukopor ® S10).

    PubMed

    Sciubba, Luigi; Bertin, Lorenzo; Todaro, Daniela; Bettini, Cristina; Fava, Fabio; Di Gioia, Diana

    2014-03-01

    This work was aimed at studying the possibility of biodegrading 4-nonylphenol and low ethoxylated nonylphenol mixtures, which are particularly recalcitrant to microbial degradation, by employing a biofilm reactor packed with a ceramic support (Vukopor® S10). A selected microbial consortium (Consortium A) was used to colonize the support. 4-Nonylphenol and ethoxylated nonylphenol degradation and mineralization capabilities were studied both in batch and continuous mode. The results showed that Vukopor® S10 was able to be colonized by an active biofilm for the degradation of the target pollutants with the reactor operating both in batch and continuous mode. On the other hand, pollutant adsorption on the support was negligible. FISH showed equal proportion of Alphaproteobacteria and Gammaproteobacteria in the Igepal CO-520 degrading reactor. A shift towards high proportion of Gammaproteobacteria was observed by supplying Igepal CO-210. PCR-density gradient gel electrophoresis (DGGE) analyses also evidenced that the biofilm evolved with time by changing the mixture applied and that Proteobacteria were the most represented phylum in the biofilm. Taken together, the data obtained provide a strong indication that the biofilm reactor packed with Vukopor® S10 and inoculated with Consortium A could potentially be used to develop a technology for the decontamination of 4-nonylphenol and low ethoxylated nonylphenol polluted effluents.

  13. Partitioning of alcohol ethoxylates and polyethylene glycols in the marine environment: field samplings vs laboratory experiments.

    PubMed

    Traverso-Soto, Juan M; Brownawell, Bruce J; González-Mazo, Eduardo; Lara-Martín, Pablo A

    2014-08-15

    Nowadays, alcohol ethoxylates (AEOs) constitute the most important group of non-ionic surfactants, used in a wide range of applications such as household cleaners and detergents. Significant amounts of these compounds and their degradation products (polyethylene glycols, PEGs, which are also used for many other applications) reach aquatic environments, and are eliminated from the water column by degradation and sorption processes. This work deals with the environmental distribution of AEOs and PEGs in the Long Island Sound Estuary, a setting impacted by sewage discharges from New York City (NYC). The distribution of target compounds in seawater was influenced by tides, consistent with salinity differences, and concentrations in suspended solid samples ranged from 1.5 to 20.5 μg/g. The more hydrophobic AEOs were mostly attached to the particulate matter whereas the more polar PEGs were predominant in the dissolved form. Later, the sorption of these chemicals was characterized in the laboratory. Experimental and environmental sorption coefficients for AEOs and PEGs showed average values from 3607 to 164,994 L/kg and from 74 to 32,862 L/kg, respectively. The sorption data were fitted to a Freundlich isotherm model with parameters n and log KF between 0.8-1.2 and 1.46-4.39 L/kg, respectively. AEO and PEG sorptions on marine sediment were also found to be mostly not affected by changes in salinity.

  14. Fate of free and linear alcohol-ethoxylate-derived fatty alcohols in activated sludge.

    PubMed

    Federle, Thomas W; Itrich, Nina R

    2006-05-01

    Pure homologues of [1-14C] C12, C14, and C16 alcohols and the linear alcohol ethoxylates, AE [1-14C alkyl] C13E9 and C16E9 were tested in a batch-activated sludge die-away system to assess their biodegradation kinetics and to predict levels of free alcohol derived from AE biodegradation in treated effluent. First-order rates for primary biodegradation were similar for all alcohols (86-113 h(-1)) and were used to predict removal under typical treatment conditions. Predicted removals of fatty alcohols ranged from 99.76% to 99.85%, consistent with published field data. During the biodegradation of the AE homologues, lower than expected levels of fatty alcohol based upon the assumption that biodegradation occurs through central fission were observed. Rather than fatty alcohols, the major metabolites were polar materials resulting from omega oxidation of the alkyl chain prior to or concurrent with central cleavage. The amounts of free fatty alcohols that were formed from AEs in influent and escape into effluent were negligible due both to their rapid degradation and to the finding that formation of free alcohol through central cleavage is only a minor degradation pathway in activated sludge.

  15. Acute aquatic toxicity of nine alcohol ethoxylate surfactants to fathead minnow and Daphnia magna

    SciTech Connect

    Wong, D.C.L.; Dorn, P.B.; Chai, E.Y.

    1995-12-31

    The aquatic toxicity of nine commercial-grade alcohol ethoxylate surfactants was studied in acute exposures to fathead minnow (Pimephales promelas) and Daphnia magna. All studies were conducted in accordance with USEPA TSCA Good Laboratory Practice Standards. Mean measured surfactant concentrations in exposure solutions showed good agreement with nominal concentrations for both fathead minnow and daphnid tests. Surfactant recoveries ranged from 59 to 97% and 67 to 106% in the fathead minnow and daphnid solutions, respectively. The response of both species to the surfactants was generally similar with the daphnids being slightly more sensitive to a few surfactants. Surfactant toxicity tended to increase with increasing alkyl chain lengths. The effect of low average EO groups on increased surfactant toxicity was more evident in the daphnid exposures. Quantitative structure-activity relationship (QSAR) models were developed form the data which relates surfactant structure to toxicity. The models predict increasing toxicity with decreasing EO number and increasing alkyl chain length. The models also indicate that alkyl chain length has a greater effect on toxicity than EO groups. Further, the models indicate that both species did not differ markedly in their sensitivity to alkyl chain length effects, while the number of EO groups had a stronger effect on daphnids than fathead minnow. Good agreement was found between QSAR model-predicted toxicity and reported toxicity values from the literature for several surfactants previously studied.

  16. 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.

  17. 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.

  18. 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.

  19. Seasonal changes and spatial distributions of nonylphenol ethoxylates in sewage treatment plant with BAF process.

    PubMed

    Gao, Da-Wen; Li, Zhe; Guan, Jun-Xue; Liang, Hong

    2017-02-01

    Recently, there has been growing concern over the prevalence of Nonylphenol ethoxylates (NPnEOs) in the natural environment as these compounds are known endocrine disruptors. This study focuses on the seasonal variation and spatial distribution of NPnEOs in the wastewater of a full scale sewage treatment plant, operating a Biological Aerated Filter (BAF), in Harbin, a city in Northeast China. Water samples were collected seasonally from 2009 to 2010, with the findings revealing remarkable seasonal variations in the concentrations of NPnEOs. The total influent concentrations of short-chain NPnEOs (NP, NP1EO and NP2EO) measured during winter was 16 mg L(-1), with decreasing concentrations observed during autumn, summer and spring of 89, 67 and 41 mg L(-1), respectively. The concentrations of the short-chain NPnEOs measured during autumn become higher (89 mg L(-1)), with summer becoming the lowest (16 mg L(-1)). Although the removal efficiencies of short-chain NPnEOs in STP showed various trends in different seasons, they all achieve relatively good performance during summer and winter. The BAF process plays the main role in the elimination of short-chain NPnEOs compounds; however, the ambient temperatures were not found to significantly influence the removal efficiency of short-chain NPnEOs compounds from the STP.

  20. Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry.

    PubMed

    Zembrzuska, Joanna; Budnik, Irena; Lukaszewski, Zenon

    2014-07-01

    Alcohol ethoxylates (AEs) are a significant component of a stream of surfactants directed to the aquatic environment. The aim of this work was the investigation of the dependence of the analytical signals of homogeneous AE homologues on liquid chromatography with tandem mass spectrometry conditions, as well as the separation of AEs from the water matrix and, on this basis, the development of an analytical procedure suitable for the determination of AEs in environmental samples. Homogeneous homologues containing dodecyl moiety and 2-9 oxyethylene subunits were investigated. The analytical signals of the investigated homologues were optimized in terms of concentration of ammonium acetate in the mobile phase (optimum 5 mM) and a column temperature (optimum 35°C) of the liquid chromatography with tandem mass spectrometry system. A separation of AEs from the water matrix by liquid-liquid extraction (ethyl acetate, chloroform) or solid-phase extraction (C18 , styrene divinylbenzene, H-RX) was investigated. In a model investigation, the best recoveries (>90%) were obtained with a styrene divinylbenzene cartridge eluted with a 1:1 mixture of chloroform and methanol. However, much worse recoveries were obtained from the river water sample. Better results were obtained for liquid-liquid extraction with ethyl acetate. Recoveries of 62-80% were obtained for homologues having 4-9 oxyethylene subunits, at the lowest spike.

  1. 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.

  2. 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).

  3. Chronic toxicity of a homologous series of alcohol ethoxylate surfactants to Daphnia magna

    SciTech Connect

    Gillespie, W.B. Jr.; Rodgers, J.H. Jr.; Wong, D.C.L.; Dorn, P.B.

    1995-12-31

    The effects of three homologous nonionic surfactants were evaluated in a series of 21 d Daphnia magna flow-through laboratory experiments. No observed effects concentrations and effects concentrations for survival and reproduction were determined for three linear alcohol ethoxylate (LAE) surfactants with average carbon chain lengths of 10, 12.5, and 14.5 and average ethylene oxide units/mole of 6, 6.5, and 7, respectively. Mean measured concentrations of LAE in laboratory experiments ranged from 0.91 to 16.91 mg/L, 0.38 to 5.21 mg/L and 0.31 to 1.83 mg/L for C{sub 10}, C{sub 12.5}, and C{sub 14.5} LAEs, respectively. Daphnid survival NOECs were 2.8 mg/L (C{sub 10}), 1.8 mg/L (C{sub 12.5}), and 0.79 mg/L (C{sub 14.5}). Daphnid survival and reproduction were equally sensitive to the C{sub 10} and C{sub 14.5} surfactants, however, reproduction was more sensitive than survival for the C{sub 12.5} surfactant. Reproduction NOECs were 2.8, 0.77, and 0.79 mg/L for the C{sub 10}, C{sub 12.5}, and C{sub 14.5} LAEs, respectively. The 21 d chronic survival NOECs for daphnids were similar to NOECs for cladoceran densities obtained in outdoor stream mesocosm studies conducted at the University of Mississippi Field Station. These results indicate a relationship of approximately 1:1 between the chronic laboratory and field results.

  4. 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

  5. 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.

  6. Study of adjuvant effect of model surfactants from the groups of alkyl sulfates, alkylbenzene sulfonates, alcohol ethoxylates and soaps.

    PubMed

    Clausen, S K; Sobhani, S; Poulsen, O M; Poulsen, L K; Nielsen, G D

    2000-11-01

    The sodium salts of representatives of anionic surfactants, dodecylbenzene sulfonate (SDBS), dodecyl sulfate (SDS) and coconut oil fatty acids, and a nonionic surfactant, dodecyl alcohol ethoxylate, were studied for adjuvant effect on the production of specific IgE antibodies in mice. The surfactants were injected subcutaneously (sc) in concentrations of 1000, 100, 10 or 1 mg/l, respectively, together with 1 microg of ovalbumin (OVA). In addition, groups of mice received OVA in saline (control group) or in Al(OH)(3) (positive adjuvant control group). After the primary immunization the mice were boosted up to three times with OVA (0.1 microg sc) in saline. OVA-specific IgE antibodies were determined by the heterologous mouse rat passive cutaneous anaphylaxis test. The results were confirmed by a specific ELISA method. After the first booster, the Al(OH)(3) group and the 10 mg/l SDS group showed a statistically significant increase in OVA specific IgE levels. After two boosters, a statistically significant suppression in OVA-specific IgE production occurred with SDS (1000 mg/l), SDBS (1000 and 100 mg/l), coconut soap (1000 mg/l) and the alcohol ethoxylate (10 mg/l). This study suggests that a limited number of surfactants possess an adjuvant effect whereas all surfactants at certain levels can suppress specific IgE production.

  7. 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.

  8. 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.

  9. 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

  10. [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.

  11. 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.)

  12. 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.

    PubMed

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

    2015-06-01

    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

  13. 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

  14. 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).

  15. Study of different Chemcatcher configurations in the monitoring of nonylphenol ethoxylates and nonylphenol in aquatic environment.

    PubMed

    Ahkola, Heidi; Herve, Sirpa; Knuutinen, Juha

    2014-01-01

    The main aim of the European Union Water Framework Directive (WFD) (2000/60/EC) is to protect rivers, lakes, coastal waters and groundwaters (EC 2000). The implementation of the WFD requires monitoring the concentration levels of several priority pollutants such as nonylphenol ethoxylates (NPEOs) and nonylphenol (NP) in the area of EU. The present practices for determining the concentration levels of various pollutants are, in many respects, insufficient, and there is an urgent need to develop more cost-effective sampling methods. A passive sampling tool named Chemcatcher was tested for monitoring NPEOs and NP in aqueous media. These environmentally harmful substances have been widely used in different household and industrial applications, and they affect aquatic ecosystems, for example, by acting as endocrine disrupting compounds. The suitability of different receiving phases which were sulfonated styrene-divinylbenzene reversed phase polymer (SDB-RPS), standard styrene-divinyl benzene polymer (SDB-XC) and C-18 (octadecyl) was assessed in laboratory and field trials. The effect of a diffusion membrane on the accumulation of studied compounds was also investigated. The SDB-XC and C-18 receiving phases collected the NPEOs and NP most effectively. The water flow affected the accumulation factor of the studied substances in the field trials, and the water concentrations calculated using sampling rates were tenfold lower than those measured with conventional spot sampling. The concentration of the analytes in spot samples taken from the sampling sites might be higher because in that case, the particle-bound fraction is also measured. The NPEOs readily attach to suspended matter, and therefore, the total concentration of such compounds in water is much higher. Also, the spot samples were not taken daily but once a week, while the passive samplers collected the compounds continuously for 2- or 4-week time periods. This may cause differences when comparing the results of

  16. Soft matter dispersions with ordered inner structures, stabilized by ethoxylated phytosterols.

    PubMed

    Libster, Dima; Aserin, Abraham; Yariv, Doron; Shoham, Gil; Garti, Nissim

    2009-11-01

    This paper describes the formation and characterization of liquid crystalline dispersions based on the hexagonal phase of GMO/tricaprylin/water. As a stabilizer of the soft particles dispersed in the aqueous phase, a non-ionic, non-polymeric surfactant--ethoxylated phytosterol with 30 oxyethylene units (PhEO) was utilized. In contrast to Pluronic copolymers, normally utilized in the stabilization of liquid crystalline dispersions with ordered inner structure, use of such non-polymeric surfactant is not a common practice in this field. We revealed how properties of these particles, such as internal structure, size, and stability, can be rationally modified by the concentration of the stabilizing agent and processing conditions. The physical stability of the hexosomes was further examined by the LUMiFuge technique. Structural effect of PhEO solubilization on the properties of the bulk H(II) mesophase system showed that phase behavior was greatly influenced following phase transitions: H(II)-->H(II)+cubic-->cubic+L(alpha)-->L(alpha). The decrease of hydrogen bonding of the hydroxyl and carbonyl groups of monoolein with water and simultaneous hydration of EO groups of PhEO appeared to be important for the observed behavior. The use of PhEO as a dispersant resulted in a soft matter multi-phase water dispersion with bimodal distribution of the particle population. Effective stabilization of hexosomes was obtained in an extremely narrow concentration range of PhEO (0.1-0.2 wt%), coexisting with small vesicles and disordered particles. At higher PhEO content, particles had disordered inner structure, and unilamellar and multilamellar vesicles, at the expense of hexosomes in consequence of incorporation of the dispersant into the hexosome structure. PhEO was found to induce lamellar phase formation, introducing disorder into the hexagonal LLC and reducing their domain size. Finally, hexosomes were evaluated as delivery vehicles for the therapeutic peptide desmopressin

  17. A catalytic biofuel production strategy involving separate conversion of hemicellulose and cellulose using 2-sec-butylphenol (SBP) and lignin-derived (LD) alkylphenol solvents.

    PubMed

    Kim, Sunghoon; Han, Jeehoon

    2016-03-01

    A strategy in which the hemicellulose and cellulose fractions of lignocellulosic biomass are converted separately to jet fuel-range liquid hydrocarbon fuels (butene oligomers) through catalytic processes is developed. Dilute sulfuric acid (SA)-catalyzed pretreatment fractionates the first biomass into cellulose and hemicellulose-derived xylose, and these are then converted separately to levulinic acid (LA) using 2-sec-butylphenol (SBP) and lignin-derived (LD) alkylphenol solvents, respectively. LA is upgraded catalytically to butene oligomers via γ-valerolactone (GVL) and butene intermediates. Separation subsystems are designed to recover the alkylphenol solvents and biomass-derived intermediates (LA and GVL) for combination with the catalytic conversion subsystems of hemicellulose, cellulose, and lignin. In addition, a heat exchanger network (HEN) design is presented to satisfy the energy requirements of the integrated process from combustion of biomass residues (degradation products). Finally, a technoeconomic analysis shows that the proposed process ($3.37/gallon of gasoline) is an economically competitive alternative to current biofuel production approaches.

  18. 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.

  19. Removal of a broad range of surfactants from municipal wastewater--comparison between membrane bioreactor and conventional activated sludge treatment.

    PubMed

    González, Susana; Petrovic, Mira; Barceló, Damià

    2007-02-01

    Elimination of alkylphenol ethoxylates (APEO) and their degradation products (alkylphenols and alkylphenoxy carboxylates), as well as linear alkylbenzene sulfonates (LAS) and coconut diethanol amides (CDEA), was studied in a pilot plant membrane bioreactor (MBR) working in parallel to a full-scale wastewater treatment plant (WWTP) using conventional activated sludge (CAS). In the CAS system 87% of parent long ethoxy chain NPEOs were eliminated, but their decomposition yielded persistent acidic and neutral metabolites which were poorly removed. The elimination of short ethoxy chain NPEOs (NP(1)EO and NP(2)EO) averaged 50%, whereas nonylphenoxy carboxylates (NPECs) showed an increase in concentrations with respect to the ones measured in influent samples. Nonylphenol (NP) was the only nonylphenolic compound efficiently removed (96%) in the CAS treatment. On the other hand, MBR showed good performance in removing nonylphenolic compounds with an overall elimination of 94% for the total pool of NPEO derived compounds (in comparison of 54%-overall elimination in the CAS). The elimination of individual compounds in the MBR was as follows: 97% for parent, long ethoxy chain NPEOs, 90% for short ethoxy chain NPEOs, 73% for NPECs, and 96% for NP. Consequently, the residual concentrations were in the low mug/l level or below it. LAS and CDEA showed similar elimination in the both wastewater treatment systems that were investigated, and no significant differences were observed between the two treatment processes. Nevertheless, for all studied compounds the MBR effluent concentrations were consistently lower and independent of the influent concentrations. Additionally, MBR effluent quality in terms of chemical oxygen demand (COD), NH(4)(+) concentration and total suspended solids (TSS) was always superior to the ones of the CAS and also independent of the influent quality, which demonstrates high potential of MBRs in the treatment of municipal wastewaters.

  20. A comparative toxicologic and genotoxic study of the herbicide arsenal, its active ingredient imazapyr, and the surfactant nonylphenol ethoxylate.

    PubMed

    Grisolia, Cesar Koppe; Bilich, Marina Rolim; Formigli, Lia Menezes

    2004-09-01

    The herbicide arsenal 250 NA, its technical-grade active ingredient imazapyr, and the surfactant nonylphenol ethoxylate (NP) were evaluated through genotoxicity and toxicity studies in different organisms. A comparative study of these three compounds was carried out to assess how the addition of surfactant components may pose the highest toxicological risk to pesticide formulations. The results showed that arsenal, imazapyr, and NP did not cause chromosome aberration in Allium cepa nor increase the frequency of micronuclei in mice. However, toxicological evaluations showed that NP was the most toxic compound to mice, A. cepa, Drosophila melanogaster, and Biomphalaria tenagophila. In this evaluation, it was observed that the adverse effects were produced by the surfactant additive of the pesticide formulation.

  1. Trans-generation study of the effects of nonylphenol ethoxylate on the reproduction of the snail Biomphalaria tenagophila.

    PubMed

    Oliveira-Filho, Eduardo Cyrino; Grisolia, Cesar Koppe; Paumgartten, Francisco Jose Roma

    2009-02-01

    Nonylphenols ethoxylates (NPEs) are surfactants used in a variety of products. They are found in domestic sewage, industrial effluents and as contaminants in water bodies. This study was undertaken to evaluate the effects of NPE with 9.5 ethoxylate units (NPE9.5; 0, 0.01, 0.1, 1.0 mg/L) on the reproduction of the snail Biomphalaria tenagophila. Adult snails (F0 generation) were exposed to NPE for 8 weeks. The F1 generation continued to be exposed from embryo to reproductive maturity while their descendants (F2) were exposed until day 10 after spawning. We determined the effects of NPE9.5 on the fecundity (8-week production of eggs and egg masses) of mature F0 and F1 snails. Developmental toxicity was investigated in F1 and F2 embryos. The two highest concentrations of NPE9.5 reduced the fecundity of F0. In the F1 generation, the lowest concentration enhanced the number of eggs laid per snail while the intermediate concentration had no effect and the highest one decreased the fecundity thereby suggesting a biphasic effect of NPE9.5. Study-derived NOECs (no-observed-effect-concentrations) for NPE were: fecundity, F0=10 microg/L, F1<10 microg/L; developmental toxicity, F1=100 microg/L, F2<10 microg/L. Results, therefore, indicated that B. tenagophila is highly vulnerable to NPE and that trans-generation exposure to NPE9.5 aggravates its reproductive toxicity.

  2. Characterization of Microemulsion Systems Formed by a Mixed 1,3-Dioxolane Ethoxylate / Octyl Glucoside Surfactant System

    SciTech Connect

    Alkhatib, Mayson H; Hayes, Douglas G; Urban, Volker S

    2009-01-01

    The phase behavior of microemulsion systems containing water (or 1.0 wt% NaCl{sub aq}), isooctane, and the binary surfactant system consisting of n-octyl-{beta}-D-glucopyranoside, C{sub 8}{beta}G{sub 1}, and the acid-cleavable alkyl ethoxylate, 4-CH{sub 3}O (CH{sub 2}CH{sub 2}O){sub 7.2}, 2-(CH{sub 2}){sub 12}CH{sub 3}, 2-(CH{sub 2})CH{sub 3}, 1,3-dioxolane, or 'cyclic ketal' ('CK-2,13'), was determined. Large temperature-insensitive one, two, and three-phase microemulsion-phase regions were obtained when equal masses of the two surfactants were employed, suggesting that C{sub 8}{beta}G{sub 1} reduces the temperature sensitivity of CK-2,13's ethoxylate group. Addition of C{sub 8}{beta}G{sub 1} to CK-2,13 greatly improves the latter's low efficiency, evidenced by the formation of a three-phase microemulsion system for surfactant concentrations at low fractions of total surfactants for systems with equal mass ratios of water to oil and CK-2,13 to C{sub 8}{beta}G{sub 1}. Analysis of the phase diagrams also suggests that CK-2,13 and C{sub 8}{beta}G{sub 1} impart hydrophobic and hydrophilic character, respectively, to the surfactant mixture, and that addition of salt further increases the hydrophilicity of C{sub 8}{beta}G{sub 1}, presumably because of the salting-in of the latter. Analysis of small-angle neutron scattering data revealed that the mixed surfactant system formed spherical oil-in-water microemulsions, and that increasing the CK-2,13 fraction among the surfactants reduced the critical microemulsion concentration but slightly increased the nanodroplet size.

  3. Comprehensive analysis of fatty alcohol ethoxylates by ultra high pressure hydrophilic interaction chromatography coupled with ion mobility spectrometry mass spectrometry using a custom-designed sub-2 μm column.

    PubMed

    Ma, Qiang; Ma, Wei; Chen, Xi; Wang, Ziming; Bai, Hua; Zhang, Lanwei; Li, Wentao; Wang, Chao; Li, Xinshi

    2015-06-01

    Comprehensive analysis of fatty alcohol ethoxylates has been conducted by coupling ultra high pressure hydrophilic interaction chromatography and ion mobility spectrometry mass spectrometry. A custom-designed sub-2 μm column was used for the chromatographic separation of fatty alcohol ethoxylates by hydrophilic interaction chromatography. Ion mobility spectrometry provided a post-ionization resolution during a very short period of 6.4 ms. Distinguishable families of singly, doubly, and triply charged fatty alcohol ethoxylates were clearly observed. By virtue of the combination of hydrophilic interaction chromatography and ion mobility spectrometry, comprehensive resolution based on both hydrophobicity difference and mobility disparity has been achieved for fatty alcohol ethoxylates. The orthogonality of the developed separation and analysis system was evaluated with the correlation coefficient and peak spreading angle of 0.0224 and 88.72°, respectively. The actual peak capacity obtained was individually 40 and 193 times than those when hydrophilic interaction chromatography and ion mobility spectrometry were used alone. The collision cross-sections of fatty alcohol ethoxylates were calculated by calibrating the traveling wave ion mobility device with polyalanine.

  4. High-efficiency inverted polymer solar cells controlled by the thickness of polyethylenimine ethoxylated (PEIE) interfacial layers.

    PubMed

    Li, Ping; Wang, Gang; Cai, Lun; Ding, Baofu; Zhou, Dachen; Hu, Yi; Zhang, Yujun; Xiang, Jin; Wan, Keming; Chen, Lijia; Alameh, Kamal; Song, Qunliang

    2014-11-21

    In this work, we investigate the effect of the thickness of the polyethylenimine ethoxylated (PEIE) interface layer on the performance of two types of polymer solar cells based on inverted poly(3-hexylthiophene) (P3HT):phenyl C61-butryric acid methyl ester (PCBM) and thieno[3,4-b]thiophene/benzodithiophene (PTB7):[6,6]-phenyl C71-butyric acid methyl ester (PC71BM). Maximum power conversion efficiencies of 4.18% and 7.40% were achieved at a 5.02 nm thick PEIE interface layer, for the above-mentioned solar cell types, respectively. The optimized PEIE layer provides a strong enough dipole for the best charge collection while maintaining charge tunneling ability. Optical transmittance and atomic force microscopy measurements indicate that all PEIE films have the same high transmittance and smooth surface morphology, ruling out the influence of the PEIE layer on these two parameters. The measured external quantum efficiencies for the devices with thick PEIE layers are quite similar to those of the optimized devices, indicating the poor charge collection ability of thick PEIE layers. The relatively low performance of devices with a PEIE layer of thickness less than 5 nm is the result of a weak dipole and partial coverage of the PEIE layer on ITO.

  5. Polyethylenimine Ethoxylated-Mediated All-Solution-Processed High-Performance Flexible Inverted Quantum Dot-Light-Emitting Device.

    PubMed

    Kim, Daekyoung; Fu, Yan; Kim, Sunho; Lee, Woosuk; Lee, Ki-Heon; Chung, Ho Kyoon; Lee, Hoo-Jeong; Yang, Heesun; Chae, Heeyeop

    2017-02-28

    We report on an all-solution-processed fabrication of highly efficient green quantum dot-light-emitting diodes (QLEDs) with an inverted architecture, where an interfacial polymeric surface modifier of polyethylenimine ethoxylated (PEIE) is inserted between a quantum dot (QD) emitting layer (EML) and a hole transport layer (HTL), and a MoOx hole injection layer is solution deposited on top of the HTL. Among the inverted QLEDs with varied PEIE thicknesses, the device with an optimal PEIE thickness of 15.5 nm shows record maximum efficiency values of 65.3 cd/A in current efficiency and 15.6% in external quantum efficiency (EQE). All-solution-processed fabrication of inverted QLED is further implemented on a flexible platform by developing a high-performing transparent conducting composite film of ZnO nanoparticles-overcoated on Ag nanowires. The resulting flexible inverted device possesses 35.1 cd/A in current efficiency and 8.4% in EQE, which are also the highest efficiency values ever reported in flexible QLEDs.

  6. Ferrocene-Functionalized Hydrophobically Modified Ethoxylated Urethane: Redox-Responsive Controlled Self-Assembly and Rheological Behavior in Aqueous Solution.

    PubMed

    Chang, Xueyi; Du, Zhukang; Hu, Feiyan; Cheng, Zhiyu; Ren, Biye; Fu, Shiyu; Tong, Zhen

    2016-11-22

    In this work, we present a novel redox-responsive ferrocene-functionalized hydrophobically modified ethoxylated urethane (Fc-HEUR) model polymer. The effects of a redox-induced hydrophobicity change of ferrocenyl hydrophobes on the self-assembly and rheological properties of Fc-HEUR in aqueous solution were investigated. In view of the redox-induced change in the hydrophilic-lipophilic balance of polymers, the Fc-HEUR polymer in aqueous solution can reversibly self-assemble into spherical micelles and larger micellar aggregates of different nanoscales and also disassemble by redox reactions immediately. Moreover, we have demonstrated that a rearrangement of micellar junctions takes place through a bridge-loop or loop-bridge transition in the concentrated polymer solution followed by redox reactions, which induces a great change in the rheological properties of the polymer solution: a viscoelastic liquid for the reduction state Fc-HEUR and a viscous liquid for the oxidation state Fc(+)-HEUR, owing to their different relaxation behaviors. Particularly, the associative structures and rheological properties of the Fc-HEUR aqueous solution can be reversibly controlled by redox reactions. This work will be useful not only for understanding of the thickening mechanism of stimuli-responsive HEURs but also for the development of reversible self-assembly and controlled rheological fluids, which may have some special application in drug delivery systems, catalyst supports, sensors, and microfluidic devices.

  7. 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

  8. 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).

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Column temperature as an active variable in the isocratic, normal-phase high-performance liquid chromatography separation of lipophilic metabolites of nonylphenol ethoxylates.

    PubMed

    Babay, Paola A; Gettar, Raquel T; Magallanes, Jorge F; Becquart, Elena T; Thiele, Björn; Batistoni, Daniel A

    2007-07-20

    Normal-phase separation of technical grade nonylphenol (t-NP, about 90% 4-nonylphenol), 4-nonylphenol mono-ethoxylate (4-NP1EO) and 4-nonylphenol di-ethoxylate (4-NP2EO) was assessed, with the inclusion of column temperature as an active variable. The compound 2,4,6-trimethylphenol was evaluated for use as internal standard. Isocratic elution with 2-propanol/hexanes mixtures from an amino-silica column and spectrometric UV detection at 277 nm were employed. Technical nonylphenol presented a significant contribution from unknown substances that eluted with retention times similar to that of 4-NP1EO. GC-MS analysis of the unknowns allowed to identify them as isomers of 2-NP. The response of the system to joint variations in flow rate, eluent composition and column temperature was investigated by means of Doehlert statistical experimental design. A model for retention of the analytes as a function of the experimental variables was proposed, and separation selectivity was studied. Selection of the optimal working zone was made through desirability function (D) calculations. Potential co-elution of 2-NP isomers with 4-NP1EO was considered when optimizing the separation. The occurrence of a restricted region of the experimental space where baseline resolution of analytes, associated impurities and internal standard results feasible (D not equal to 0) is apparent.

  1. Gas chromatography-mass spectrometry screening methods for select UV filters, synthetic musks, alkylphenols, an antimicrobial agent, and an insect repellent in fish.

    PubMed

    Mottaleb, Mohammad A; Usenko, Sascha; O'Donnell, John G; Ramirez, Alejandro J; Brooks, Bryan W; Chambliss, C Kevin

    2009-01-30

    Two screening methods have been developed for simultaneous determination of ten extensively used personal care products (PCPs) and two alkylphenol surfactants in fish. The methods consisted of extraction, clean-up, derivatization and analysis by gas chromatography-mass spectrometry with selected ion monitoring (GC-SIM-MS) or gas chromatography-tandem mass spectrometry (GC-MS/MS) techniques. Among solvents tested to assess recovery of target compounds from 1-g tissue homogenates, acetone was selected as optimal for extracting compounds with dissimilar physicochemical properties from fish tissue. Initial experiments confirmed that GC-SIM-MS could be applied for analysis of lean fillet tissue (<1% lipid) without gel-permeation chromatography (GPC), and this approach was applied to assess the presence of target analytes in fish fillets collected from a regional effluent-dominated stream in Texas, USA. Benzophenone, galaxolide, tonalide, and triclosan were detected in 11 of 11 environmental samples at concentrations ranging from; 37 to 90, 234 to 970, 26 to 97, and 17 to 31 ng/g, respectively. However, performance of this analytical approach declined appreciably with increasing lipid content of analyzed tissues. Successful analysis of samples with increased lipid content was enabled by adding GPC to the sample preparation protocol and monitoring analytes with tandem mass spectrometry. Both analytical approaches were validated using fortified fillet tissue collected from locations expected to be minimally impacted by anthropogenic influences. Average analyte recoveries ranged from 87% to 114% with RSDs <11% and from 54% to 107% with RSDs <20% for fish tissue containing <1% and 4.9% lipid, respectively. Statistically derived method detection limits (MDLs) for GC-SIM-MS and GC-MS/MS methodologies ranged from 2.4 to 16 ng/g, and 5.1 to 397 ng/g, respectively.

  2. 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

    2017-03-24

    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.

  3. Crystal Structure and Functional Analysis of the Extradiol Dioxygenase LapB from a Long-chain Alkylphenol Degradation Pathway in Pseudomonas*

    PubMed Central

    Cho, Jang-Hee; Jung, Du-Kyo; Lee, Kyoung; Rhee, Sangkee

    2009-01-01

    LapB is a non-heme Fe(II)-dependent 2,3-dioxygenase that catalyzes the second step of a long-chain alkylphenol (lap) degradation pathway in Pseudomonas sp. KL28 and belongs to the superfamily of type I extradiol dioxygenases. In this study, the crystal structures of substrate-free LapB and its complexes with a substrate or product were determined, along with a functional analysis of the active site residues. Structural features of the homotetramer are similar to those of other type I extradiol dioxygenases. In particular, the active site is located in the C-domain of each monomer, with a 2-His-1-carboxylate motif as the first coordination shell to iron ion. A comparison of three different structures in the catalytic cycle indicated catalysis-related local conformational changes in the active site. Specifically, the active site loop containing His-248 exhibits positional changes upon binding of the substrate and establishes a hydrogen-bonding network with Tyr-257, which is near the hydroxyl group of the substrate. Kinetic analysis of the mutant enzymes H248A, H248N, and Y257F showed that these three mutant enzymes are inactive, suggesting that this hydrogen-bonding network plays a crucial role in catalysis by deprotonating the incoming substrate and leaving it in a monoanionic state. Additional functional analysis of His-201, by using H201A and H201N mutants, near the dioxygen-binding site also supports its role as base and acid catalyst in the late stage of catalysis. We also noticed a disordered-to-ordered structural transition in the C-terminal region, resulting in the opening or closing of the active site. These results provide detailed insights into the structural and functional features of an extradiol dioxygenase that can accommodate a wide range of alkylcatechols. PMID:19828456

  4. Fluorometric flow-immunoassay for alkylphenol polyethoxylates on a microchip containing a fluorescence detector comprised of an organic light emitting diode and an organic photodiode.

    PubMed

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

    2015-03-01

    A compact fluorescence detector was constructed on a microchip from an organic light emitting diode (OLED) as the light source and an organic photodiode (OPD) as the photo-detector and was used in an immunoassay for alkylphenol polyethoxylates (APE). The OLED based on a terbium complex emitted a sharp light at the main wavelength of 546 nm with a full width at half maximum of 9 nm. The incident photo-to-current conversion efficiency (IPCE) of the OPD fabricated with Fullerene 70 (C70) and tris[4-(5-phenylthiopen-2-yl)phenyl]-amine (TPTPA) was approximately 44% for light at a wavelength of 586 nm. The performance of the fluorescence detector was evaluated for the determination of resorufin (λ(em)=586 nm) and the photocurrent of the OPD due to the fluorescence of resorufin was proportional to the concentration of resorufin in the range from 0 to 18 µM with a detection limit (S/N=3) of 0.6 µM. The fluorescence detector was successfully utilized in a competitive enzyme-linked immunosorbent assay for APE, where an anti-APE antibody was immobilized on the surface of the channel of the Polydimethylsiloxane (PDMS) microchip or on the surface of magnetic microbeads. After an immunoreaction with a sample solution of APE containing a horse radish peroxidase (HRP)-labeled APE, the fluorescence of resorufin generated just after introduction of a mixed solution of Amplex Red and H2O2 was measured using the fluorescence detector. The calibration curve for the photocurrent signals of the OPD due to the fluorescence of resorufin against the logarithmic concentration of APE was sigmoidal in shape. The detection limits defined as IC80 were ca. 1 ppb and ca. 2 ppb, respectively, for the methods using the anti-APE antibody immobilized on the surface of the microchannel and in the case where the antibody was immobilized on the surface of magnetic microbeads.

  5. Solid phase microextraction procedure for the determination of alkylphenols in water by on-fiber derivatization with N-tert-butyl-dimethylsilyl-N-methyltrifluoroacetamide.

    PubMed

    Pan, Yi-Ping; Tsai, Shih-Wei

    2008-08-29

    The solid phase microextraction (SPME) technique with on-fiber derivatization was evaluated for the analysis of alkylphenols (APs), including 4-tert-octylphenol (4-t-OP), technical nonylphenol isomers (t-NPs) and 4-nonylphenol (4-NP), in water. The 85 microm polyacrylate (PA) fiber was used and a two-step sample preparation procedure was established. In the first step, water sample of 2 mL was placed in a 4 mL PTFE-capped glass vial. Headspace extraction of APs in water was then performed under 65 degrees C for 30 min with 800 rpm magnetic stirring and the addition of 5% of sodium chloride. In the second step, the SPME fiber was placed in another 4 mL vial, which contained 100 microL of N-tert-butyl-dimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) with 1% tert-butyl-dimethylchlorosilane (TBDMCS). Headspace extraction of MTBSTFA and on-fiber derivatization with APs were performed at 45 degrees C for 10 min. Gas chromatography/mass spectrometry (GC/MS) was used for the analysis of derivatives formed on-fiber. The adsorption-time profiles were also examined. The precision, accuracy and method detection limits (MDLs) for the analysis of all the APs were evaluated with spiked water samples, including detergent water, chlorinated tap water, and lake water. The relative standard deviations were all less than 10% and the accuracies were 100+/-15%. With 2 mL of water sample, MDLs were in the range of 1.58-3.85 ng L(-1). Compared with other techniques, the study described here provided a simple, fast and reliable method for the analysis of APs in water.

  6. 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

  7. 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

  8. 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

  9. An ethoxylated surfactant enhances the penetration of the sulfated laminarin through leaf cuticle and stomata, leading to increased induced resistance against grapevine downy mildew.

    PubMed

    Paris, Franck; Krzyżaniak, Yuko; Gauvrit, Christian; Jamois, Frank; Domergue, Frédéric; Joubès, Jérôme; Ferrières, Vincent; Adrian, Marielle; Legentil, Laurent; Daire, Xavier; Trouvelot, Sophie

    2016-03-01

    Some β-1,3-glucans and particularly sulfated laminarin (PS3) are known as resistance inducers (RIs) in grapevine against the downy mildew. However, their efficacy in vineyard is still often too low, which might be caused by a limited penetration through the leaf cuticle following spray application. We used (14) C-sucrose uptake experiments with grapevine leaves in order to select a surfactant as saccharide penetration enhancer. Our results showed that although sucrose foliar uptake was low, it was strongly enhanced by Dehscofix CO125 (DE), a highly ethoxylated surfactant. Fluorescent saccharides were then produced and laser scanning microscopy was used to analyze their foliar diffusion pattern in Arabidopsis thaliana and grapevine. Interestingly, sucrose and PS3 were seemingly able to penetrate the leaf cuticle only when formulated with DE. Diffusion could preferentially occur via stomata, anticlinal cell walls and trichomes. In grapevine, PS3 penetration rate was much higher on the stomateous abaxial surface of the leaf than on the adaxial surface. Finally, using DE allowed a higher level of downy mildew control by PS3, which corroborated diffusion observations. Our results have practical consequences for the improvement of treatments with saccharidic inducers on grape. That is, formulation of such RIs plays a critical role for their cuticular diffusion and consequently their efficacy. Also, spray application should preferentially target the abaxial surface of the leaves in order to maximize their penetration.

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

    SciTech Connect

    Miles-Richardson, S.R.; Pierens, S.L.; Nichols, K.M.; Kramer, V.J.; Snyder, E.M.; Snyder, S.A.; Render, J.A.; Fitzgerald, S.D.; Giesy, J.P.

    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 the 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.

  11. Effect of a commercial alcohol ethoxylate surfactant (C11-15E7) on biodegradation of phenanthrene in a saline water medium by Neptunomonas naphthovorans.

    PubMed

    Li, Jing-Liang; Bai, Renbi

    2005-02-01

    Biodegradation of poorly soluble polycyclic aromatic hydrocarbons (PAHs) has been a challenge in bioremediation. In recent years, surfactant-enhanced bioremediation of PAH contaminants has attracted great attention in research. In this study, biodegradation of phenanthrene as a model PAHs solubilized in saline micellar solutions of a biodegradable commercial alcohol ethoxylate nonionic surfactant was investigated. The critical micelle concentration (CMC) of the surfactant and its solubilization capacity for phenanthrene were examined in an artificial saline water medium, and a type of marine bacteria, Neptunomonas naphthovorans, was studied for the biodegradation of phenanthrene solubilized in the surfactant micellar solutions of the saline medium. It is found that the solubility of phenanthrene in the surfactant micellar solutions increased linearly with the surfactant concentrations, but, at a fixed phenanthrene concentration, the biodegradability of phenanthrene in the micellar solutions decreased with the increase of the surfactant concentrations. This was attributed to the reduced bioavailability of phenanthrene, due to its increased solubilization extent in the micellar phase and possibly lowered mass transfer rate from the micellar phase into the aqueous phase or into the bacterial cells. In addition, an inhibitory effect of the surfactant on the bacterial growth at high surfactant concentrations may also play a role. It is concluded that the surfactant largely enhanced the solubilization of phenanthrene in the saline water medium, but excess existence of the surfactant in the medium should be minimized or avoided for the biodegradation of phenanthrene by Neptunomonas naphthovorans.

  12. Behaviour of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol ethoxylates (4-NP1EO, 4-NP2EO) in oxidative water treatment processes.

    PubMed

    Lenz, K; Beck, V; Fuerhacker, M

    2004-01-01

    Endocrine disrupting chemicals (EDCs) such as natural and synthetic hormones or industrial chemicals can adversely affect the endocrine system at very low concentrations. As such substances can be present in raw water used for drinking-water production, they potentially pose a health risk to humans. In this study laboratory tests were performed to determine removal efficiencies of selected oxidative drinking water treatment processes, namely ozonation (1.4 mg/l O3) and chlorination, using sodium hypochlorite (0.5 mg/l NaClO) and chlorine dioxide (0.4-0.6 mg/l ClO2) under conditions applied in technical plants. 500-300,000 ng/l of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol-n-ethoxylates (NPnEO) were selected for investigations and measured by HPLC/FLD and HPLC/MS. To investigate possible oxidation by-products, adsorbable organic halogens (AOX) were determined and estrogenic activities were assessed with the help of an estrogen receptor binding assay (YES). Ozonation and chlorination with ClO2 removed both 4-NP and BPA below detection limits, corresponding with AOX and estrogenic activity. Concerning NPnEO ozonation removed NP1EO and NP2EO up to 28% and 30%, respectively, whereas ClO2 showed high removal efficiencies, eliminating >94% and 92%, respectively. NaCIO removed 4-NP and BPA below detection limits, but estrogenic activities increased and AOX could be measured. NP1EO and NP2EO were only marginally reduced corresponding to the slight decrease of estrogenic potential.

  13. Polymer monolith microextraction using poly(butyl methacrylate-co-1,6-hexanediol ethoxylate diacrylate) monolithic sorbent for determination of phenylurea herbicides in water samples.

    PubMed

    Lin, Shu-Ling; Wu, Yu-Ru; Fuh, Ming-Ren

    2016-01-15

    In this study, recently developed 1,6-hexanediol ethoxylate diacrylate (HEDA)-based polymeric monoliths were utilized as sorbents for efficient extraction of phenylurea herbicides (PUHs) from water samples. The HEDA-based monolithic sorbents were prepared in a fused silica capillary (0.7mm i.d., 4.5-cm long) for polymer monolith microextraction (PMME). The experimental parameters of PMME microextraction including sample loading speed, pH of sample solution, composition of elution solvent, and addition of salt were optimized to efficiently extract PUHs from environmental water samples. The extracted PUHs were determined using ultra-high performance liquid chromatography (UHPLC) with UV-photodiode array detection. The extraction recoveries for PUHs-spiked water samples were 91.1-108.1% with relative standard deviations lower than 5%. The linearity range was 0.025-25ngmL(-1) for each PUH and the detection limits of PUHs were estimated at 0.006-0.019ng mL(-1). In addition, good intra-day/inter-day precision (0.1-8.7%/0.2-8.9%) and accuracy (92.0-108.0%/96.5-105.2%) of the proposed method were obtained. The extraction capacity of the monolith-filled capillary was also determined to be approximately 1μg. Moreover, each monolith-filled capillary could be reused up to 8 times without carry-over. According to the European Union regulations, the allowed permissible limit of any single herbicide in drinking water is 0.1ng mL(-1). This permissible level fell in the linear range examined in this study. In addition, the proposed method provided detection limits lower than the allowed permissible level, which demonstrated the feasibility of utilizing the HEDA-based monolithic sorbent to perform PMME for determining contaminants, such as PUHs, in environmental application.

  14. 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.

  15. Genotoxicity of 4-nonylphenol and nonylphenol ethoxylate mixtures by the use of Saccharomyces cerevisiae D7 mutation assay and use of this text to evaluate the efficiency of biodegradation treatments.

    PubMed

    Frassinetti, Stefania; Barberio, Claudia; Caltavuturo, Leonardo; Fava, Fabio; Di Gioia, Diana

    2011-03-01

    Nonylphenol ethoxylates (NPnEOs, where n is the number of ethoxylic units in the molecule) are non-ionic surfactants widely used for domestic and industrial purposes. 4-Nonylphenol (4-NP), the main product of NPnEO biodegradation, is a toxic xenobiotic compound classified as endocrine disrupter. While numerous studies reported the toxicity and oestrogenic activity of nonylphenols, little is known about the mutagenicity of these compounds. In this paper, the genotoxicity of 4-NP and NPnEO mixtures was evaluated by using the D7 strain of Saccharomyces cerevisiae as experimental model. The same genotoxicity tests were applied to effluents deriving from experimental packed-bed bioreactors, developed for the treatment of NPnEO contaminated wastewater, in order to evaluate the residual genotoxic potential with respect to the influent waste. The target compounds fed to the bioreactors were 4-NP and NPnEO mixtures possessing an average of 5 or 1.5 ethoxylic units (Igepal CO-520 and Igepal CO-210, respectively). The results showed that 4-NP induced significant cytotoxic effect on S. cerevisiae cells at 50 mg/L, as well as mutagenic effects at the lowest tested concentrations (12 and 25 mg/L). 4-NP was the most genotoxic compound among those assayed, followed by Igepal CO-210, whereas Igepal CO-520 did not induce genotoxicity at any of the assayed concentrations. The genotoxic effects of 4-NP on yeast cells disappeared after the treatment of 4-NP artificially contaminated water in the bioreactor. This indicates that the biological treatment is capable of removing not only the pollutant, but also the toxicity associated to the compound and its degradation metabolites. This study represents, to the best of our knowledge, the first report that evaluates the genotoxicity of both 4-NP, NPnEOs and their potential aerobic degradation products on an eukaryotic organism. The obtained results suggest that the S. cerevisiae D7 strain is a very effective model microorganism to study the

  16. Occurrence of Highly-Substituted Ethoxy-Carboxylates in Runoff Waters Near an Aircraft Deicing Facility

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reports documenting the occurrence of the metabolites of alkylphenol ethoxylates (APEs) are common. However, few data show the occurrence of the oxidative metabolite of the APEs, the carboxylates, and especially those with substitution greater than the 5 ethoxymer. An important reason for this has...

  17. Event-based quantification of emerging pollutant removal for an open stormwater retention basin - loads, efficiency and importance of uncertainties.

    PubMed

    Sébastian, C; Becouze-Lareure, C; Lipeme Kouyi, G; Barraud, S

    2015-04-01

    Up to now, emerging contaminants have not been further-studied in in-situ stormwater best management practices and especially in detention basins. In this article, the efficiency of a dry stormwater detention basin was investigated regarding the removal of 7 alkylphenols and alkylphenol ethoxylates, 9 polybrominated diphenyl ethers, 45 pesticides and bisphenol A. Concentrations of contaminants were obtained by chemical analysis on dissolved and particulate phase distinctly. The removal efficiency was assessed on total, dissolved and particulate phase accounting for the global chain of uncertainty with a 95% confidence interval. Results showed that pesticides (rather hydrophilic) are not trapped in the detention basin but are released contrarily to B209 which is mostly in particulate phase. Alkylphenols and alkylphenol ethoxylates are present in both phases and the efficiency is storm event-dependent. Uncertainty consideration in efficiency determination revealed efficiency data, usually presented by raw values are not relevant to conclude on the performance of a detention basin. In this case study, efficiency data with a 95% confidence interval indicate that only 35%, 50% and 41% of campaigns showed an impact (in trapping or releasing) of the detention basin on alkylphenols and ethoxylates, polybrominated diphenyl ethers and pesticides respectively.

  18. Low-dose exposure to alkylphenols adversely affects the sexual development of Atlantic cod (Gadus morhua): acceleration of the onset of puberty and delayed seasonal gonad development in mature female cod.

    PubMed

    Meier, Sonnich; Morton, H Craig; Andersson, Eva; Geffen, Audrey J; Taranger, Geir Lasse; Larsen, Marita; Petersen, Marianne; Djurhuus, Rune; Klungsøyr, Jarle; Svardal, Asbjørn

    2011-09-01

    Produced water (PW), a by-product of the oil-production process, contains large amount of alkylphenols (APs) and other harmful oil compounds. In the last 20 years, there have been increasing concerns regarding the environmental impact of large increases in the amounts of PW released into the North Sea. We have previously shown that low levels of APs can induce disruption of the endocrine and reproductive systems of Atlantic cod (Gadus morhua). The aims of this follow-up study were to: (i) identify the lowest observable effect concentration of APs; (ii) study the effects of exposure to real PW, obtained from a North Sea oil-production platform; and (iii) study the biological mechanism of endocrine disruption in female cod. Fish were fed with feed paste containing several concentrations of four different APs (4-tert-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol and 4-n-heptylphenol) or real PW for 20 weeks throughout the normal period of vitellogenesis in Atlantic cod from October to January. Male and female cod, exposed to AP and PW, were compared to unexposed fish and to fish fed paste containing 17β-oestradiol (E(2)). Approximately 60% of the females and 96% of the males in the unexposed groups were mature at the end of the experiment. Our results show that exposure to APs and E(2) have different effects depending on the developmental stage of the fish. We observed that juvenile females are advanced into puberty and maturation, while gonad development was delayed in both maturing females and males. The AP-exposed groups contained increased numbers of mature females, and significant differences between the untreated group and the AP-treated groups were seen down to a dose of 4 μg AP/kg body weight. In the high-dose AP and the E(2) exposed groups, all females matured and no juveniles were seen. These results suggest that AP-exposure can affect the timing of the onset of puberty in fish even at extremely low concentrations. Importantly, similar effects were not

  19. 40 CFR 721.5800 - Sulfurized alkylphenol.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... section. (2) The significant new uses are: (i) Hazard communication program. A significant new use of this... manufactured, imported, processed, or used in the employer's workplace, the employer must add the new information to an MSDS before the substance is reintroduced into the workplace. (B) The employer must...

  20. 40 CFR 721.5800 - Sulfurized alkylphenol.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... substance is any manner or method of manufacture, import, or processing associated with any use of this... days from the time the employer becomes aware of the new information. (ii) Industrial, commercial,...

  1. Fabrication and evaluation of an organic monolithic column based upon the polymerisation of hexyl methacrylate with 1,6-hexanediol ethoxylate diacrylate for the separation of small molecules by capillary liquid chromatography.

    PubMed

    Alshitari, Wael; Quigley, Cristina Legido; Smith, Norman

    2015-08-15

    This paper describes the fabrication of a new porous monolith, prepared in 100μm i.d. capillaries by the co-polymerisation of hexyl methacrylate with 1,6-hexanediol ethoxylate diacrylate, poly (HMA-co-1,6 HEDA), in the presence of azobisisobutyronitrile, 1, 4-butanediol and 1-propanol were used as porogens for the monoliths; the monoliths were then used as a stationary phase for capillary liquid chromatography. Two cross linkers namely 1,6 HEDA and EDMA were utilised in order to investigate the effects of cross linker length on the separation efficiency of small molecules, and it was found that the efficiency of the separation improved tenfold when using the longer cross linker, 1,6 HEDA. This improvement is associated with the increase in number of methylene groups which resulted in an increased number of mesopores, less than 50nm. The 1,6 HEDA based monolith showed a high porosity (90%) and no evidence of swelling or shrinking with the use of organic solvents. Moreover, the 1,6 HEDA monolith demonstrated high reproducibility for the separation of the retained compounds anisole and naphthalene; these showed retention time RSDs of 1.79% and 2.74% respectively. The fabricated monolith also demonstrated high selectivity for neutral non-polar molecules, weak acids, and basic molecules. The asymmetry factors for basic molecules (nortriptyline and amitriptyline) were 1.5 and 1.3 respectively, indicating slight tailing, which is often noticeable on silica based phases due to secondary interactions between basic moieties and the hydroxyl groups of the silica.

  2. Effects of nonionic surfactants on the microbial mineralization of phenanthrene in soil-water systems. [Quarterly report

    SciTech Connect

    Laha, S.; Luthy, R.G.

    1992-05-01

    The purpose of the work reported in this paper was to determine whether the inhibitory effect on microbial degradation of phenanthrene was specific to the nonionic surfactants used previously, i.e., the alkylethoxylate and alkylphenol ethoxylate surfactants. Thus, a number of nonionic surfactants of varying structures and properties were selected for further investigation. In addition, several tests were performed to verify results from earlier experiments.

  3. 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.

  4. Acute aquatic toxicity of alkyl phenol ethoxylates

    SciTech Connect

    Schueuermann G2 )

    1991-04-01

    The recently derived log Kow (octanol/water partition coefficient in logarithmic form) increment for a nonterminal oxyethylene unit was used to calculate a quantitative structure-activity relationships for literature data on the acute crustacean toxicity of polyoxyethylene surfactants. The resulting log Kow regression parameters are between the corresponding values for nonpolar and polar narcosis, which supports an interpretation of the surfactants' aquatic toxicity on the basis of another distinct mode of action. Furthermore, a comparison with calculated water solubility data indicates that for log Kow greater than 5 an aquatic toxicity decrease due to a solubility limit is expected, which gets support from two other sets on toxicity data of nonyl phenol polyethoxylates.

  5. Characterisation of ethoxylated fatty chains of anionic surfactants and determination of residual ethoxylated fatty alcohols.

    PubMed

    Morvan, Julien; Saluden, Magali; Agasse, Valérie; Barbot, Florence; Cardinael, Pascal; Bouillon, Jean-Philippe; Decock, Gautier

    2006-03-01

    Bachus et al. [1] recently described a new derivatisation method using 2-furoyl chloride for the characterisation of mixtures of polyethoxylated alcohols and their corresponding sulfates. This paper deals with the control of the derivatisation steps; hydrolysis and extraction conditions were optimised. The method is extended to the characterisation of alkyl sulfosuccinates, alkyl sulfoacetates and alkyl phosphates and to the analysis of residual polyethoxylated alcohols in surfactants. Extraction of non-ionic compounds using solid-phase extraction cartridges was performed before derivatisation. Residual amounts of alcohol were determined in five commercial anionic surfactants. Moreover, direct derivatisation without preliminary SPE in the same anionic surfactants proved to be efficient for dry samples.

  6. 40 CFR 721.4700 - Metalated alkylphenol copolymer (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... program. Requirements as specified in § 721.72 (b)(1)(i)(C), (b)(1)(ii), (b)(1)(iii), (b)(1)(iv), (b)(2.... Requirements as specified in § 721.80(j) (industrial coating material). (iii) Disposal. Requirements as specified in § 721.85 (a)(1), (a)(3), (b)(1), (b)(3), (c)(1), and (c)(3). (iv) Release to...

  7. 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.

  8. [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.

  9. 75 FR 44917 - Castor Oil, Ethoxylated, Dioleate; Tolerance Exemption

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-30

    ... not limited to: Crop production (NAICS code 111). Animal production (NAICS code 112). Food..., Preston, PR5 6BL, United Kingdom. The petition requested that 40 CFR 180.960 be amended by establishing...

  10. 21 CFR 172.834 - Ethoxylated mono- and diglycerides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 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...

  11. 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...

  12. 21 CFR 172.834 - Ethoxylated mono- and diglycerides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 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...

  13. 21 CFR 172.834 - Ethoxylated mono- and diglycerides.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 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 percent by... of the finished frozen desserts. 6. As an emulsifier in edible vegetable fat-water emulsions...

  14. 21 CFR 172.834 - Ethoxylated mono- and diglycerides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 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...

  15. 40 CFR 721.10026 - Cashew, nutshell liq., ethoxylated.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) Industrial, commercial, and consumer activities. Requirements as specified in § 721.80(k) (any manufacturing, processing, or use of the PMN substance with less than 55 moles of the ethoxy or with an average...

  16. 40 CFR 721.10026 - Cashew, nutshell liq., ethoxylated.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...) Industrial, commercial, and consumer activities. Requirements as specified in § 721.80(k) (any manufacturing, processing, or use of the PMN substance with less than 55 moles of the ethoxy or with an average...

  17. 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.

  18. 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.

  19. 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 LC50 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.

  20. Toxicological properties of thio- and alkylphenols causing flavor tainting in fish from the upper Wisconsin River

    SciTech Connect

    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).

  1. Migration of plasticizers phthalates, bisphenol A and alkylphenols from plastic containers and evaluation of risk.

    PubMed

    Guart, A; Bono-Blay, F; Borrell, A; Lacorte, S

    2011-05-01

    This study investigates the potential migration of plasticisers, plastic components and additives from several plastic water bottles. Compounds studied were phthalates (dimethyl phthalate, di-n-butyl phthalate, benzylbutyl phthalate, bis(2-ethylhexyl) phthalate), bis(2-ethylhexyl) adipate, octylphenol, 4-nonylphenol and bisphenol A. Polycarbonate (PC), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene terephthalate (PET) and polystyrene (PS) plastics used in the water bottling sector were tested using three kinds of total or specific migration tests: (1) standard method UNE-EN ISO 177; (2) ultrasonic forced extraction; and (3) standard method UNE-EN 13130-1. In addition, bottled waters contained in different plastic materials were analysed to determine the potential migration of target compounds in real conditions. In all cases, samples were solid-phase extracted using Oasis HLB 200 mg cartridges and analysed using GC-MS in scan-acquisition mode. Bisphenol A and 4-nonylphenol were detected in incubated samples, indicating that migration from food plastics can occur at the experimental conditions tested. The total daily intake was calculated according to the levels detected in bottled water and the assessment of the consumers' risk was evaluated taking into consideration toxicological and legislative values.

  2. 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...

  3. Biodegradation and attenuation of steroidal hormones and alkylphenols by stream biofilms and sediments.

    PubMed

    Writer, Jeffrey H; Barber, Larry B; Ryan, Joseph N; Bradley, Paul M

    2011-05-15

    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.

  4. 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.

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

    PubMed

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

    2012-03-15

    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 (5.42μg/g) versus the fall (0.99μg/g) tand these differences were shared by differences in the water concentrations (spring - 11.47 versus fall - 3.44μg/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 3.5μg/g in the bass for the spring, the PBDE-congener 47 and p,p'-DDE averaged 1.0μg/g and 0.5μg/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.

  6. Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain).

    PubMed

    Köck-Schulmeyer, Marianne; Ginebreda, Antoni; Postigo, Cristina; López-Serna, Rebeca; Pérez, Sandra; Brix, Rikke; Llorca, Marta; de Alda, Miren López; Petrović, Mira; Munné, Antoni; Tirapu, Lluís; Barceló, Damià

    2011-01-01

    The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ngL(-1) range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals>alkylphenols>pesticides>illicit drugs≫estrogens.

  7. 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.

  8. Development and validation of a method using on-line solid-phase extraction and liquid chromatography with ultraviolet detection for the determination of bisphenol A, octylphenol, and nonylphenol in groundwater.

    PubMed

    Careri, M; Elviri, L; Mangia, A

    2001-01-01

    Alkylphenols are nonbiodegradable metabolites arising from various pathways of aerobic and anaerobic degradation of the nonionic surfactants alkylphenol ethoxylates. A method based on the use of on-line solid-phase extraction (SPE) and liquid chromatography (LC) with UV detection was developed to determine bisphenol A, octylphenol, and nonylphenol at trace levels in water. The on-line coupled SPE procedure automatically enables an approximately 300-fold preconcentration of analytes, which can be further enhanced by an increase in applied sample volume. By using C18 cartridges, recoveries of >90% were obtained for all the analytes. A validation procedure was carried out with a groundwater sample to ensure the quality of the results; performance criteria such as detection limits (LODs), quantitation limits (LOQs), linearity, and precision were evaluated. LODs and LOQs in the range of 0.17-0.36 and 0.35-1.88 microg/L, respectively, were found; for all the analytes, linearity was established over 2 orders of magnitude (r2 >0.997, n = 54). The intraday repeatability values expressed as relative standard deviations were <5.3%; a nested analysis of variance was performed to verify the influence of 3 different factors, i.e., different days, extraction procedure, and LC replicate injection, on data precision.

  9. The TSCA Interagency Testing Committee (ITC) proposed strategy for identifying and coordinating U.S. government data needs for endocrine-disrupting chemicals

    SciTech Connect

    Walker, J.D.

    1995-12-31

    The ITC`s Endocrine-Disrupting Chemicals Subcommittee will implement a proposed strategy for identifying and coordinating the US government ecological and health effects data needs for endocrine-disrupting chemicals, These include chemicals with potential to cause reproductive, developmental, immunological, neurologic or other biological effects by adversely affecting endocrine tissues, hormones or receptors in fish, wildlife or humans. To meet these needs, the Subcommittee will consider three options. First, the information collecting authority of the Toxic Substances Control Act (TSCA) will be considered as a cost-effective mechanism to rapidly (within 60 days) obtain unpublished health and ecological effects studies related to reproductive effects and endocrine-disrupting activity. Second, the chemical testing authority of TSCA will be considered as a method to request that the manufacturers of endocrine-disrupting chemicals conduct tests that are amenable to standardization. Third, consideration will be given to coordinating standardized testing with testing related to research and to using the results of this research to develop standardized methods for assessing the effects of endocrine-disrupting chemicals. The Subcommittee will focus on 16 alkylphenol and alkylphenol ethoxylates with 1989 production or importation volumes greater than 1 million pounds that were identified using the Substructure based Computerized Chemical Selection Expert System (SuCCSES). The ITC`s proposed strategy will be discussed.

  10. 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.

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

    PubMed

    Cantero, Manuel; Rubio, Soledad; Pérez-Bendito, Dolores

    2005-03-04

    The capability of hemimicelles-based solid phase extraction (SPE)/liquid chromatography/atmospheric pressure chemical ionisation in positive mode, ion trap mass spectrometry (LC/(APCl+-IT)-MS) for the concentration, separation and quantitation of non-ionic surfactants has been investigated. Concentration was based on the formation of mixed aggregates of analytes [alkylphenol ethoxylates (APE, octyl and nonyl) and alkyl ethoxylates (AE, C12-C16)] with the anionic surfactant sodium dodecyl sulphate (SDS) that is adsorbed on alumina. Parameters affecting SPE were investigated on the basis that hemimicelles are dynamic entities in equilibrium with the aqueous phase. The performance of ion trap mass spectrometry for MS and MS/MS quantitation of non-ionic homologues was assessed. Recoveries of analytes from wastewater influent and effluent and river water samples ranged between 91 and 98% and were found independent on the length of the alkyl chain under the optimised conditions. Anionic surfactants did not interfere to the levels found in environmental samples. The detection limits ranged between 14 and 111 ng/l for wastewater influent, 10 and 40 for wastewater effluent and 4 and 35 for river water, after concentration of 250, 500 and 750 ml of sample, respectively. The approach was applied to the determination of AE and APE in influent and effluent samples from four wastewater treatment plants and four river samples. The concentrations of individual non-ionic surfactants found ranged between 0.3 and 373 microg/l.

  12. 77 FR 75085 - Proposed Significant New Use Rule on Ethoxylated, Propoxylated Diamine Diaryl Substituted...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-19

    ... Diamine Diaryl Substituted Phenylmethane Ester With Alkenylsuccinate, Dialkylethanolamine Salt AGENCY..., dialkylethanolamine salt, which was the subject of premanufacture notice (PMN) P-01-384. This action would require... diaryl substituted phenylmethane ester with alkenylsuccinate, dialkylethanolamine salt...

  13. 78 FR 25388 - Significant New Use Rule on Ethoxylated, Propoxylated Diamine Diaryl Substituted Phenylmethane...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-01

    ... Diaryl Substituted Phenylmethane Ester With Alkenylsuccinate, Dialkylethanolamine Salt AGENCY..., dialkylethanolamine salt, which was the subject of premanufacture notice (PMN) P-01-384. This action requires persons..., dialkylethanolamine salt. The following list of North American Industrial Classification System (NAICS) codes is...

  14. 75 FR 74628 - Tristyrylphenol Ethoxylates; Exemption From the Requirement of a Tolerance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-01

    ... Docket in Rm. S-4400, One Potomac Yard (South Bldg.), 2777 S. Crystal Dr., Arlington, VA. The Docket... Office's e-CFR site at http://www.gpoaccess.gov/ecfr . C. How can I file an objection or hearing request? Under FFDCA section 408(g), 21 U.S.C. 346a, any person may file an objection to any aspect of...

  15. 75 FR 22234 - Phosphate Ester, Tallowamine, Ethoxylated; Exemption from the Requirement of a Tolerance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-28

    ... Corporation submitted a petition to EPA under the Federal Food, Drug, and Cosmetic Act (FFDCA), requesting.... Specific information on the studies received and the nature of the adverse effects caused by PETAE as well as the no-observed- adverse-effect-level (NOAEL) and the lowest-observed-adverse-effect- level...

  16. 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...

  17. 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...

  18. In vivo and in vitro effects of prochloraz and nonylphenol ethoxylates on trout spermatogenesis.

    PubMed

    Le Gac, F; Thomas, J L; Mourot, B; Loir, M

    2001-08-01

    We investigated the effects of in vivo exposure to non-lethal concentrations of two chemicals commonly discharged into the aquatic environment, prochloraz and nonylphenol diethoxylate (NP2EO - Igepal(R) 210), on the development of spermatogenesis in trout. The in vitro effects on basal and insulin-like growth factor-1 (IGF-I) stimulated DNA synthesis by early germ cells were also studied. In vivo, rainbow trout were exposed for 2 or 3 weeks to waterborne prochloraz (21 and 175 nmol/l) and/or NP2EO (68-970 nmol/l) renewed continuously, or periodically. Only the highest concentrations of NP2EO (225-970 nmol/l) induced a significant increase in blood plasma vitellogenin in juvenile or maturing male trout. When prepubertal fish were exposed for 15 days to prochloraz, the spermatogenetic process was significantly inhibited as shown by the stage of gonadal development reached 3 weeks after exposure. This effect was, to a great extent, reversible within 9 weeks post-exposure. When fish in the initial stage of spermatogenesis were exposed for 21-27 days to 580 nmol/l NP2EO, a 20-40% reduction of the gonadosomatic index was observed 4.5 weeks post-exposure, and the spermatogenetic process was partly inhibited. In vitro, testicular cells obtained at different stages of spermatogenesis were cultured for 4.5 days in the presence or not of the tested molecules and with IGF-I or not. 3H-thymidine (3H-Tdr) incorporation was measured according to Loir (Mol. Reprod. Dev. 53 (1999) 424) and 125I-IGF-I specific binding was determined according to Le Gac et al. (Mol. Reprod. Dev. 44 (1996) 35). Irrespective of the spermatogenetic stage, basal 3H-Tdr incorporation was decreased by prochloraz concentrations > or =10 micromol/l. The presence of IGF-I (10-100 ng/ml) stimulated 3H-Tdr incorporation; this response to IGF-I began to decrease at 25-50 micromol/l prochloraz. In parallel, a dose-dependent increase of IGF-I specific binding was induced by prochloraz 1-100 micromol/l. Similarly, basal and IGF-I-stimulated 3H-Tdr incorporation was decreased by nonylphenol polyethoxylate (NpnEO; starting at 10 micromol/l), NP2EO and NP (30 micromol/l); a dose-dependent increase of IGF-I specific binding was also induced by NP and NPnEO. While 1-100 nmol/l 17beta-estradiol had no effect in our in vitro system, Triton(R) X-100 acted as NPnEO on 3H-Tdr incorporation. Beside their known endocrine disrupting effects on sex steroid production or action, these lipophilic molecules could act on germ cells by disrupting cell membrane receptivity to peptide hormones like growth factors.

  19. 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.

  20. [Determination of alkyl-phenols in textiles by in-tube capillary solid-phase extraction-gas chromatography].

    PubMed

    Zhang, Luohong; Du, Ting; Zhong, Jiayu

    2015-10-01

    An in-tube capillary solid-phase extraction (SPE) -gas chromatography (GC) method was developed for confirmation and quantitative determination of octylphenol (OP) and nonylphenol (NP) in textiles. To make the in-tube capillary SPE column, the best SPE cartridge was chosen from four kinds of SPE cartridges. The adsorbent in the cartridge was used as the filling material to make the in-tube capillary SPE column. The nature, volume used, flow rate and adsorption capacity of the eluent were compared. Finally, the in-tube capillary solid-phase extraction was combined with gas chromatography to detect the alkyl phenols (APs). Abselut NEXUS extraction cartridge was chosen as the best solid phase extractant. The optimal in-tube capillary SPE extraction conditions were as follows: 1.2 μL methanol and 1.2 μL ultra-pure water for activating the extraction column, 1.2 μL methanol for eluting, 0.4 μL/min for solution loading. The method showed a good linear relationship in the low concentration range, and the enrichment ratios for the APs were about 100 times. The detection limits of octylphenol and nonylphenol were 3.7 μg/L and 4.5 μg/L, respectively. The recoveries of octylphenol were 85.6%-98.2%, and those of nonylphenol were 83.8%-95.7%. The experimental results demonstrated that the method is simple, rapid, and useful for detecting APs in textiles.

  1. Estrogenic alkylphenols in fish tissues, sediments, and waters from the U.K. Tyne and Tees estuaries

    SciTech Connect

    Lye, C.M.; Frid, C.L.J.; Gill, M.E.; Cooper, D.W.; Jones, D.M.

    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 sediments 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.

  2. Solvent Extraction of Sodium Hydroxide Using Alkylphenols and Fluorinated Alcohols: Understanding the Extraction Mechanism by Equilibrium Modeling

    SciTech Connect

    Kang, Hyun-Ah; Engle, Nancy L.; Bonnesen Peter V.; Delmau, Laetitia H.; Haverlock, Tamara J.; Moyer, Bruce A.

    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 for 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.

  3. Chemical analysis of fish bile extracts for monitoring endocrine disrupting chemical exposure in water: Bisphenol A, alkylphenols, and norethindrone.

    PubMed

    Wu, Minghong; Pan, Chenyuan; Yang, Ming; Xu, Bentuo; Lei, Xiangjie; Ma, Jing; Cai, Ling; Chen, Jingsi

    2016-01-01

    The present study determined concentrations of estrogenic bisphenol A (BPA), nonylphenol, octylphenol (4-tert-octylphenol), butylphenol (4-tert-butylphenol), and progestogenic norethindrone by liquid chromatography-tandem mass spectrometry in bile extracts from field fish from the Xin'an River and market fish in Shanghai, China. Compared with the field fish, endocrine disrupting chemical (EDC) concentrations in market fish bile were at relatively high levels with high detectable rates. The average concentrations of BPA, nonylphenol, 4-tert-octylphenol, 4-tert-butylphenol, and norethindrone in field fish bile were 30.1 µg/L, 203 µg/L, 4.69 µg/L, 7.84 µg/L, and 0.514 µg/L, respectively; in market fish bile they were 240 µg/L, 528 µg/L, 76.5 µg/L, 12.8 µg/L, and 5.26 µg/L, respectively; and in the surface water of Xin'an River they were 38.8 ng/L, 7.91 ng/L, 1.98 ng/L, 2.66 ng/L, and 0.116 ng/L, respectively. The average of total estrogenic activity of river water was 3.32 ng/L estradiol equivalents. High bioconcentration factors (BCFs) were discovered for all 5 EDCs (≧998-fold) in field fish bile. Furthermore, the authors analyzed the BCF value of BPA in fish bile after 30-d exposure to environmentally relevant concentrations of BPA in the laboratory, and the analysis revealed that BCF in fish bile (BCF(Fish bile)) changed in an inverse concentration-dependent manner based on the log10-transformed BPA concentration in water. Strikingly, the data from the field study were well fitted within this trend. The data together suggested that analysis of fish bile extracts could be an efficient method for assessing waterborne EDCs exposure for aquatic biota.

  4. Development of Molecularly Imprinted Polymer in Porous Film Format for Binding of Phenol and Alkylphenols from Water

    PubMed Central

    Gryshchenko, Andriy O.; Bottaro, Christina S.

    2014-01-01

    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. PMID:24447925

  5. Occurrence of emerging organic contaminants in a tropical urban catchment in Singapore.

    PubMed

    Xu, Yonglan; Luo, Fei; Pal, Amrita; Gin, Karina Yew-Hoong; Reinhard, Martin

    2011-05-01

    Emerging organic contaminants (EOCs) occurring in urban runoff can negatively impact sensitive ecosystems and drinking water resources. The occurrence of 13 EOCs was characterized in the Marina Catchment, a large urban catchment approximately one-sixth the area of Singapore. The 13 EOCs included alkylphenol ethoxylate metabolites (APEMs), hormones, pharmaceuticals, bisphenol A, and a pesticide (fipronil). The APEMs were most prevalent with concentrations of nonylphenol ethoxyacetic acid (NP1EC) and nonlyphenol (NP) ranging from several ng L(-1) to 6 μg L(-1) and 4 μg L(-1), respectively, while concentrations of octylphenol ethoxyacetic acid (OP1EC), dicarboxylated alkylphenol ethoxyacetic acid (CA3P1EC, CA4P1EC) were as high as 0.9 μg L(-1). Other EOCs were present in the ng L(-1) range: chloramphenicol 1-15 ng L(-1), ibuprofen 2-76 ng L(-1), naproxen 8-108 ng L(-1), bisphenol A 30-625 ng L(-1), fipronil 1-72 ng L(-1), estrone 1-304 ng L(-1), estriol 3-451 ng L(-1). The APEMs and EOCs detected appear to enter canals and rivers from non-point sources, possibly from runoff and leaking sewer lines. The closure of Marina Bay with a barrage has resulted in significantly higher levels of APEMS compared to when the bay was open to the sea. Depth profiles show that NP1EC and OP1EC were notably lower in deep waters compared to surface waters. NP, estrone and estriol exceeded literature-based Predicted No Effect Concentration (PNEC) values.

  6. Evaluation of estrogenic activities of aquatic herbicides and surfactants using an rainbow trout vitellogenin assay.

    PubMed

    Xie, Lingtian; Thrippleton, Kelly; Irwin, Mary Ann; Siemering, Geoffrey S; Mekebri, Abdou; Crane, David; Berry, Kevin; Schlenk, Daniel

    2005-10-01

    Estrogenic potencies of four herbicides (triclopyr, 2,4-dichlorophenoxyacetic acid (2,4-D), diquat dibromide, glyphosate), two alkylphenol ethoxylate-containing surfactants (R-11 and Target Prospreader Activator (TPA)), and the binary mixture of surfactants with the herbicides were evaluated using an in vivo rainbow trout vitellogenin assay. Juvenile rainbow trout exposed to 2,4-D (1.64 mg/l) for 7 days had a 93-fold increase in plasma vitellogenin (Vtg) levels compared with untreated fish, while rainbow trout exposed to other pesticides alone did not show elevated vitellogenin levels compared to the control fish. When combined with surfactants, trends indicated enhanced estrogenicity for all combinations, but only 2,4-D and triclopyr caused significant induction of Vtg. Concentration-response studies demonstrated that the lowest observed effect concentrations (LOECs) for 2,4-D and triclopyr were 0.164 mg/l and 1 mg/l, respectively. In terms of measured 4-nonylphenol (4-NP), the LOECs of R-11 and TPA were 20 micro/l and 9.5 microg/l, respectively. Binary mixtures of TPA and 2,4-D showed a greater than additive estrogenic response at the lowest concentrations tested, but a less than additive response at the highest combined concentrations. Binary mixtures of TPA with triclopyr also caused greater than additive Vtg responses in two middle concentrations when compared to TPA or triclopyr alone. When trout were exposed to water collected from a site where triclopyr was used in combination with TPA, a concentration-dependent increase in Vtg expression was observed. Measured values of 4-NP were 3.7 microg/l, and triclopyr concentrations were below detection (<5 ng/l). Estradiol equivalents (EEQs) of the lake water were calculated from an estradiol concentration-response curve and were similar (8.5 +/- 7.7 ng/l) to the mean values for the combined triclopyr + TPA treatments (9.9-12.2 ng/l) in the laboratory, suggesting the estrogenicity of the water may have been due to

  7. Detection of estrogenic activity in sediment-associated compounds using in vitro reporter gene assays.

    PubMed

    Legler, Juliette; Dennekamp, Martine; Vethaak, A Dick; Brouwer, Abraham; Koeman, Jan H; van der Burg, Bart; Murk, Albertinka J

    2002-07-03

    Sediments may be the ultimate sink for persistent (xeno-)estrogenic compounds released into the aquatic environment. Sediment-associated estrogenic potency was measured with an estrogen receptor-mediated luciferase reporter gene (ER-CALUX) assay and compared with a recombinant yeast screen. The ER-CALUX assay was more sensitive to 17beta-estradiol (E2) than the recombinant yeast screen, with an EC50 of 6 pM E2 compared to 100 pM in the yeast screen. Yeast cells were unable to distinguish the anti-estrogens ICI 182,780 and (4-hydroxy)tamoxifen, which were agonistic in the yeast. Acetone-soluble fractions of hexane/acetone extracts of sediments showed higher estrogenic potency than hexane-soluble extracts in the ER-CALUX assay. Sediments obtained from industrialized areas such as the Port of Rotterdam showed the highest estrogenic potency of the 12 marine sediments tested (up to 40 pmol estradiol equivalents per gram sediment). The estrogenic activity of individual chemicals that can be found in sediments including: alkylphenol ethoxylates and carboxylates; phthalates; and pesticides, was tested. Increasing sidechain length of various nonylphenol ethoxylates resulted in decreased estrogenic activity. Of the phthalates tested, butylbenzylphthalate was the most estrogenic, though with a potency approximately 100,000 times less than E2. The organochlorine herbicides atrazine and simazine failed to induce reporter gene activity. As metabolic activation may be required to induce estrogenic activity, a metabolic transformation step was added to the ER-CALUX assay using incubation of compounds with liver microsomes obtained from PCB-treated rats. Results indicate that metabolites of E2, NP and bisphenol A were less active than the parent compounds, while metabolites of methoxychlor were more estrogenic following microsomal incubations.

  8. 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, ...

  9. 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.

  10. Magnetic recovery of modified activated carbon powder used for removal of endocrine disruptors present in water.

    PubMed

    Borghi, Chiara Caterina; Fabbri, Massimo

    2014-01-01

    This paper was aimed at studying sustainable solutions for the treatment of water polluted by octylphenols and nonylphenols that are xenoextrogen compounds affecting human health and dangerous for the aquatic environment. We studied the removal of 4-octylphenol and 4-n-nonylphenol with concentrations of the order of 5-10 mg/l on a laboratory scale. A mixing time of 10 min with 0.1 g/l of magnetic-activated carbons (MACs) was enough to obtain 95 +/- 5% adsorption of both 4-octylphenol and 4-n-nonylphenol. The adsorption of the surfactants IGEPAL CO-630 and TRITON X-100, which are precursors of branched 4-nonylphenol and the carcinogenic 4-tert-octylphenol, respectively, was also studied using the same technique. For concentrations between 2 and 10mg/l of these alkylphenols ethoxylated, after 10min mixing with 0.5 g/l of MACs, a 95 +/- 5% adsorption was obtained. A 97 +/- 1% removal of MACs was achieved after 10min of continuous-flow magnetic filtration (14.5 l/min). The filter used was made of SUS440C magnetic steel spheres. Srm-Co permanent magnets provided a uniform flux density field of about 500 mT.

  11. Fouling-release and chemical activity effects of a siloxane-based material on tunicates.

    PubMed

    Filip, Natalia; Pustam, Amanda; Ells, Veronica; Grosicki, Kathleen M T; Yang, Jin; Oguejiofor, Ikenna; Bishop, Cory D; DeMont, M Edwin; Smith-Palmer, Truis; Wyeth, Russell C

    2016-05-01

    The antifouling performance of a siloxane-based elastomeric impression material (EIM) was compared to that of two silicone fouling-release coatings, Intersleek 757 and RTV-11. In field immersion trials, the EIM caused the greatest reduction in fouling by the solitary tunicate Ciona intestinalis and caused the longest delay in the progression of fouling by two species of colonial tunicate. However, in pseudobarnacle adhesion tests, the EIM had higher attachment strengths. Further laboratory analyses showed that the EIM leached alkylphenol ethoxylates (APEs) that were toxic to C. intestinalis larvae. The EIM thus showed the longest duration of chemical activity measured to date for a siloxane-based coating (4 months), supporting investigations of fouling-release coatings that release targeted biocides. However, due to potential widespread effects of APEs, the current EIM formulation should not be considered as an environmentally-safe antifoulant. Thus, the data also emphasize consideration of both immediate and long-term effects of potentially toxic constituents released from fouling-release coatings.

  12. 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.

  13. Toxic effects of octylphenol on the expression of genes in liver identified by suppression subtractive hybridization of Rana chensinensis.

    PubMed

    Li, Xin-Yi; Xiao, Ning; Zhang, Yu-Hui

    2014-01-01

    Octylphenol (OP) is the degradative product of alkylphenol ethoxylates that are widely used to produce rubber, pesticides, and paints. It is chemically stable substance and demonstrates estrogenic effects, toxicity and carcinogenic effects in the environment. The toxin accumulates rapidly in the liver where it exerts most of its damage, but the molecular mechanisms behind its toxicity remain unclear. Due to limited information concerning the effect of OP on liver, this study investigates how OP causes hepatotoxicity in liver. Here, suppression subtractive hybridization was used to identify the alterations in gene transcription of the frog (Rana chensinensis) after exposure to OP. After hybridization and cloning, the subtractive cDNA libraries were obtained. At random, 207 positive clones were selected and sequenced from the subtractive libraries, which gave a total of 75 gene fragment sequences. The screening identified numerous genes involved in apoptosis, signal transduction, cytoskeletal remodeling, innate immunity, material and energy metabolism, translation and transcription which were extensively discussed. Two sequenced genes were analyzed further using real time quantitative PCR. The two genes from the library were found to be transcriptionally up-regulated. These results confirmed the successful construction of the subtractive cDNA library that was enriched for the genes that were differentially transcribed in the amphibian liver challenged with OP, and for the first time present the basic data on toxicity effect of OP on liver.

  14. 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

    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.

  15. Hazardous substances in the aquatic environment of Estonia.

    PubMed

    Roots, Ott; Roose, Antti

    2013-09-01

    The Water Framework Directive (WFD) aims to regulate the management of European surface water bodies. Directive 2008/105/EC, which establishes the environmental quality standards of priority substances and certain other pollutants, the content of which in the surface water should be monitored, has been transposed by the Estonian Ministry of Environment 9 September 2010 Regulation No. 49. Sampled hazardous substances were selected primarily based on their toxicity, as well as their lifetime in environment and ability to accumulate in living organisms (bioaccumulation). The contents of hazardous substances and their groups determined from Estonian surface waters remained below the limits of quantifications of used analysis methods in most cases. However, the content of some heavy metals, mono- and dibasic phenols in the surface water/waste water and sewage sludge/bottom sediments can still reach the delicate levels in the Estonian oil shale region in particular. Among new substances analysed in Estonia historically first time in 2010, amounts of organotin compounds in sediments and some alkylphenols, their ethoxylates and phthalates were found in various sample matrices.

  16. Alteration of hepatic anti-oxidant systems by 4-nonylphenol, a metabolite of alkylphenol polyethoxylate detergents, in Far Eastern catfish Silurus asotus

    PubMed Central

    Park, Kwan Ha

    2015-01-01

    Objectives This study aimed to estimate the effects of 4-nonylphenol (NP), a ubiquitously present surfactant in aquatic environments, on the anti-oxidant systems of the liver in the Far Eastern catfish Silurus asotus. Methods Changes in biochemical parameters involved in glutathione (GSH)-related and other anti-oxidant systems were analyzed following 4 weeks of 4-NP administration (0.1 and 1.0 mg/kg diet) via a formulated diet to catfish. Results 4-NP exposure induced an elevation in hepatic lipid peroxide levels and an accompanying decrease in reduced state GSH after 2 weeks, suggesting pro-oxidant effects of the chemical in catfish. This oxidative stress was associated with an inhibition of the GSH-utilizing enzyme glutathione peroxidase at the same time point. This inhibition was restored after 4 weeks. The activities of other anti-oxidant enzymes, i.e., glutathione reductase, superoxide dismutase and catalase were increased after 4 weeks. These enzyme increases occurred more strongly at the higher 4-NP concentration (1.0 mg/kg diet). Conclusions 4-NP given to catfish at 0.1 to 1.0 mg/kg diet, concentrations relevant to environmental levels, depletes the endogenous anti-oxidant molecule GSH and temporarily inhibits GSH-related anti-oxidant enzymes. Such declines in anti-oxidant capacity and elevated oxidative stress seem to be compensated eventually by subsequent activation of various anti-oxidant enzyme systems. PMID:26602557

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Urban streams are an integral part of the municipal wastewater treatment process by providing a point of discharge for wastewater treatment plant (WWTP) effluents and additional attenuation through dilution and transformation processes. The receiving surface waters also are a conduit for contaminan...

  18. Changes of concentrations and possibility of accumulation of bisphenol A and alkylphenols, depending on biomass and composition, in zooplankton of the Southern Baltic (Gulf of Gdansk).

    PubMed

    Staniszewska, Marta; Nehring, Iga; Mudrak-Cegiołka, Stella

    2016-06-01

    The focus of the present study was to find the relationship between concentrations of bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in zooplankton and seasonal changes in the composition and biomass of particular zooplankton taxa in the Gulf of Gdansk (Southern Baltic) in the years 2011-2012. Assays of BPA, OP and NP in water and zooplankton samples were performed using the HPLC/FL system. High mean concentrations of the studied compounds, determined in spring (405.9 (BPA); 25.7 (OP); 111.2 (NP) ng g(-1) dw), can be linked to the high proportion of meroplankton in that season. Rotifera also had an influence on the rise in concentrations of the studied compounds but to a lesser degree, while the lowest concentrations (determined in summer) can be associated with the high participation of Copepoda and Cladocera in zooplankton biomass. It was also observed that juvenile forms can be more susceptible to accumulating endocrine disrupting compounds (EDCs). This is indicated by the positive correlation between BPA concentration in zooplankton and the proportion of Copepoda nauplii biomass in spring (r = 0.90; p < 0.05). In most cases, greater zooplankton biomass accumulated higher concentrations and loads of the studied compounds. With biomass growth (to 123.32 μg m(-3)), the bioconcentration factor also rose (to max 46.1·10(3)), demonstrating that unlike typical hydrophobic compounds the studied EDCs do not become "diluted" in zooplankton biomass. The highest BPA concentrations from all compounds may be connected with anthropogenic sources located in the coastal zone.

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

    EPA Science Inventory

    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 fo...

  20. Reproductive responses of male fathead minnows exposed to wastewater treatment plant effluent, effluent treated with XAD8 resin, and an environmentally relevant mixture of alkylphenol compounds

    USGS Publications Warehouse

    Barber, L.B.; Lee, K.E.; Swackhamer, D.L.; Schoenfuss, H.L.

    2007-01-01

    On-site, continuous-flow experiments were conducted during August and October 2002 at a major metropolitan wastewater treatment plant (WWTP) to determine if effluent exposure induced endocrine disruption as manifested in the reproductive competence of sexually mature male fathead minnows (Pimephales promelas). The fathead minnows were exposed in parallel experiments to WWTP effluent and WWTP effluent treated with XAD8 macroreticular resin to remove the hydrophobic-neutral fraction which contained steroidal hormones, alkylphenolethoxylates (APEs), and other potential endocrine disrupting compounds (EDCs). The effluent composition varied on a temporal scale and the continuous-flow experiments captured the range of chemical variability that occurred during normal WWTP operations. Exposure to WWTP effluent resulted in vitellogenin induction in male fathead minnows, with greater response in October than in August. Concentrations of ammonia, APEs, 17??-estradiol, and other EDCs also were greater in October than in August, reflecting a change in effluent composition. In the October experiment, XAD8 treatment significantly reduced vitellogenin induction in the male fathead minnows relative to the untreated effluent, whereas in August, XAD8 treatment had little effect. During both experiments, XAD8 treatment removed greater than 90% of the APEs. Exposure of fish to a mixture of APEs similar in composition and concentration to the WWTP effluent, but prepared in groundwater and conducted at a separate facility, elicited vitellogenin induction during both experiments. There was a positive relation between vitellogenin induction and hepatosomatic index (HSI), but not gonadosomatic index (GSI), secondary sexual characteristics index (SSCI), or reproductive competency. In contrast to expectations, the GSI and SSCI increased in males exposed to WWTP effluent compared to groundwater controls. The GSI, SSCI, and reproductive competency were positively affected by XAD8 treatment of the WWTP effluent. ?? 2007 Elsevier B.V. All rights reserved.

  1. Chemosystematics in the Opiliones (Arachnida): a comment on the evolutionary history of alkylphenols and benzoquinones in the scent gland secretions of Laniatores.

    PubMed

    Raspotnig, Günther; Bodner, Michaela; Schäffer, Sylvia; Koblmüller, Stephan; Schönhofer, Axel; Karaman, Ivo

    2015-04-01

    Large prosomal scent glands constitute a major synapomorphic character of the arachnid order Opiliones. These glands produce a variety of chemicals very specific to opilionid taxa of different taxonomic levels, and thus represent a model system to investigate the evolutionary traits in exocrine secretion chemistry across a phylogenetically old group of animals. The chemically best-studied opilionid group is certainly Laniatores, and currently available chemical data allow first hypotheses linking the phylogeny of this group to the evolution of major chemical classes of secretion chemistry. Such hypotheses are essential to decide upon a best-fitting explanation of the distribution of scent-gland secretion compounds across extant laniatorean taxa, and hence represent a key toward a well-founded opilionid chemosystematics.

  2. 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

    SciTech Connect

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

    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-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 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.

  3. 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.

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

    USGS Publications Warehouse

    Bradley, Paul M.; Journey, Celeste; 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. 

  5. The Impact of 4-Nonylphenol on the Viability and Hormone Production of Mouse Leydig Cells.

    PubMed

    Jambor, T; Lukáčová, J; Tvrdá, E; Kňažická, Z; Forgács, Z; Lukáč, N

    2016-01-01

    Exogenous substances altering the function of the endocrine system and exhibiting adverse health effects on the organism are defined as endocrine disruptors. Nonylphenol is one of the most abundant alkylphenol ethoxylate derivatives, being detected in food products. Diverse studies have classified nonylphenol as hazardous to the health, especially to male reproduction. This in vitro study aimed to examine the effects of 4-nonylphenol on androstenedione and testosterone production as well as on the viability of Leydig cells of NMRI mice. The cells were cultured for 44 h with addition of 0.04; 0.2; 1.0; 2.5 and 5.0 μg/ml of 4-nonylphenol and compared to the control. Quantification of testosterone and androstenedione directly from aliquots of the medium was performed by enzyme-linked immunosorbent assay. Cell viability was measured by the metabolic activity assay for mitochondrial functional activity. Androstenedione production significantly (P < 0.001) increased with 1.0; 2.5 and 5.0 μg/ml 4-nonylphenol. Although cAMP-stimulated testosterone production was not significantly affected by 4-nonylphenol, a tendency to attenuate the level of testosterone in the Leydig cells treated with 2.5 and 5.0 μg/ml 4-nonylphenol was observed. The viability of mouse Leydig cells was slightly increased at the lowest doses of 4-nonylphenol (0.04 and 0.2 μg/ml). We also observed an increase at higher concentrations of the substance (1.0; 2.5 and 5.0 μg/ml), but this increase was not significant. Further investigations are required to establish the biological significance and possible reproductive implications.

  6. 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).

  7. Occurrence of eight household micropollutants in urban wastewater and their fate in a wastewater treatment plant. Statistical evaluation.

    PubMed

    Pasquini, Laure; Munoz, Jean-François; Pons, Marie-Noëlle; Yvon, Jacques; Dauchy, Xavier; France, Xavier; Le, Nang Dinh; France-Lanord, Christian; Görner, Tatiana

    2014-05-15

    The occurrence in urban wastewater of eight micropollutants (erythromycin, ibuprofen, 4-nonylphenol (4-NP), ofloxacin, sucralose, triclosan, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS)) originating from household activities and their fate in a biological wastewater treatment plant (WWTP) were investigated. Their concentrations were assessed in the liquid and solid phases (sewage particulate matter and wasted activated sludge (WAS)) by liquid chromatography-tandem mass spectrometry. The analysis of sewage from two different urban catchments connected to the WWTP showed a specific use of ofloxacin in the mixed catchment due to the presence of a hospital, and higher concentrations of sucralose in the residential area. The WWTP process removed over 90% of ibuprofen and triclosan from wastewater, while only 25% of ofloxacin was eliminated. Erythromycin, sucralose and PFOA were not removed from wastewater, the influent and effluent concentrations remaining at about 0.7 μg/L, 3 μg/L and 10 ng/L respectively. The behavior of PFOS and 4-nonylphenol was singular, as concentrations were higher at the WWTP outlet than at its inlet. This was probably related to the degradation of some of their precursors (such as alkylphenol ethoxylates and polyfluorinated compounds resulting in 4-NP and PFOS, respectively) during biological treatment. 4-NP, ofloxacin, triclosan and perfluorinated compounds were found adsorbed on WAS (from 5 ng/kg for PFOA to 1.0mg/kg for triclosan). The statistical methods (principal component analysis and multiple linear regressions) were applied to examine relationships among the concentrations of micropollutants and macropollutants (COD, ammonium, turbidity) entering and leaving the WWTP. A strong relationship with ammonium indicated that some micropollutants enter wastewater via human urine. A statistical analysis of WWTP operation gave a model for estimating micropollutant output from the WWTP based on a measurement of

  8. 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.

  9. Steroid estrogens, nonylphenol ethoxylate metabolites, and other wastewater contaminants in groundwater affected by a residential septic system on cape cod, MA

    USGS Publications Warehouse

    Swartz, C.H.; Reddy, S.; Benotti, M.J.; Yin, H.; Barber, L.B.; Brownawell, Bruce J.; Rudel, R.A.

    2006-01-01

    Septic systems serve approximately 25% of U.S. households and may be an important source of estrogenic and other organic wastewater contaminants (OWC) to groundwater. We monitored several estrogenic OWC, including nonylphenol (NP), nonylphenol mono- and diethoxycarboxylates (NP1EC and NP2EC), the steroid hormones 17??-estradiol (E2), estrone (E1) and their glucuronide and sulfate conjugates, and other OWC such as methylene blue active substances (MBAS), caffeine and its degradation product paraxanthine, and two fluorescent whitening agents in a residential septic system and in downgradient groundwater. E1 and E2 were present predominantly as free estrogens in groundwater, and near-source groundwater concentrations of all OWC were highest in the suboxic to anoxic portion of the wastewater plume, where concentrations of most OWC were similar to those observed in the septic tank on the same day. NP and NP2EC were up to 6- to 30-fold higher, and caffeine and paraxanthine were each 60-fold lower than septic tank concentrations, suggesting net production and removal, respectively, of these constituents. At the most shallow, oxic depth, concentrations of all OWC except for NP2EC were substantially lower than in the tank and in deeper wells. Yet boron, specific conductance, and the sum of nitrate-and ammonia-nitrogen were highest at this shallow depth, suggesting preferential losses of OWC along the more oxic flow lines. As far as 6.0 m downgradient, concentrations of many OWC were within a factor of 2 of near-source concentrations. The results suggest that there is the potential for migration of these OWC, which are unregulated and not routinely monitored, in groundwater. ?? 2006 American Chemical Society.

  10. 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...

  11. Microextraction with polyethersulfone for bisphenol-A, alkylphenols and hormones determination in water samples by means of gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry analysis.

    PubMed

    Ros, O; Vallejo, A; Blanco-Zubiaguirre, L; Olivares, M; Delgado, A; Etxebarria, N; Prieto, A

    2015-03-01

    In the present work, the suitability of polyethersulfone (PES) tube was assessed for the simultaneous sorptive microextraction of commonly found endocrine disrupting compounds in natural waters such as bisphenol-A (BPA), nonylphenol technical mixture (NP mix), 4-tert-octylphenol (4tOP), 4-n-octylphenol (4-nOP), 17β-estradiol (E2) and 17α-ethynilestradiol (EE2). After the concentration of target compounds in the PES polymer, the analytes were recovered soaking the polymer with a suitable solvent (ethyl acetate or methanol), derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane (BSTFA+1% TMCS) and determined by gas chromatography-mass spectrometry (GC-MS). The analysis was also performed without derivatization step by means of liquid chromatography-tandem mass spectrometry (LC-MS/MS). Extraction parameters (addition of MeOH, ionic strength, extraction speed and time and desorption time) were evaluated and the optimum conditions were fixed as follows: 150 mL water samples containing a 10% (w/v) of sodium chloride and using 5 tubular PES sorbent fibers (1.5 cm length×0.7 mm o.d.). Equilibrium conditions were achieved after 9 h, with absolute extraction efficiencies ranging from 27 to 56%. On the whole, good apparent recoveries were achieved (68-103% and 81-122% for GC-MS and LC-MS/MS, respectively) using deuterated analogues as surrogates. Achieved quantification limits (LOQs) varied between 2-154 ng/L and 2-63 ng/L for all the compounds using GC-MS and LC-MS/MS, respectively. The effect of organic matter was evaluated previous to apply the final method to the analysis of estuarine and wastewater real samples. The comparison of both methods showed that overall, PES-LC-MS/MS provided shorter sample preparation time and better LODs, but PES-silylation-GC-MS allowed the simultaneous determination of all the studied compounds with adequate repeatability and accuracy.

  12. Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations, sampling season and location.

    PubMed

    Hamers, Timo; van den Brink, Paul J; Mos, Lizzy; van der Linden, Sander C; Legler, Juliette; Koeman, Jan H; Murk, Albertinka J

    2003-01-01

    any particular pesticides. Besides, the contribution of non-analyzed xeno-estrogens as alkylphenol(-ethoxylates) and bisphenol-A to the estrogenic potency of rainwater could not be excluded. Further research should focus on the chemical identification of estrogenic compounds in rainwater. In addition, more attention should be given to the ecological consequences of atmospheric deposition of individual pesticides and of total toxic potencies that regularly exceed environmental criteria for Dutch surface waters and/or toxic threshold values for aquatic organisms.

  13. 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

  14. 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

  15. Capillary electrochromatography-mass spectrometry of nonionic surfactants.

    PubMed

    Norton, Dean; Shamsi, Shahab A

    2007-12-15

    The Triton X (TX)-series are alkylphenol polyethoxylates -type nonionic surfactants of varying numbers of ethylene oxide units. Applications include industrial and household detergent formulations as well as emulsifying agents. For analysis of these surfactants, capillary electrochromatography-electrospray ionization-mass spectrometry (CEC-ESI-MS) offers several unique advantages over the traditional hyphenation methods based on HPLC-MS. These include higher plate numbers attainable in CEC-MS, as well as more compatible flow rate (submicroliter) when coupled to ESI-MS and, perhaps most importantly, less consumption of toxic and costly organic solvents. In this work, different CEC-ESI-MS parameters such as mobile-phase composition, sheath liquid, and spray chamber parameters were optimized to provide suitable and sensitive analysis of short-, medium-, and long-chain length (e.g., n = 1-16) TX-series nonionic surfactants. The optimized CEC-ESI-MS conditions were mobile phase containing 90/10 ACN/2.5 mM Tris, pH 8, sheath liquid containing 50/50 MeOH/10 mM HCO(2)NH(4) delivered at 5 microL/min, spray chamber set to drying gas flow of 6 mL/min, nebulizer pressure of 5 psi, and drying gas temperature set to 200 degrees C. This optimization is followed by the more challenging separation of very long chain TX-series with a large number (n = 30-70) of ethoxy units, which were initially found to exhibit extreme retention using the developed method. It was observed that through the addition of small volume fraction of polar-aprotic tetrahydrofuran solvent to the running buffer, the retention time could be significantly reduced thus enhancing the feasibility for CEC-ESI-MS analysis of these very long chain nonionic surfactants for the first time. The detection limit was approximately 37 microg/mL total octylphenol ethoxylate for TX-45; acceptable precision of migration time (<1% RSD, n = 3) and peak area ( approximately 4% RSD, n = 3) were achieved.

  16. Aquatic hazard assessment of MON 0818, a commercial mixture of alkylamine ethoxylates commonly used in glyphosate-containing herbicide formulations. Part 1: Species sensitivity distribution from laboratory acute exposures.

    PubMed

    Rodriguez-Gil, Jose L; Prosser, Ryan; Poirier, David; Lissemore, Linda; Thompson, Dean; Hanson, Mark; Solomon, Keith R

    2017-02-01

    The sensitivity of 15 aquatic species, including primary producers, benthic invertebrates, cladocerans, mollusks, and fish, to MON 0818, a commercial surfactant mixture of polyoxyethylene tallow amines, was evaluated in standard acute (48-96-h) laboratory tests. In addition, the potential for chronic toxicity (8 d) was evaluated with Ceriodaphnia dubia. Exposure concentrations were confirmed. No significant effects on any endpoint were observed in the chronic test. A tier-1 hazard assessment was conducted by comparing species sensitivity distributions based on the generated data, as well as literature data, with 4 exposure scenarios. This assessment showed moderate levels of hazard (43.1% of the species exposed at or above median effective concentration levels), for a chosen worst-case scenario-unintentional direct over-spray of a 15-cm-deep body of water with the maximum label application rate for the studied formulations (Roundup Original, Vision Forestry Herbicide; 12 L formulation ha(-1) , equivalent to 4.27 kg acid equivalent [a.e.] ha(-1) ). The hazard decreased to impairment of 20.9% of species under the maximum application rate for more typical uses (6 L formulation ha(-1) , 2.14 kg a.e. ha(-1) ), and down to 6.9% for a more frequently employed application rate (2.5 L formulation ha(-1) , 0.89 kg a.e. ha(-1) ). Finally, the percentage (3.8%) was less than the hazardous concentration for 5% of the species based on concentrations of MON 0818 calculated from maximum measured concentrations of glyphosate in the environment. Environ Toxicol Chem 2017;36:501-511. © 2016 SETAC.

  17. Aquatic hazard assessment of MON 0818, a commercial mixture of alkylamine ethoxylates commonly used in glyphosate-containing herbicide formulations. Part 2: Roles of sediment, temperature, and capacity for recovery following a pulsed exposure.

    PubMed

    Rodriguez-Gil, Jose L; Prosser, Ryan; Hanta, Gregory; Poirier, David; Lissemore, Linda; Hanson, Mark; Solomon, Keith R

    2017-02-01

    A series of toxicity tests with MON 0818, a commercial surfactant mixture of polyoxyethylene tallow amines, were performed: 1) in the presence of sediment for benthic invertebrates and fish: 2) to examine the recovery capacity of Daphnia magna and 4 primary producers after a pulsed (24-h) exposure; and 3) to examine the potential effect of increased water temperature on toxicity of MON 0818 to 2 cold-water fishes. In the presence of sediment, no acute (24-h) mortality was observed for 3 of the 5 species up to 10 mg L(-1) . The median effective concentrations for the other 2 species were significantly greater than for water only tests. The EC50 at 15 °C for Salvelinus alpinus was statistically lower than that at 10 °C. Latent effects of a 24-h exposure (1 mg L(-1) ) were observed for Rhabdocelis subcapitata and Chlorella vulgaris, as indicated by delayed growth during recovery phase; however, both cultures were able to recover, as indicated by a lack of changes in maximum absolute growth rates. No significant effects of a 24-h exposure to MON 0818 were observed for Oophila sp. (1.5 mg L(-1) ) or Lemna minor (100 mg L(-1) ). Latent mortality after a 24-h exposure to 5 mg L(-1) was observed during the recovery phase for D. magna; however, reproduction endpoints on surviving individuals were not altered. The results indicate that quick dissipation of MON 0818 in the presence of sediment can reduce the effects on exposed organisms, and that full recovery from 24-h exposures to concentrations of MON 0818 equal to, or greater than, those expected in the environment is possible. Environ Toxicol Chem 2017;36:512-521. © 2016 SETAC.

  18. Modified-Atmospheric Pressure-Matrix Assisted Laser Desorption/Ionization Identification of Friction Modifier Additives Oleamide and Ethoxylated Tallow Amines on Varied Metal Target Materials and Tribologically Stressed Steel Surfaces.

    PubMed

    Widder, Lukas; Ristic, Andjelka; Brenner, Florian; Brenner, Josef; Hutter, Herbert

    2015-11-17

    For many tasks in failure and damage analysis of surfaces deteriorated in heavy tribological contact, the detailed characterization of used lubricants and their additives is essential. The objective of the presented work is to establish accessibility of tribostressed surfaces for direct characterization via modified atmospheric pressure-matrix assisted laser desorption/ionization-mass spectrometry (m-AP-MALDI-MS). Special target holders were constructed to allow target samples of differing shape and form to fit into the desorption/ionization chamber. The best results of desorption and ionization on different target materials and varying roughnesses were achieved on smooth surfaces with low matrix/substrate interaction. M-AP-MALDI characterization of tribologically stressed steel surfaces after pin-on-disc sliding wear tests (SRV-tribotests) yielded positive identification of used friction modifier additives. Further structure elucidation by electrospray ionization mass spectrometry (ESI-MS) and measurements of worn surfaces by time-of-flight-secondary ion mass spectrometry (TOF-SIMS) accompanied findings about additive behavior and deterioration during tribological contact. Using m-AP-MALDI for direct offline examinations of worn surfaces may set up a quick method for determination of additives used for lubrication and general characterization of a tribological system.

  19. 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

  20. 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

  1. 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.

  2. Methods for degrading lignocellulosic materials

    DOEpatents

    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 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.

  3. Methods for degrading lignocellulosic materials

    DOEpatents

    Vlasenko, Elena; Cherry, Joel; Xu, Feng

    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.

  4. 75 FR 5405 - Sixty-Fifth Report of the TSCA Interagency Testing Committee to the Administrator of the...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-02

    ... alkylphenols, 12 lead compounds, 16 chemicals with insufficient dermal absorption rate data, and 207 HPV... Volume (HPV) Challenge Program orphan chemicals 56 August 2005 4 HPV Challenge Program Recommended...

  5. p-Nonyl-phenol: an estrogenic xenobiotic released from "modified" polystyrene.

    PubMed Central

    Soto, A M; Justicia, H; Wray, J W; Sonnenschein, C

    1991-01-01

    Alkylphenols are widely used as plastic additives and surfactants. We report the identification of an alkylphenol, nonylphenol, as an estrogenic substance released from plastic centrifuge tubes. This compound was extracted with methanol, purified by flash chromatography and reverse-phase high performance liquid chromatography, and identified by gas chromatography-mass spectrometry. Nonylphenol induced both cell proliferation and progesterone receptor in human estrogen-sensitive MCF7 breast tumor cells. Nonylphenol also triggered mitotic activity in rat endometrium; this result confirms the reliability of the MCF7 cell proliferation bioassay. The estrogenic properties of alkylphenols, specifically nonylphenols, indicate that the use of plasticware containing these chemicals in experimental and diagnostic tests may lead to spurious results, and these compounds as well as alkylphenol polyethoxylates may also be potentially harmful to exposed humans and the environment at large. PMID:1935846

  6. Tree nut phytochemicals: composition, antioxidant capacity, bioactivity, impact factors. A systematic review of almonds, Brazils, cashews, hazelnuts, macadamias, pecans, pine nuts, pistachios and walnuts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  7. 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...

  8. 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

  9. Mechanism for biotransformation of nonylphenol polyethoxylates to Xenoestrogens in Pseudomonas putida.

    PubMed

    John, D M; White, G F

    1998-09-01

    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.

  10. Surfactant-Enhanced In Situ Soils Washing

    DTIC Science & Technology

    1987-09-01

    technology . Several shortfa-- were observed and have been documented in this report. The report also contains. information on the operation of a groundwater...is 5.5 to 6.0. Atomic absorbtion analysis indicated dissolved iron levels as high as 24 mg/L in areas of high organic contamination. This iron...percent surfactant, consisting of a 50/50 mix of an ethoxylated alkyl phenol and ethoxylated fatty acid were passed through each column. Leachates from

  11. Robotic System Joint Project Office (RSJPO) Interoperability Profiles

    DTIC Science & Technology

    2011-08-25

    domains • Payloads, sensors , software & computing devices anticipated to evolve much faster than base platforms • User requirements calling for...NASA • CERDEC • NAVEODTECHDIV • PEO GCS APEO SE • TRADOC ARCIC •MSCOE • PEO U&W (Navy) • TCM UAS • USASOC • AMRDEC • AFRL • JIEDDO • Sandia National... Labs • OSD Unclassified R O B O T IC S Y S T E M S J P O L e a d e r s h i p • S e r v i c e • I n n o v a t i o n For Official Use Only For

  12. Assessing the aquatic hazard of some branched and linear nonionic surfactants by biodegradation and toxicity

    SciTech Connect

    Dorn, P.B.; Salanitro, J.P.; Evans, S.H.; Kravetz, L. . Westhollow Research Center)

    1993-10-01

    An aquatic hazard assessment was conducted for branched and linear nonionic surfactants using toxicity and biodegradation measurements. Four nonionic alcohol ethoxylate surfactants with different degrees of branching were evaluated for neat surfactant toxicity, degradation in laboratory sewage treatment units, and aquatic toxicity of treated effluents. Acute testing with neat surfactants showed ranges for EC50s of 1.3 to 11.6 mg/L for Daphnia, 1.6 to 6.1 mg/L for Pimephales promelas (fathead minnow), and 1.5 to 11.4 mg/L for Microtox[reg sign]. Chronic testing of algae showed NOECs of 1 to 10 mg/L and maximum acceptable toxicant concentrations (MATCs) of 0.8 to 14.2 mg/L. Seven-day chronic estimation tests showed MATCs of 0.6 to 41.4 mg/L for Pimephales promelas and 1 to 14 mg/L for Daphnia. Effluents collected from treatment units receiving a 50-mg/L surfactant feed at 25 C showed no acute toxicity to either Daphnia or fathead minnows, with the exception of a unit containing nonylphenol ethoxylate. Chronic effluent toxicity was greatest in effluent from the nonylphenol ethoxylate unit and least in the effluent from the linear alcohol ethoxylate unit. Chronic toxicity of the highly branched C[sub 13] alcohol ethoxylate effluent was greater than that for the linear alcohol ethoxylate unit effluent.

  13. 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.

  14. Role of ion-pair interactions on asphaltene stabilization by alkylbenzenesulfonic acids.

    PubMed

    Goual, Lamia; Sedghi, Mohammad

    2015-02-15

    The dispersion of asphaltenes by dodecylbenzenesulfonic acid (DBSA) has been the subject of several studies in the past. However, it is unclear how these interactions affect the structure of asphaltenes and why asphaltene aggregates are larger in the presence of ionic DBSA. The main goal of this study was to address these points using a combination of high-resolution transmission electron microscopy (HRTEM) and molecular dynamics (MD) simulations. Another objective was to compare ionic DBSA (i.e., dodecylbenzenesulfonate or DBS(-)) to nonionic amphiphiles such as alkylphenols. A striking similarity between dodecylbenzenesulfonate and alkylphenols was that both favored the formation of filamentary rather than globular asphaltene flocculates. However the mechanism by which those filaments formed was very different. Two strong electrostatic interactions between DBSA and asphaltenes were found: (i) those between protonated asphaltenes (i.e., AH(+)) and DBS(-) molecules, which were fifteen times stronger than asphaltene-alkylphenol interactions, and (ii) those between two asphaltene-dispersant pairs (i.e., AH(+)-DBS(-) ion pairs), which did not exist with alkylphenols. These interactions promoted the formation of large and compact asphaltene flocculates, as compared to small and loose ones formed without DBSA. Flocculates with DBSA could further bind to each other through ion-pair interactions. The binding occurred in series (generating long filaments) or in parallel (generating lateral ramifications). However the series configuration was energetically favored due to less steric effects generated by the side aliphatic chains of asphaltenes and DBSA.

  15. 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...

  16. METHOD OF OBTAINING AN ADDITIVE FOR LUBRICATING OILS,

    DTIC Science & Technology

    The method of obtaining an additive to lubricating oils , consisting of treating boron trifluoride with alkylphenol and alkylamine, is known. In this...case, (aminotrifluoralkyl)phenoxyborate is obtained which may be used as an antiwear additive for lubricating oils . The proposed method differs from

  17. 77 FR 75349 - Seventy-First Report of the TSCA Interagency Testing Committee to the Administrator of the...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-19

    ... revising the TSCA section 4(e) Priority Testing List by removing 16 High Production Volume (HPV) Challenge... 16 HPV Challenge Program orphan chemicals. B. Status of the Priority Testing List The Priority Testing List includes 16 chemicals with insufficient dermal absorption rate data, 2 alkylphenols, 148...

  18. Mixed surfactant systems for enhanced oil recovery

    SciTech Connect

    Llave, F.M.; Gall, B.L.; Noll, L.A.

    1990-12-01

    The results of an evaluation of mixed surfactant systems for enhanced oil recovery are described. Several surfactant combinations have been studied. These include alkyl aryl sulfonates as primary surfactants and carboxymethylated ethoxylated (CME) surfactants and ethoxylated sulfonates (ES) as secondary surfactants. The ethoxylated surfactants increase the salinity tolerance of the primary surfactants and, in theory, allow tailoring of the surfactant system to match selected reservoir conditions. The experiments conducted included interfacial tension (IFT) measurements, phase behavior measurements, adsorption and/or chromatographic separation of mixed surfactant systems, measurements of solution properties such as the critical micelle concentration (CMC) of surfactant mixtures, and crude oil displacement experiments. The effects of temperature, surfactant concentration, salinity, presence of divalent ions, hydrocarbon type, and component proportions in the mixed surfactant combinations, and injection strategies on the performance potential of the targeted surfactant/hydrocarbon systems were studied. 40 refs., 37 figs., 8 tabs.

  19. 75 FR 6795 - Designation of Biobased Items for Federal Procurement

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-10

    ... availability. USDA recognizes that the performance needs for a given application are important criteria in... phenol ethoxylates, ethylene glycol ethers, and volatile organic compounds. In addition, both require...Preferred Web site. Exemptions. Products used in spacecraft systems and launch support applications...

  20. 76 FR 43327 - Certain New Chemicals; Receipt and Status Information

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-20

    .../2011 CBI (G) Base oil (G) Fatty acid for lubricant. esters. P-11-0404 5/26/2011 8/23/2011 Matteson.../2011 CBI (G) Additive, (G) Reaction product open, non- of ethoxylated dispersive use. alcohol and... 5/16/2011 (G) Fluorochemical acrylate copolymer. P-10-0592 5/23/2011 5/20/2011 (G) Fatty...

  1. 21 CFR 178.3570 - Lubricants with incidental food contact.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... the alkyl groups are derived from hydrogenated tallow fatty acids (C14-C18) and where the aluminum... formaldehyde and subsequent ethoxylation with 4 to 12 moles of ethylene oxide; and 3. n-Tridecyl alcohol... Reg. No. 56831-62-0) Fatty acids derived from animal or vegetable sources, and the hydrogenated...

  2. 21 CFR 178.3570 - Lubricants with incidental food contact.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... the alkyl groups are derived from hydrogenated tallow fatty acids (C14-C18) and where the aluminum... formaldehyde and subsequent ethoxylation with 4 to 12 moles of ethylene oxide; and 3. n-Tridecyl alcohol... Reg. No. 56831-62-0) Fatty acids derived from animal or vegetable sources, and the hydrogenated...

  3. 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

    ... hydrocarbons; surfactants such as polyoxyethylene polymers and fatty acids; carriers such as clay and.... and children). Chronic dietary NOAEL= 10 mg/kg/day UFA Chronic RfD = 0.1 mg/kg/ 2-Generation (All... exposure models in the dietary exposure analysis and risk assessment for octylphenol ethoxylate....

  4. 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...

  5. 21 CFR 177.1400 - Hydroxyethyl cellulose film, water-insoluble.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false 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...

  6. 21 CFR 177.1400 - Hydroxyethyl cellulose film, water-insoluble.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false 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...

  7. 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...

  8. 21 CFR 177.1400 - Hydroxyethyl cellulose film, water-insoluble.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false 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...

  9. 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.

  10. 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

  11. Purification and characterization of vanillyl-alcohol oxidase from Byssochlamys fulva V107.

    PubMed

    Furukawa, H; Wieser, M; Morita, H; Sugio, T; Nagasawa, T

    1999-01-01

    Vanillyl-alcohol oxidase from Byssochlamys fulva V107 was purified to apparent homogeneity as shown by SDS-PAGE and gel-permeation HPLC. The enzyme is a homodimeric flavoenzyme consisting of two 58 kDa subunits. It catalyzes the dehydrogenation of different 4-hydroxybenzylic structures, including the conversion of 4-hydroxybenzyl alcohols such as vanillyl alcohol to the corresponding aldehydes, eugenol to coniferyl alcohol, and 4-alkylphenols to 1-(4-hydroxyphenyl)alcohols. The latter reaction was S-stereospecific and was used for the synthesis of S-1-(4-hydroxyphenyl)ethanol and -propanol with enantiomeric excesses of 81.9 and 86.0%, respectively. The catalytic and structural similarities to a Penicillium vanillyl-alcohol oxidase and Pseudomonas 4-alkylphenol methylhydroxylases are discussed.

  12. 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

  13. High performance solid-phase analytical derivatization of phenols for gas chromatography-mass spectrometry.

    PubMed

    Kojima, Miki; Tsunoi, Shinji; Tanaka, Minoru

    2004-07-09

    The solid-phase analytical derivatization of phenols with pentafluoropyridine is performed. Fourteen phenols including chlorophenols and alkylphenols, could be efficiently adsorbed on a strong anion-exchange solid phase, Oasis MAX. The phenols adsorbed on Oasis MAX as phenolate ions were desorbed after derivatization with pentafluoropyridine. After optimization of the adsorption and derivatization, we established a procedure for the determination of the phenols in water samples by means of GC-MS. Under the optimized conditions, calibration curves were linear in the range of 10-1000 ng/l for the alkylphenols (100-10000 ng/l for nonylphenol) and 50-1000 ng/l for the others. By processing 100 ml samples, the method detection limits (MDLs) were in the range of 0.45-2.3 ng/l for the alkylphenols (8.5 ng/l for nonylphenol) and 2.4-16 ng/l for the others. Compared with the biphasic reaction system, the signal-to-noise ratios obtained by the solid-phase analytical derivatization were significantly higher. This is ascribed to the fact that coexisting neutral and acidic compounds are efficiently removed from the sample solution by this solid-phase analytical derivatization system.

  14. Phase behavior and oil recovery investigations using mixed and alkaline-enhanced surfactant systems

    SciTech Connect

    Llave, F.M.; Gall, B.L.; French, T.R.; Noll, L.A.; Munden, S.A.

    1992-03-01

    The results of an evaluation of different mixed surfactant and alkaline-enhanced surfactant systems for enhanced oil recovery are described. Several mixed surfactant systems have been studies to evaluate their oil recovery potential as well as improved adaptability to different ranges of salinity, divalent ion concentrations, and temperature. Several combinations of screening methods were used to help identify potential chemical formulations and determine conditions where particular chemical systems can be applied. The effects of different parameters on the behavior of the overall surfactant system were also studied. Several commercially available surfactants were tested as primary components in the mixtures used in the study. These surfactants were formulated with different secondary as well as tertiary components, including ethoxylated and non-ethoxylated sulfonates and sulfates. Improved salinity and hardness tolerance was achieved for some of these chemical systems. The salinity tolerance of these systems were found to be dependent on the molecular weight, surfactant type, and concentration of the surfactant components.

  15. Degradation of polycyclic aromatic hydrocarbons in the presence of synthetic surfactants

    SciTech Connect

    Tiehm, A. )

    1994-01-01

    The biodegradation of polycyclic aromatic hydrocarbons (PAH) often is limited by low water solubility and dissolution rate. Nonionic surfactants and sodium dodecyl sulfate increased the concentration of PAH in the water phase because of solubilization. The degradation of PAH was inhibited by sodium dodecyl sulfate because this surfactant was preferred as a growth substrate. Growth of mixed cultures with phenanthrene and fluroanthrene solubilized by a nonionic surfactant prior to inoculation was exponential, indicating a high bioavailability of the solubilized hydrocarbons. Nonionic surfactants of the alkylethoxylate type and the alkylphenolethoxylate type with an average ethoxylate chain length of 9 to 12 monomers were toxic to a PAH-degrading Mycobacterium sp. and to several PAH-degrading mixed cultures. Toxicity of the surfactants decreased with increasing hydrophilicity, i.e., with increasing ethoxylate chain length. Nontoxic surfactants enhanced the degradation of fluorene, phenanthrene, anthracene, fluoranthene, and pyrene.

  16. Constituents with radical scavenging effect from Opuntia dillenii: structures of new alpha-pyrones and flavonol glycoside.

    PubMed

    Qiu, Yingkun; Chen, Yingjie; Pei, Yupin; Matsuda, Hisashi; Yoshikawa, Masayuki

    2002-11-01

    The aqueous ethanolic extract from the fresh stems of Opuntia dillenii HAW. showed potent radical scanvenging activity. Three new compounds, opuntioside I, 4-ethoxyl-6-hydroxymethyl-alpha-pyrone, and kaempferol 7-O-beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranoside, were isolated from the extract. The structures of the new compounds were determined on the basis of chemical and physicochemical evidence and the radical scavenging effects of principal constituents were examined.

  17. 46 CFR Table 1 to Part 153 - Summary of Minimum Requirements

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ..., .408, .525, .526, .527, .912(a)(2), .933, .1002, .1004, .1020, .1035 I-D Acetonitrile III S II B/3 PV...(7-12)ethoxylates B P III NR Open Open A .409, .440, .908(a), (b) NA Alcohol(C9-C11) poly(2.5-9... NSR .252, .526, .527, .554, .557, .933, .1045, .1052 I-B 2-(2-Aminoethoxy) ethanol D S III NR...

  18. 46 CFR Table 1 to Part 153 - Summary of Minimum Requirements

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ..., .408, .525, .526, .527, .912(a)(2), .933, .1002, .1004, .1020, .1035 I-D Acetonitrile III S II B/3 PV...(7-12)ethoxylates B P III NR Open Open A .409, .440, .908(a), (b) NA Alcohol(C9-C11) poly(2.5-9... NSR .252, .526, .527, .554, .557, .933, .1045, .1052 I-B 2-(2-Aminoethoxy) ethanol D S III NR...

  19. 46 CFR Table 1 to Part 153 - Summary of Minimum Requirements

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ..., .408, .525, .526, .527, .912(a)(2), .933, .1002, .1004, .1020, .1035 I-D Acetonitrile III S II B/3 PV...(7-12)ethoxylates B P III NR Open Open A .409, .440, .908(a), (b) NA Alcohol(C9-C11) poly(2.5-9... NSR .252, .526, .527, .554, .557, .933, .1045, .1052 I-B 2-(2-Aminoethoxy) ethanol D S III NR...

  20. 46 CFR Table 1 to Part 153 - Summary of Minimum Requirements

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ..., .408, .525, .526, .527, .912(a)(2), .933, .1002, .1004, .1020, .1035 I-D Acetonitrile III S II B/3 PV...(7-12)ethoxylates B P III NR Open Open A .409, .440, .908(a), (b) NA Alcohol(C9-C11) poly(2.5-9... NSR .252, .526, .527, .554, .557, .933, .1045, .1052 I-B 2-(2-Aminoethoxy) ethanol D S III NR...

  1. 46 CFR Table 1 to Part 153 - Summary of Minimum Requirements

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ..., .408, .525, .526, .527, .912(a)(2), .933, .1002, .1004, .1020, .1035 I-D Acetonitrile III S II B/3 PV...(7-12)ethoxylates B P III NR Open Open A .409, .440, .908(a), (b) NA Alcohol(C9-C11) poly(2.5-9... NSR .252, .526, .527, .554, .557, .933, .1045, .1052 I-B 2-(2-Aminoethoxy) ethanol D S III NR...

  2. 77 FR 13596 - Certain New Chemicals; Receipt and Status Information

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-07

    ... isocyanate and polyether glycol. P-12-0174 02/02/2012 05/01/2012 CBI (G) Rubber (G) Polyurethane. adhesive... 02/13/2012 05/12/2012 CBI (G) Open, non (G) Polyurethane dispersive use. dispersion. P-12-0180 02/13.../03/2012 01/05/2012 (G) Alkyl ethoxylate. P-10-0209 02/02/2012 01/05/2012 (G) Polyurethane resin....

  3. Environmentally Friendly Cleaners for Removing Tar from Metal Surfaces

    DTIC Science & Technology

    2009-04-01

    sions have lower viscosities than neat asphalts and can be used in low temperature applications. After applying the emulsion , the water evaporates...Derbyshire SK17 9RZ Tel : 01298 26226 sales@selden.co.uk Tar n’ Glue Remover 1,2,4-Trimethylbenzene, Alcohol Ethoxylate Anionic Detergent...sales@soysolv.com SOYsolve Industrial Strength Mixed fatty & methyl esters Linoleic, Oleic, Palmitic, Linolenic, Stearic, Palmitoleic Erui

  4. Preparation of Copper Nanoparticles in Liquid by Matrix Sputtering Process

    NASA Astrophysics Data System (ADS)

    Nakagawa, Ko; Narushima, Takashi; Udagawa, Satoshi; Yonezawa, Tetsu

    2013-03-01

    As a new method for nanoparticles preparation, magnetron sputtering of metal atoms and clusters into organic liquids has been intensively used recently. In this study, metallic copper nanoparticles dispersed in pentaerythritol ethoxylate were prepared by this process. Their size control was achieved by controlling the sputtering current. Specific absorption at ca. 580 nm was detected by UV-Vis measurement which is attributed to the specific plasmon absorption of metallic copper. TEM observation also revealed the formation of metallic nanoparticles.

  5. 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.

  6. Structures similar to lipid emulsions and liposomes. Dipalmitoylphosphatidylcholine, cholesterol, Tween 20-Span 20 or Tween 80-Span 80 in aqueous media.

    PubMed

    Juárez-Osornio, Carlos; Gracia-Fadrique, Jesús

    2017-06-01

    In the present work, we show that we obtained nanometric structures made of water, 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC), cholesterol (Chol), and a mixture of ethoxylated and non-ethoxylated sorbitan fatty acid esters (Tween 20, Span 20, Tween 80, and Span 80) by mixing all of them near the cloud point temperature (cp) of the ethoxylated surfactant. The influence that the constituents had on the size of the particle was determined by a pseudo-ternary phase diagram of water/Tween-Span/DPPC-Chol; the colloidal particles obtained were studied by differential scanning calorimetry, confocal fluorescence microscopy, scanning electron microscopy, and atomic force microscopy. These studies were made for all the systems with at least 23 d of colloidal stability. The most stable system was obtained with the Tween 80-Span 80 pair, behaving as a typical suspension for 48 d; this system was made of water, Tween 80-Span 80 (80:20), DPPC-Chol (95:5) in a corresponding molar ratio of 48:37:100:10. The colloidal particles obtained were a kind of emulsion and liposome structures. The second stable system was obtained with the same mixture, but in a molar ratio of 8:6:9:0, its structure was also a kind of emulsion particles. In both systems and in other less stable ones, the "emulsion particle" was completely new, it structurally corresponds to a nucleus of mixed micelles surrounded by at least one bilayer of DPPC.

  7. Rate-limited mass transfer of octane, decane, and dodecane into nonionic surfactants solutions under laminar flow conditions.

    PubMed

    Prak, Dianne J Luning

    2008-05-01

    A key component to predicting the success of utilizing surfactants to enhance the removal of organic liquids from soil system is quantifying micellar solubilization kinetics. In this study, a flow reactor was employed to investigate the influence of surfactant ethoxylate chain length on the rates of solubilization of octane, decane, and dodecane in micellar solutions of a homologous series of purified dodecyl alcohol ethoxylates. Effluent concentration data were fit using a finite element model utilizing a linear-driving-force model to represent mass transfer at the interface. For flow rates between 0.1 and 2 ml min(-1), mass transfer coefficients ranged from 5 x 10(-8) to 7 x 10(-7)m s(-1) and did not vary in a systematic way with either solute structure or surfactant ethoxylate chain length and were lower than those found in pure water. Correlations developed for the Sherwood number based on diffusion coefficients of surfactant micelles containing organic material (organic-laden micelle) exhibit a velocity dependence similar to that found for systems based on aqueous diffusion. These results suggest that under gentle flowing conditions, the mass transfer is limited by diffusion of the organic-laden micelle. Although these trends are specific for this experimental system, the results demonstrate the importance of selecting the proper diffusion coefficient when modeling surfactant solubilization processes.

  8. Occupation and occupational exposure to endocrine disrupting chemicals in male breast cancer: a case-control study in Europe

    PubMed Central

    Villeneuve, Sara; Cyr, Diane; Lynge, Elsebeth; Orsi, Laurent; Sabroe, Svend; Merletti, Franco; Gorini, Giuseppe; Morales-Suarez-Varela, Maria; Ahrens, Wolfgang; Baumgardt-Elms, Cornelia; Kaerlev, Linda; Eriksson, Mikael; Hardell, Lennart; Févotte, Joëlle; Guénel, Pascal

    2010-01-01

    Objectives Male breast cancer is a rare disease of largely unknown etiology. Besides genetic or hormone-related risk factors, a large number of environmental chemicals are suspected to play a role in breast cancer. The identification of occupations or occupational exposures associated with an increased incidence of breast cancer in men may help to identify mammary carcinogens in the environment. Methods Occupational risk factors of male breast cancer were investigated in a multi-centre case-control study conducted in 8 European countries, including 104 cases and 1901 controls. Lifetime work history was obtained during in-person interviews. Occupational exposures to endocrine disrupting chemicals (alkylphenolic compounds, phthalates, PCBs and dioxins) were assessed on a case-by-case basis from expert judgment. Results Male breast cancer incidence was more particularly increased in motor vehicle mechanics (OR=2.1, CI 1.0–4.4) with a dose-effect relationship with duration employment. It was also increased in paper makers and painters, and in workers in forestry and logging, health and social work, and manufacture of furniture. The odds ratio for exposure to alkylphenolic compounds above median was 3.8 (CI 1.5–9.5). This association persisted after adjustment for occupational exposures to other environmental estrogens. Conclusion These findings suggest that some environmental chemicals are possible mammary carcinogens. Gasoline, organic petroleum solvents or PAH can be suspected from the consistent elevated risk of male breast cancer observed in motor vehicle mechanics. Endocrine disruptors such as alkylphenolic compounds may play a role in breast cancer. PMID:20798010

  9. 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

  10. 6-alkylsalicylic acids and 6-alkylresorcylic acids from ants in the genus Crematogaster from Brunei.

    PubMed

    Jones, T H; Brunner, S R; Edwards, A A; Davidson, D W; Snelling, R R

    2005-02-01

    The defensive chemistry of two species of ants from Brunei in the genus Crematogaster (Physocrema group) has been investigated. Ants in this group release a white secretion from hypertrophied metapleural glands on their thorax when they are disturbed. Previously, one species in this group has been shown to produce alkylphenols and alkylresorcinols. In the present investigation, similar compounds along with salicylic acids and resorcylic acids that are anacardic acid and olivetolic acid homologs, respectively, are described from two species. The structures of these compounds were suggested by their spectroscopic data and confirmed by direct comparison with synthetic samples. Some of these compounds occur in lichens and have well documented physiological activities.

  11. Alkylation of phenol with polybutenes in the presence of benzenesulfonic acid

    SciTech Connect

    Belov, P.S.; Gulyaev, I.A.; Korenev, K.D.; Yakovlev, V.B.; Zakupra, V.A.

    1982-09-01

    The purpose of this work is to test benzenesulfonic acid (BSA) as a catalyst in the alkylation of phenol with polyisobutylene (PIB). This material is used as a catalyst in the production of technical C/sub 5/-C/sub 12/ tert-alkylphenol. Finds that the optimal compromise between acceleration of the reaction and the alkylate viscosity increase that limits the reaction rate is achieved at a temperature of about 105 C and a BSA/PIB mole ratio of 0.15. Recommends BSA as an effective replacement for boron fluoride, boron fluoride complexes, and other highly corrosive catalysts used in the alkylation of phenol with polybutenes.

  12. 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

  13. 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

  14. Defensive secretions of the carabid beetle Chlaenius cordicollis: chemical components and their geographic patterns of variation.

    PubMed

    Holliday, A E; Holliday, N J; Mattingly, T M; Naccarato, K M

    2012-03-01

    The defensive secretion of the ground beetle Chlaenius cordicollis is predominantly 3-methylphenol. Adult C. cordicollis were collected in Pennsylvania and Manitoba and induced to discharge defensive secretion in a vial. The headspace was sampled by solid phase microextraction, and samples were analyzed by gas chromatography-mass spectrometry. Five alkylphenolic compounds were detected: all beetles secreted 3-methlyphenol, 2,5-dimethylphenol, and 3-ethylphenol, and most beetles from each locality secreted detectable amounts of 2,3-dimethlyphenol and 3,4-dimethylphenol. In about 80% of beetles, we detected small amounts of the alkoxyphenolic compounds 2-methoxy-4-methylphenol and 2-methoxy-5-methylphenol. Multivariate compositional analysis of relative peak areas of alkylphenolic compounds revealed geographic variation and sexual dimorphism in defensive secretions. Compared with samples from Manitoba, relative peak areas of samples from Pennsylvania were lower for 2,3-dimethylphenol and higher for 3-methylphenol. Sexual dimorphism was detected only in Manitoba where, compared with samples from males, relative peak areas for samples from females were higher for 2,5-dimethylphenol and lower for 3-ethylphenol. This is the first report of geographic variation in defensive secretions of carabid beetles, and it demonstrates the need for knowledge of patterns of variation before characterizing the defensive secretions of a species as a whole.

  15. Organic micropollutants in coastal waters from NW Mediterranean Sea: sources distribution and potential risk.

    PubMed

    Sánchez-Avila, Juan; Tauler, Romà; Lacorte, Silvia

    2012-10-01

    This study provides a first estimation on the sources, distribution and risk of organic micropollutants (OMPs) in coastal waters from NW Mediterranean Sea. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, polybrominated diphenyl ethers, phthalates and alkylphenols were analyzed by solid phase extraction and gas chromatography coupled to tandem mass spectrometry (SPE-GC-EI-MS/MS). River waters and wastewater treatment plant effluents discharging to the sea were identified as the main sources of OMPs to coastal waters, with an estimated input amount of around of 25,800 g d(-1). The concentration of ΣOMPs in coastal areas ranged from 17.4 to 8442 ng L(-1), and was the highest in port waters, followed by coastal and river mouth seawaters. A summarized overview of the patterns and sources of OMP contamination on the investigated coastal sea waters of NW Mediterranean Sea, as well as of their geographical distribution was obtained by Principal Component Analysis of the complete data set after its adequate pretreatment. Alkylphenols, bisphenol A and phthalates were the main contributors to ΣOMPs and produced an estimated significant pollution risk for fish, algae and the sensitive mysid shrimp organisms in seawater samples. The combination of GC-MS/MS, chemometrics and risk analysis is proven to be useful for a better control and management of OMP discharges.

  16. Laboratory studies on acid-oil microemulsion for use in acidizing

    SciTech Connect

    Zhou Yasong; Chen Yuezhu; Sun Yuehua

    1996-12-31

    Two serious of anionic-nonionic surfactants, alkylphenol polyoxyethylene ether phosphates (OPP-n) and sodium salts of carboxymethyl alkylphenol polyoxyethylene ether (OPC-n), where n denotes the average EO number in the molecular, are synthesized to prepare the acid/oil Microemulsions for acidizing. Through components screening tests a work formulation of acidizing microemulsion is established: 13.0% OPP-10, 3.0% OPC-25, 30% n-Hexanol, 36.7% Kerosine and 18.3%(15.0%-concentrated) Hydrochloric Acid. This microemulsion reacts with marble at 30{degrees}C and atmospheric pressure with the lowest acid consuming rate as compared with other retarded acid fluids. Calcium ion accelerates the acid/marble reaction and the suggested microemulsion can tolerate up to 0.69%(W) Calcium ion. No aqueous phase would be separated from the microemulsion until all acid exhausted. The acid/oil microemulsions can be recommended for both matrix and fracture acidizing in depth. The transmission of hydrogen ion in the microemulsion is investigated by using a liquid film supported by solid (SLMS) technique. The mechanism {open_quotes}transmission by exchanging{close_quotes} is suggested. 2 refs., 6 figs., 1 tab.

  17. 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.

  18. Rotational diffusion of coumarin 153 in nanoscopic micellar environments of n-dodecyl-β-D-maltoside and n-dodecyl-hexaethylene-glycol mixtures.

    PubMed

    Hierrezuelo, J M; Ruiz, C Carnero

    2012-12-27

    The microstructure of mixed micelles containing n-dodecyl-β-D-maltoside and n-dodecyl-hexaethylene-glycol, two nonionic surfactants belonging to the alkyl polyglucoside and polyoxyethyelene alkyl ether families, respectively, has been investigated. With the aim of understanding how the micellar composition affects the microenvironmental properties of micelles, we have examined the photophysics and dynamics of the neutral probe coumarin 153 in the binary mixtures of the surfactants across the entire composition range. We present data on the steady-state absorption and emission spectra of the probe, as well as fluorescence lifetimes and both steady-state and time-resolved fluorescence anisotropies. These data indicate that the participation of the ethoxylated surfactant in the mixed micelle induces an increasing hydration in the palisade layer of the micelle, which forces the probe to migrate toward the inner micellar region, where it senses a slightly less polar environment. The time-resolved fluorescence anisotropy data were analyzed on the basis of the two-step and wobbling-in-cone model. The average reorientation time of the probe molecule was found to decrease with the presence of the ethoxylated surfactant, in good agreement with steady-state fluorescence anisotropy data, suggesting a reduction of the microviscosity in the solubilization site of the probe. The behavior of all diffusion reorientation parameters was analyzed on the basis of two factors: the micellar hydration and the headgroup flexibility of both surfactants. It was concluded that the increasing participation of the ethoxylated surfactant induces a greater hydration in the micellar palisade layer, producing the formation of a less compact microenvironment where the probe experiences a faster rotational reorientation.

  19. Nonylphenol in the environment: a critical review on occurrence, fate, toxicity and treatment in wastewaters.

    PubMed

    Soares, A; Guieysse, B; Jefferson, B; Cartmell, E; Lester, J N

    2008-10-01

    Nonylphenol is a toxic xenobiotic compound classified as an endocrine disrupter capable of interfering with the hormonal system of numerous organisms. It originates principally from the degradation of nonylphenol ethoxylates which are widely used as industrial surfactants. Nonylphenol ethoxylates reach sewage treatment works in substantial quantities where they biodegrade into several by-products including nonylphenol. Due to its physical-chemical characteristics, such as low solubility and high hydrophobicity, nonylphenol accumulates in environmental compartments that are characterised by high organic content, typically sewage sludge and river sediments, where it persists. The occurrence of nonylphenol in the environment is clearly correlated with anthropogenic activities such as wastewater treatment, landfilling and sewage sludge recycling. Nonylphenol is found often in matrices such as sewage sludge, effluents from sewage treatment works, river water and sediments, soil and groundwater. The impacts of nonylphenol in the environment include feminization of aquatic organisms, decrease in male fertility and the survival of juveniles at concentrations as low as 8.2 microg/l. Due to the harmful effects of the degradation products of nonylphenol ethoxylates in the environment, the use and production of such compounds have been banned in EU countries and strictly monitored in many other countries such as Canada and Japan. Although it has been shown that the concentration of nonylphenol in the environment is decreasing, it is still found at concentrations of 4.1 microg/l in river waters and 1 mg/kg in sediments. Nonylphenol has been referred to in the list of priority substances in the Water Frame Directive and in the 3rd draft Working Document on Sludge of the EU. Consequently there is currently a concern within some industries about the possibility of future regulations that may impose the removal of trace contaminants from contaminated effluents. The significance of

  20. Prevention of Endotoxin-Induced Pulmonary Hypertension in Primates by the Use of a Selective Thromboxane Synthetase Inhibitor, OXY 1581

    DTIC Science & Technology

    1982-09-01

    inhibitor to prevent endotoxin-induced Chemical name: Sodium-(E) - 3 -[ 4 - ( 3 -pyridylmethyl) phenyll -2- pulmonary hypertension in subhuman primates...1:B4, 6 mg/kg) and Group II (n = 6) received a bolus of 2 mg/kg of Results are expressed as mean ± S.EM. OKY 1581 (fig. I) (sodium-(E)- 3 -[ 4 -( 3 ...UK 37248 endotoxines. Ann. Inst. Pasteur 73: 565. 1947. [ 4 -(2- 1H -imidazole-lyl)ethoxyl benzoic acid], given to humans, DELAUNAY, A., LEBRUN, J

  1. 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.

  2. 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.

  3. Contact sensitivity to nonoxynols as a cause of intolerance to antiseptic preparations.

    PubMed

    Dooms-Goossens, A; Deveylder, H; de Alam, A G; Lachapelle, J M; Tennstedt, D; Degreef, H

    1989-10-01

    Twelve cases of allergic contact dermatitis caused by antiseptic preparations are presented. The reactions resulted not from the active principles but rather from nonoxynols used in the offending substances as nonionic surface-active agents. Nonoxynols are ethoxylated alkyl phenols or nonylphenylethers that conform in general to the formula C9H19C6H4(OCH2CH2)nOH. They have emulsifying, wetting, foaming, and solubilizing properties and are used in a large number of industrial, household, agricultural, cosmetic, and pharmaceutical products. They also are used as spermicides. There are very few reports in the literature of skin problems caused by nonoxynols.

  4. A double-coated magnetite-based magnetic fluid evaluation by cytometry and genetic tests

    NASA Astrophysics Data System (ADS)

    Freitas, M. L. L.; Silva, L. P.; Azevedo, R. B.; Garcia, V. A. P.; Lacava, L. M.; Grisólia, C. K.; Lucci, C. M.; Morais, P. C.; Da Silva, M. F.; Buske, N.; Curi, R.; Lacava, Z. G. M.

    2002-11-01

    Magnetite nanoparticles pre-coated with dodecanoic acid and ethoxylated alcohol (DE) were used to obtain a physiologically stable magnetic fluid (DE-MF) sample. Three different doses of DE-MF were intraperitoneally applied to mice. Blood and peritoneum cytometry and micronucleus test were performed for 1-21 days after injection to investigate the DE-MF toxicity. Changes in cell population, peritoneum inflammation, and potential DE-MF genotoxic action were all time and dose dependent. At the lowest dose (5×10 15 particles/kg), DE-MF seems to be useful as a drug precursor with both diagnostic and therapeutic values.

  5. Rust inhibiting additive compositions for oils

    SciTech Connect

    Haugen, H.

    1980-09-23

    Compositions which include mixtures of a calcium hydroxide overbased oil-soluble calcium sulfonate, hexylene glycol and a surfactant consisting of an ethoxylated aliphatic amine, particularly, diethoxylated cocoamine or diethoxylated soyamine, are useful as rust inhibiting additives for oils and the like. By incorporating these compositions in petroleum based oils such as petroleum based oils of lubricating oil quality which come into contact with metal surfaces under conditions such that the metal surfaces tend to rust or otherwise be subject to deterioration it is possible to inhibit rust formation on such metal surfaces.

  6. Micropolarity and water penetration in micellar aggregates of linear and branched hydrocarbon surfactants

    SciTech Connect

    Varadaraj, R.; Bock, J.; Valint, P. Jr.; Brons, N. )

    1990-08-01

    The micropolarity of aqueous micellar solutions of ethoxylates, sodium ethoxy sulfates, and sulfates derived from linear and branched hydrocarbon alcohols was investigated by using a solvatochromic pyridinio-N-phenoxide betaine, ET-30, polarity probe. Branching of the hydrophobe resulted in a more porous micellar aggregate. Thermosolvatochromism of ET-30 allowed an investigation of the effect of temperature on micropolarity. Increase in temperature was observed to expel water from the hydrophobic regions of the aggregate and decrease the effective micropolarity in linear and branched surfactants.

  7. Compositions for use in oil recovery and method of use

    SciTech Connect

    Bretherick, L.; Hodgson, P. K. G.

    1985-02-05

    Betaines containing the morpholine nucleus, some of which are novel per se, are dissolved in sea water or formation water, the concentration of betaine being from 200 to 100,000 ppm to give a surfactant solution suitable for displacing crude oil from a formation in an enhanced oil recovery process. Included in the solution can be an anionic surfactant containing in its structure an ethoxylated benzene ring which shows a synergistic effect with the betaine in lowering the interfacial tension of the surfactant solution against oil. These betaines have high tolerance towards divalent metal cations and high temperature stability as compared with betaines previously proposed for enhanced oil recovery.

  8. Research on the Influence of the Type of Surfactant and Concentrator in Aqueous Dispersion of Pigments.

    PubMed

    Makarewicz, Edwin; Michalik, Agnieszka

    2014-01-01

    This work reports tests performed to evaluate the stability of aqueous dispersions of inorganic oxide pigments with different specific surface areas, with the use of anionic and non-ionic surfactants and concentrators. Color mixtures of oxide compounds of blue, green, olive and brown with the unit cell spinel structure were used as pigments. The sodium salt of sulfosuccinic acid monoester, oxyethylenated nonylphenol and ethoxylated derivatives of lauryl alcohol, fatty alcohol and fatty amine were used as surfactants. The concentrators used were: poly(vinyl alcohol), the sodium salt of carboxymethyl cellulose as well as a water-based polyurethane oligomer. The highest dispersion efficiency was found for dispersed systems in which surfactant and concentrator were incorporated in the formula. The one containing the sodium salt of carboxymethyl cellulose or polyurethane oligomer with ethoxylated saturated fatty alcohol or fatty amine was found to be the most efficient. It was discovered that a higher dispersion efficiency corresponds to pigments with larger specific surface. The efficiency is also found to improve when the concentrator is an acrylic polymer or copolymer made up of two acrylic species. In this case, the concentrator interaction with the surfactant is more effective if the value of its boundary viscosity number is higher. This observation confirms the existence of interactions between macro-chains of the concentrator and surfactant molecules forming micelles with the pigment particles.

  9. 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.

  10. Characterization of polyoxyethylene tallow amine surfactants in technical mixtures and glyphosate formulations using ultra-high performance liquid chromatography and triple quadrupole mass spectrometry.

    PubMed

    Tush, Daniel; Loftin, Keith A; Meyer, Michael T

    2013-12-06

    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.

  11. Formation and morphology of reverse micelles formed by nonionic surfactants in "dry" organic solvents.

    PubMed

    Pérez, Sofía V; Olea, Andres F; Gárate, M Pilar

    2014-01-01

    The formation of reverse micelles by nonionic alcohol ethoxylates surfactants in two "dry" non polar solvents, heptane and dibutoxymethane (DBM), has been studied. These surfactants are formed by a linear hydrocarbon chain consisting of i carbons, and a poly(ethylene oxide) chain with j ethoxylate units (EO) ending with a hydroxyl group, CiEOj. The study is focused on the determination of the critical micelle concentration CMC and the size and morphology of the formed aggregates. The CMC was obtained from the decreasing of interfacial tension with increasing surfactant concentration and by using pyrene sulfonic acid sodium salt as fluorescence probe. The results show that the CMC in heptane is one order of magnitude higher than in DBM and two orders of magnitude higher than those determined in aqueous solution. The self-diffusion coefficients D of C8EO5, C8EO4 and C10EO6 in heptane, were obtained by diffusion ordered spectroscopy (DOSY (1)H-NMR). The experimental values of D were then fitted to four different configurations to determine the most probable morphology of the formed aggregates. In all cases the presence of large and compact aggregates, with aggregation numbers going from a few dozens of monomers to a hundred of them, was shown.

  12. Application technology for the entomopathogenic nematodes Heterorhabditis indica and Steinernema sp. (Rhabditida: Heterorhabditidae and Steinernematidae) to control Spodoptera frugiperda (Smith) (Lepidoptera: Noctuidae) in corn.

    PubMed

    Garcia, Luiz C; Raetano, Carlos G; Leite, Luis G

    2008-01-01

    The effects of different application technologies were evaluated on the concentration, viability, and efficiency of infective juveniles of the nematodes Heterorhabditis indica Poinar, Karunakar & David and Steinernema sp. (IBCB-n6) to control Spodoptera frugiperda Smith on corn plants. Two hundred and eighty infective juveniles of Steinernema sp. were required to kill 100% third-instar fall armyworms in petri dishes, as compared to 400 infective juveniles of the H. indica nematode to obtain 75% fall armyworm control. It is possible to spray entomopathogenic nematodes without significant loss in their concentration and viability, with equipment that produces electrical charges to the spraying mix, and with those using hydraulic and rotary nozzle tips. The concentrations of infective juveniles of H. indica and Steinernema sp. nematodes were reduced by 28% and 53%, respectively, when hydraulic spraying nozzles that require 100-mesh filtrating elements were used. Tensoactive agents of the organosilicone and ethoxylate groups did not affect the viability of infective juveniles of Steinernema sp. juveniles. Spraying corn plants (V6 growth stage) with up to 288 million infective juveniles of Steinernema sp. per hectare, diluted in the spraying mix up to 800 L ha-1, with 0.01% ethoxylate tensoactive agent, or at the same volume followed by artificial rain (6 mm water depth) was not sufficient to control S. frugiperda in a controlled environment.

  13. Separation and quantitative analysis of alkyl sulfate ethoxymers by HPLC.

    PubMed

    Morvan, Julien; Hubert-Roux, Marie; Agasse, Valérie; Cardinael, Pascal; Barbot, Florence; Decock, Gautier; Bouillon, Jean-Philippe

    2008-01-01

    Separation of alkyl sulfate ethoxymers is investigated on various high-performance liquid chromatography (HPLC) stationary phases: Acclaim C18 Surfactant, Surfactant C8, and Hypercarb. For a fixed alkyl chain length, ethoxymers are eluted in the order of increasing number of ethoxylated units on Acclaim C18 Surfactant, whereas a reversed elution order is observed on Surfactant C8 and Hypercarb. Moreover, on an Acclaim C18 Surfactant column, non-ethoxylated compounds are eluted in their ethoxymers distribution and the use of sodium acetate additive in mobile phase leads to a co-elution of ethoxymers. HPLC stationary phases dedicated to surfactants analysis are evaluated by means of the Tanaka test. Surfactant C8 presents a great silanol activity whereas Acclaim C18 Surfactant shows a high steric selectivity. For alkyl sulfates, linearity of the calibration curve and limits of detection and quantitation are evaluated. The amount of sodium laureth sulfate raw material found in commercial body product is in agreement with the specification of the manufacturer.

  14. Estrogenic responses of larval sunshine bass (Morone saxatilis x M. Chrysops) exposed to New York City sewage effluent.

    PubMed

    Todorov, Julia R; Elskus, Adria A; Schlenk, Daniel; Ferguson, P Lee; Brownawell, Bruce J; McElroy, Anne E

    2002-01-01

    To determine the estrogenicity of effluents from sewage treatment plants (STPs) to larval fish, 2-day-old sunshine bass were exposed to effluents from three STPs serving New York City (NYC), varying in size and treatment level. Estrogenic response was evaluated by measuring vitellogenin (VTG) and estrogen receptor (ER) expression in cytosolic fractions of whole body homogenates. Concentrations of the presumptive endocrine disruptors in the effluents were also measured. VTG and ER levels in sewage-exposed fish were 3-5 times that observed in controls. Combined concentrations of estradiol and estrone ranged from 5 to 13 ng/l and nonylphenol-ethoxylate metabolites (NPEOs: 4-nonylphenol, and 1-, 2-, and 3-nonylphenol-ethoxylates) ranged from 180 to 470 microg/l in chlorinated effluent. Results indicate that both ER and VTG can be used as biomarkers for endocrine disruption in larval fish, and that 4-day exposure to sewage effluent is sufficient to elicit significant expression of these markers in sunshine bass larvae. The extremely higher concentrations of NPEOs found in effluent relative to hormones (approximately 40,000-fold) indicates that surfactant metabolites may be contributing significantly to the estrogenic effects observed.

  15. Mechanisms of Neutral and Anionic Surfactant Sorption to Solid-Phase Microextraction Fibers.

    PubMed

    Haftka, Joris J-H; Hammer, Jort; Hermens, Joop L M

    2015-09-15

    Octanol-water partitioning (Kow) is considered a key parameter for hydrophobicity and is often applied in the prediction of the environmental fate and exposure of neutral organic compounds. However, surfactants can create difficulties in the determination of Kow because of emulsification of both water and octanol phases. Moreover, not only is sorption behavior of ionic surfactants related to hydrophobicity, but also other interactions are relevant in sorption processes. A different approach to develop parameters that can be applied in predictive modeling of the fate of surfactants in the environment is therefore required. Distribution between solid-phase microextraction (SPME) fibers and water was used in this study to measure the affinity of surfactants to a hydrophobic phase. Fiber-water sorption coefficients of alcohol ethoxylates, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates were determined at pH 7 by equilibration of the test analytes between fiber and water. Distribution between fiber and water of anionic compounds with pKa ∼ 5 (i.e., alkyl carboxylates) was dominated by the neutral fraction. Anionic surfactants with pKa ≤ 2 (i.e., alkyl sulfates and alkyl sulfonates) showed strong nonlinear distribution to the fiber. The fiber-water sorption coefficients for alcohol ethoxylates and alkyl sulfates showed a linear trend with bioconcentration factors from the literature. Fiber-water sorption coefficients are promising as a parameter to study the effects of hydrophobicity and other potential interactions on sorption behavior of neutral and anionic surfactants.

  16. Crystallization and X-ray analysis of the salmon-egg lectin SEL24K

    SciTech Connect

    Murata, Kenji; Fisher, Andrew J.; Hedrick, Jerry L.

    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 belongs 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.

  17. 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.

  18. Influence of chemical surfactants on the biodegradation of crude oil by a mixed bacterial culture.

    PubMed

    Van Hamme, J D; Ward, O P

    1999-02-01

    The effects of surfactant physicochemical properties, such as the hydrophile-lipophile balance (HLB) and molecular structure, on the biodegradation of 2% w/v Bow River crude oil by a mixed-bacterial culture were examined. Viable counts increased 4.6-fold and total petroleum hydrocarbon (TPH) biodegradation increased 57% in the presence of Igepal CO-630, a nonylphenol ethoxylate (HLB 13, 0.625 g/L). Only the nonylphenol ethoxylate with an HLB value of 13 substantially enhanced biodegradation. The surfactants from other chemical classes with HLB values of 13 (0.625 g/L) had no effect or were inhibitory. TPH biodegradation enhancement by Igepal CO-630 occurred at concentrations above the critical micelle concentration. When the effect of surfactant on individual oil fractions was examined, the biodegradation enhancement for the saturate and aromatic fractions was the same. In all cases, biodegradation resulted in increased resin and asphaltene concentrations. Optimal surfactant concentrations for TPH biodegradation reduced resin and asphaltene formation. Chemical surfactants have the potential to improve crude oil biodegradation in complex microbial systems, and surfactant selection should consider factors such as molecular structure, HLB, and surfactant concentration.

  19. Method for reducing the effect of environmental contamination of Sol-gel optical coatings

    SciTech Connect

    Burnham, A. K.; Ertel, J. R.; Frieders, S. C.; Thomas, I. M.

    1998-07-28

    AR coatings prepared from colloidal suspensions of silica have a large surface area because of their porosity. The surface is quite polar and readily absorbs vapor contamination to the detriment of the optical performance and the laser damage threshold. This effect is particularly bad in ''dirty'' vacuum systems such as target chambers. The polar surface is due to residual Si-OH and Si-ethoxyl groups formed as a result of the method of preparation of the coating suspension. We have now found that these groups can be removed by further treatment of the coating after preparation. This involves two steps, the first being exposure to ammonia and water vapor which hydrolyzes the ethoxyl groups to hydroxyl groups with the formation of more Si-OH groups. Some of these react further by self condensation to Si-0-Si linkages. The remaining Si-OH groups are removed in the second step by reaction with hexamethyl-disilazane (HMDS) which converts them to trimethylsilyl groups. The latter are completely non-polar and substantially eliminate vapor absorption. We have carried out a series of tests involving exposure of treated and untreated coatings to various types of vapor contamination and followed the degree of contamination by the reduction in optical transmission. In all cases the treated coatings showed a significant reduction in transmission loss. These tests also provide guidance as to which materials are acceptable for use.

  20. The in-situ decontamination of sand and gravel aquifers by chemically enhanced solubilization of multiple-component DNAPLS with surfactant solutions. Topical report

    SciTech Connect

    1995-01-01

    Laboratory, numerical simulation, and field studies have been conducted to assess the potential use of micellar-surfactant solutions to solubilize chlorinated solvents contaminating sand and gravel aquifers. Laboratory studies were conducted at the State University of New York at Buffalo (SUNY) while numerical simulation and field work were undertaken by INTERA Inc. in collaboration with Martin Marietta Energy Systems Inc. at the Paducah Gaseous Diffusion Plant (PGDP) in Kentucky. Ninety-nine surfactants were screened for their ability to solubilize trichloroethene (TCE), perchloroethylene (PCE), and carbon tetrachloride (CTET). Ten of these were capable of solubilizing TCE to concentrations greater than 15,000 mg/L, compared to its aqueous solubility of 1,100 mg/L. Four surfactants were identified as good solubilizers of all three chlorinated solvents. Of these, a secondary alcohol ethoxylate was the first choice for in situ testing because of its excellent solubilizing ability and its low propensity to sorb. However, this surfactant did not meet the Commonwealth of Kentucky`s acceptance criteria. Consequently, it was decided to use a surfactant approved for use by the Food and Drug Administration as a food-grade additive. As a 1% micellar-surfactant solution, this sorbitan monooleate has a solubilization capacity of 16,000 mg TCE/L, but has a higher propensity to sorb to clays than has the alcohol ethoxylate.

  1. Optimal operation for timely adaptation of activated sludge plants to changes in the surfactant composition of wastewater.

    PubMed

    Carvalho, G; Novais, J M; Vanrolleghem, P A; Pinheiro, H M

    2002-01-01

    The composition of a textile industry wastewater is highly variable, as the industrial process has to follow fashion and season trends. Surfactants represent one of the largest COD fractions in a typical textile wastewater. Therefore, it was the aim of this paper to model the acclimatisation behaviour of an activated sludge system when subjected to composition variations in the surfactant containing feed. The model was based on data obtained in SBR experiments in which a linear alkyl ethoxylate as sole carbon source in the feed was replaced by another with a longer ethoxylate chain. A previously developed model (Fractionated Degradation Model) was applied to each of the 21 SBR cycles carried out in this study. The resulting best-fit parameters were investigated and sub-models were further developed, to create an acclimatisation model, able to predict the sludge acclimatisation level. Using the information given by this model, it was possible to propose an optimal operation scheme to pre-acclimatise the sludge before a surfactant replacement is made in the textile process. A cost analysis was carried out to compare different scenarios, with and without the application of this operation scheme. It was concluded that the proposed pre-acclimatisation process may be cost effective as compared to other scenarios if a cheap surfactant-containing product was employed.

  2. Non-specific SIRT inhibition as a mechanism for the cytotoxicity of ginkgolic acids and urushiols.

    PubMed

    Ryckewaert, Lucie; Sacconnay, Lionel; Carrupt, Pierre-Alain; Nurisso, Alessandra; Simões-Pires, Claudia

    2014-09-02

    Ginkgolic acids and urushiols are natural alkylphenols known for their mutagenic, carcinogenic and genotoxic potential. However, the mechanism of toxicity of these compounds has not been thoroughly elucidated so far. Considering that the SIRT inhibitory potential of anacardic acids has been hypothesized by in silico techniques, we herein demonstrated through both in vitro and computational methods that structurally related compounds such as ginkgolic acids and urushiols are able to modulate SIRT activity. Moreover, their SIRT inhibitory profile and cytotoxicity were comparable to sirtinol, a non-specific SIRT inhibitor (SIRT1 and SIRT2), and different from EX-527, a SIRT1 specific inhibitor. This is the first report on the SIRT inhibition of ginkgolic acids and urushiols. The results reported here are in line with previously observed effects on the induction of apoptosis by this class of compounds, and the non-specific SIRT inhibition is suggested as a new mechanism for their in vitro cytotoxicity.

  3. 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

  4. Chemical composition of shale oil. 1; Dependence on oil shale origin

    SciTech Connect

    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 the abundance, relative to the total amount of volatiles in the oil, of alkylbenzenes and alkylphenols.

  5. 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.

  6. Analytical strategies based on chromatography-mass spectrometry for the determination of estrogen-mimicking compounds in food.

    PubMed

    Capriotti, Anna Laura; Cavaliere, Chiara; Colapicchioni, Valentina; Piovesana, Susy; Samperi, Roberto; Laganà, Aldo

    2013-10-25

    Food safety can be compromised by the presence of a wide variety of substances, deriving from both natural and anthropogenic sources. Among these substances, compounds exhibiting various degrees of estrogenic activity have been widely studied in environmental samples, whereas less attention has been devoted to food matrices. The aim of the present review is to give a general overview on the recent analytical methods based on gas or liquid chromatography coupled to mass spectrometry for the determination of estrogen-like compounds in foods, including new developments, improvements and upcoming trends in the field. Attention will be focused on four representative groups of compounds, i.e. natural and synthetic estrogens, mycoestrogens, phytoestrogens, and alkylphenols.

  7. Assessment of the effects of a marine urban outfall discharge on caged mussels using chemical and biomarker analysis.

    PubMed

    de los Ríos, Ana; Juanes, José A; Ortiz-Zarragoitia, Maren; López de Alda, Miren; Barceló, Damià; Cajaraville, Miren P

    2012-03-01

    To assess the presence of endocrine disruptors in treated marine outfall discharges and their possible effects, mussels (Mytilus galloprovincialis) were caged in the environmental mixing zone of the outfall of the Santander sanitation system and in one control area. After 30, 60 and 90 days, samples were collected to perform chemical analyses (metals, anionic surfactants, alkylphenols, bisphenol A, phthalates and estrogenic hormones), biomarkers of general stress (lysosomal membrane stability-LMS, histopathology) and biomarkers of endocrine disruption (vitellogenin-like proteins and gonad index). There were no significant differences between outfall and control sites on contaminant levels, except for 4-tert-octylphenol which was higher in the outfall site. Bacteriological counts were higher in the outfall area. No relevant differences in biomarkers were detected between treated and control mussels. A significant reduction in LMS occurred in both groups after 90 days caging, indicating a stress situation possibly related to caging or to post-spawning reproductive state.

  8. 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.

  9. 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.

  10. Phenolic endocrine disrupting chemicals (EDCs) in Anzali Wetland, Iran: elevated concentrations of 4-nonylphenol, octhylphenol and bisphenol A.

    PubMed

    Mortazavi, Samar; Bakhtiari, Alireza Riyahi; Sari, Abbas Esmaili; Bahramifar, Nader; Rahbarizade, Fatemeh

    2012-05-01

    We have studied the distribution and value of phenolic endocrine disrupting chemicals (EDCs) in surface sediment samples taken from Anzali Wetland, Iran. These samples were collected from 22 stations during the time span of June-May 2010. In each of the sampling stations, we detected 4-nonylphenol (4-NP), octylphenol (OP), and bisphenol A (BPA) with maximal concentrations of 29, 4.3, and 7 μg g(-1) dry weight (dw), respectively. High levels of alkylphenols (APs) and BPA were also found near urban areas. Furthermore there were no significant differences between those stations in terms of the detected levels. One of the important factors in controlling the fate of these compounds in the aquatic environment appeared to be Total Organic Carbon (TOC). Hierarchical cluster analysis showed differences in the biomarker characteristics of EDCs and TOC between the stations. Our findings indicate that EDCs are ubiquitous in sediments from northeast Wetlands of Iran, contaminating the aquatic habitats in this area.

  11. Oxidative metabolism of the trifluoromethoxy moiety of OSI-930.

    PubMed

    Dihel, Larry; Kittleson, Christine; Mulvihill, Kristen; Johnson, William W

    2009-01-01

    Cytochrome P450 can catalyze a wide array of remarkable oxidations, including O-dealkylations, which are performed via oxidation of the alpha-carbon of the ether. When C-H bonds are replaced with C-F bonds, however, the bond strength is much greater, and it significantly deters oxidation at the carbon. Another recently elucidated reaction catalyzed by P450, ipso substitution, results in displacement of aromatic ring substituents such as an alkoxy group via hydroxyl substitution. Through LC/MS/MS, we show the CYP-mediated oxidative displacement of the trifluoromethoxy group from the phenyl constituent in OSI-930, a novel small molecule c-Kit/VEGF-r inhibitor in clinical studies to treat cancer. Based on C-F bond strength, reported phenacetin studies, and alpha-quaternary alkylphenol studies, we propose an ipso-substitution mechanism for this oxidative biotransformation. In vivo, this hydroxylated metabolite goes on to form the ether conjugate with glucuronide.

  12. 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.

  13. Impact of oestrogenic substances from oil production at sea.

    PubMed

    Lye, C M

    2000-03-15

    The possibility that chemicals present in the environment may mimic hormones, causing deleterious physiological effects to wildlife, has been given considerable attention. Although the question of ecological significance of 'endocrine disrupters' is not yet settled, and standard assessment procedures have not yet been established, proposals to control these chemicals into the marine environment are now being made under the Oslo and Paris Commission (OSPAR) and the Helsinki Commission (HELCOM). A possible source of such emissions is offshore-drilling, where applications containing polyaromatic hydrocarbons (PAHs) and alkylphenols, indicated as environmental oestrogens, historically have been used. This paper examines available evidence regarding the potential impact of these substances on aquatic organisms living around offshore platforms.

  14. Method of using an aqueous chemical system to recover hydrocarbon and minimize wastes from sludge deposits in oil storage tanks

    SciTech Connect

    Goss, M.L.

    1992-02-04

    This patent describes a process for separating and removing a hydrocarbon, water and solid components of sludge deposited in an oil storage tank. It comprises: introducing a sufficient amount of a nonionic surfactant in an aqueous solution to form a layer of the solution above the sludge layer; the nonionic surfactant comprising: C{sub 8}-C{sub 12} alkylphenol-ethylene oxide adducts of about 55%-75% by weight ethylene oxide, and at least one castor oil-ethylene oxide adduct of about 55%-75% by weight ethylene oxide; the nonionic surfactant being present in a quantity sufficient to separate hydrocarbon component from the sludge without forming an emulsion, adding a diluent, immiscible with the aqueous layer, for extracting the hydrocarbons, and separately draining the diluent layer and aqueous layer from the tank.

  15. Multi-residue analytical method for the determination of endocrine disruptors and related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass spectrometry.

    PubMed

    Gorga, Marina; Petrovic, Mira; Barceló, Damià

    2013-06-21

    The present study describes a novel, fully automated method, based on column switching using EQuan™ columns for an integrated sample preconcentration and liquid chromatography coupled to tandem mass spectrometry (LC-LC-MS/MS). The method allows the unequivocal identification and quantification of the most relevant environmental endocrine disruptors compounds (EDCs) and compounds suspected to be EDCs, such as natural and synthetic estrogens and their conjugates, antimicrobials, parabens, bisphenol A, alkylphenolic compounds, benzotriazoles, and organophosphorus flame retardants, in surface river water and wastewater samples. Applying this technique, water samples were directly injected into the chromatographic system and the target compounds were concentrated into the loading column. Thereafter, the analytes were transferred into the analytical column for subsequent detection by MS-MS (QqQ). A comparative study employing three types of columns, with different chemical modifications, was performed in order to determine the optimal column that allowed maximum retention and subsequent elution of the analytes. Using this new optimized methodology a fast and easy online methodology for the analysis of EDCs in surface river water and wastewater with low limits of quantification (LOQ) was obtained. LOQs ranged from 0.008 to 1.54 ng/L for surface river water and from 0.178/0.364 to 12.5/25.0 ng/L (except for alkylphenol monoethoxylates) for effluent/influent waste water. Moreover, employing approximately 1h, a complete analysis was performed which was significant improvement in comparison to other methods reported previously. This method was used to track the presence and fate of target compounds in the Ebro River which is the most important river in Spain whose intensive agricultural and industrial activities concentrate mainly close to the main cities in the basin, deteriorating soil and water quality.

  16. 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).

  17. Evaluation of low-cost materials for sorption of hydrophobic organic pollutants in stormwater.

    PubMed

    Björklund, Karin; Li, Loretta

    2015-08-15

    Conventional stormwater treatment techniques such as sedimentation and filtration are inefficient for removing the dissolved and colloidal phases of hydrophobic organic compounds (HOCs) present in stormwater. Adsorption could be a promising technique for removing colloidal and dissolved pollutants. Five low-cost sorbent materials were investigated in this project, including two minerals – vermiculite and perlite – and three waste products – two pine barks and a sawdust – as potential adsorbents for removal of polycyclic aromatic hydrocarbons (PAHs), alkylphenols and phthalates; HOCs commonly found in stormwater. Adsorption capacity and kinetics were studied through batch adsorption tests using synthetic stormwater spiked with a mixture of HOCs. Vermiculite and perlite exhibited insignificant removal of the organic contaminants. The three wood-based materials retained >80% of the initial HOC concentration (10-300 μg/L). The two barks exhibited slightly higher adsorption capacities of HOCs than the sawdust. For all compounds tested, maximum adsorption onto the wood-based media was reached in <10 min. The highest adsorption capacity was found for PAHs (up to 45 μg/g), followed by alkylphenols and phthalates. No correlation was found between adsorption capacity and physical-chemical parameters such as solubility and partition coefficients (log K(ow)). Agreement between empirical data and the pseudo-second order kinetic model suggest chemisorption of HOCs onto a monolayer on wood-based media. This could lead to early saturation of the materials and should be investigated in future studies through repeated adsorption of HOCs, for example in column studies.

  18. Determination of uptake kinetics and sampling rates for 56 organic micropollutants using "pharmaceutical" POCIS.

    PubMed

    Morin, Nicolas; Camilleri, Julien; Cren-Olivé, Cécile; Coquery, Marina; Miège, Cécile

    2013-05-15

    The literature increasingly reports sampling rates (Rs) for Polar Organic Chemical Integrative Samplers (POCIS) but the data obtained come from various calibration systems that are not always well-defined (agitation, temperature, measured micropollutant concentrations in water,…). In order to obtain accurate laboratory Rs for priority and emerging substances, POCIS need to be exposed in a robust and well-defined calibration system. Thus, we built a flow-through calibration system containing tap water spiked with 56 organic micropollutants (alkylphenols and phenols, hormones, pesticides, pharmaceuticals, UV filter). POCIS were immersed for up to 28 days. Tap water micropollutant concentrations and additional parameters (temperature, pH, conductivity, dissolved organic carbon, flow velocities) were kept constant and controlled throughout the calibration experiment. Based on the observed uptake kinetics, we distinguished four types of micropollutant accumulation patterns: curvilinear accumulation (30 molecules, group 1), accumulation with an inflexion point (13 molecules, group 2), random accumulation (eight molecules, group 3), and no or very low accumulation (five molecules, group 4). Rs was calculated for 43 out of 56 micropollutants (groups 1 and 2). Calculated Rs values ranged from 0.030 L/d to 0.398 L/d. POCIS can supply TWA concentrations for hormones, pesticides, several pharmaceuticals, a few alkylphenols, and the UV filter. Our Rs results are generally less than two fold-different (higher or lower depending on target molecule) to the literature data using the same type of calibration system or for micropollutants with log Kow>2.65. We found a quadratic correlation between Rs and log D for betablockers, herbicides and hormones.

  19. Priority Substances and Emerging Organic Pollutants in Portuguese Aquatic Environment: A Review.

    PubMed

    Ribeiro, Cláudia; Ribeiro, Ana Rita; Tiritan, Maria Elizabeth

    Aquatic environments are among the most noteworthy ecosystems regarding chemical pollution due to the anthropogenic pressure. In 2000, the European Commission implemented the Water Framework Directive, with the aim of progressively reducing aquatic chemical pollution of the European Union countries. Therefore, the knowledge about the chemical and ecological status is imperative to determine the overall quality of water bodies. Concerning Portugal, some studies have demonstrated the presence of pollutants in the aquatic environment but an overall report is not available yet. The aim of this paper is to provide a comprehensive review about the occurrence of priority substances included in the Water Framework Directive and some classes of emerging organic pollutants that have been found in Portuguese aquatic environment. The most frequently studied compounds comprise industrial compounds, natural and synthetic estrogens, phytoestrogens, phytosterols, pesticides, pharmaceuticals and personal care products. Concentration of these pollutants ranged from few ng L(-1) to higher values such as 30 μg L(-1) for industrial compounds in surface waters and up to 106 μg L(-1) for the pharmaceutical ibuprofen in wastewaters. Compounds already banned in Europe such as atrazine, alkylphenols and alkylphenol polyethoxylates are still found in surface waters, nevertheless their origin is still poorly understood. Beyond the contamination of the Portuguese aquatic environment by priority substances and emerging organic pollutants, this review also highlights the need of more research on other classes of pollutants and emphasizes the importance of extending this research to other locations in Portugal, which have not been investigated yet.

  20. 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.

  1. 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

  2. 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%.

  3. 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

  4. Migration assessment and the 'Threshold of Toxicological Concern' applied to the safe-design of an acrylic adhesive for food contact laminates.

    PubMed

    Canellas, Elena; Vera, Paula; Nerín, Cristina

    2017-03-23

    Adhesives are widely used in food packaging. The suitability of an acrylic adhesive used on food packaging has been studied. Six potential migrants have been identified using GC-MS and UPLC-QTOF. Five compounds were intentionally added (2-butoxyethanol and 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) and TMDD ethoxylates). Moreover, one of the compounds identified as 2-(12-(methacryloyloxy)dodecyl)malonic acid was a non-intenionally added substance (NIAS), that could be a methyl metacrylate derivative. This has demonstrated that the identification of compounds in food packaging is an essential step when the risk evaluation of the package is being studied. A migration study of the adhesive compounds from multilayers with the structure paper-adhesive-film was carried out. The films used for the multilayers were both non-biodegradable substrates (polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET) and biodegradable substrates [polylactic acid (PLA) and Ecovio F2223® that is a mixture of biodegradable polyester with PLA]. All the non-volatile compounds, including the NIAS identified, migrated into the dry food simulant Tenax®. In fact the five compounds (surfactants) based on TMDD were found to migrate from all 5 laminates into Tenax® at levels from 0.05-0.6 mg/kg. The results showed that the lowest migration (0.01 mg/kg for 2-(12-(methacryloyloxy)dodecyl)malonic acid to 0.07 for TMDD mg/kg) occured when the compounds passed through the PLA demostrating its functional barrier properties to these compounds. On the contrary, PE (migration values from 0.11 mg/kg for 2-(12-(methacryloyloxy)dodecyl)malonic acid to 0.57 mg/kg for TMDD ethoxylate n=1 m=1) and Ecovio® (migration values from 0.1 mg/kg for 2-(12-(methacryloyloxy)dodecyl)malonic acid to 0.56 mg/kg for TMDD ethoxylate n=1 m=1) showed the worst barrier properties to these compounds. To evaluate the migration results the threshold of toxicological concern strategy was applied. The

  5. Endocrine disrupters in the aquatic environment: the Austrian approach--ARCEM.

    PubMed

    Bursch, W; Fuerhacker, M; Gemeiner, M; Grillitsch, B; Jungbauer, A; Kreuzinger, N; Moestl, E; Scharf, S; Schmid, E; Skutan, S; Walter, I

    2004-01-01

    A consortium of Austrian scientists (ARCEM) carried out a multidisciplinary environmental study on Austrian surface and ground waters including chemical monitoring, bioindication, risk assessment and risk management for selected endocrine disrupters: 17beta-estradiol, estriol, estrone, 17alpha-ethinylestradiol, 4-nonylphenol, 4-nonylphenol ethoxylates (4-NP1EO, 4-NP2EO) and their degradation products, ocytlphenol, ocytlphenol ethoxylates (OP1EO, OP2EO) as well as bisphenol A. To obtain data representative for Austria, a material flow analysis served to select relevant compounds and water samples were collected monthly over one year at those sites routinely used in Austrian water quality control. The following results were obtained and conclusions drawn: 1. Chemical monitoring: As compared to other countries, relatively low levels of pollution with endocrine disrupters were detected. 2. Bioindication: In the surface waters under study, male fish showed significant signs of feminization and demasculinization (increased production of the egg-yolk protein and histological changes of the gonads. 3. Risk assessment: For humans, exposure via either drinking water abstraction (ground water) or fish consumption was considered. The exposure levels of the compounds under study were below those considered to result in human health risks. Likewise, for bisphenol A and octylphenols, there was no indication for risk posed upon the aquatic environment (fish). However, nonylphenol or 17alpha-ethinylestradiol exposure along with results of bioindication (2) suggest a borderline estrogenic activity in a considerable number of surface waters. Consequently the emissions of these substances into the surface waters affected have to be reduced. 4. Risk management: Waste water treatment experiments revealed a positive correlation between the removal rate of endocrine disrupters from the waste water and the sludge retention time in the treatment plants. These substances are removed to a

  6. Additive composition, for gasoline

    SciTech Connect

    Vataru, M.

    1989-01-10

    An admixture is described that comprises Diesel fuel and an additive composition added thereto which is between about 0.05 to about 2.0 percent by weight of the fuel, the composition comprising: (a) between about 0.05 and 25% relative weight parts of an organic peroxide, and (b) between about 0.1 and 25% relative weight parts of detergent selected from the component group that consists of: (i) fatty amines; (ii) ethoxylated and propoxylated derivatives of fatty amines; (iii) fatty diamines; (iv) fatty imidazlines; (v) polymeric amines and derivatives thereof; (vi) combination of one or more of the (i) through (v) components with carboxylic acid or acids having from three to forth carbon atoms, (c) from about 99.0 to about 50% by weight of a hydrocarbon solvent.

  7. Time-Dependent Flow Properties of Transient Hydrogels with Temporal Network Junctions

    NASA Astrophysics Data System (ADS)

    Kaneda, Isamu; Koga, Tsuyoshi; Tanaka, Fumihiko

    The nonlinear rheological behavior under startup shear flows in aqueous solutions of telechelic hydrophobically ethoxylated urethane carrying branched alkyl end-chains, 2-decyl-tetradecyl, (referred to as C24-HEUR) was studied by strain-controlled rheomery. Unusual stress upturn (known as strain hardening), followed by the stress overshoot, was observed for 3 wt% aqueous solution above a critical shear rate. The phenomenon is explained by our recent transient network theory in terms of nonlinear chain stretching occurring during the stress build-up. Upon addition of glycerol, the relaxation time was shortened, while the equilibrium modulus increased with the concentration of glycerol. The stress upturn disappeared above a certain value of the glycerol concentration, strongly suggesting that glycerol affects the dynamics of the transient network through the interaction with the micellar junctions.

  8. Addition of surfactants in ozonated water cleaning for the suppression of functional group formation and particle adhesion on the SiO2 surface

    NASA Astrophysics Data System (ADS)

    Yang, Jahyun; Im, Kyungtaek; Lim, Sangwoo

    2011-04-01

    Various kinds of surfactants were added to a cleaning solution and deionized (DI) water, and their effect on the suppression of organic function group formation and particle adhesion to a SiO2 surface was analyzed using multi-internal reflection Fourier transform infrared spectroscopy. The results implied that attached organic functional groups are affected by the chemical structure of a surfactant in DI water. Furthermore, the addition of anionic glycolic acid ethoxylate 4-tert-butylphenyl ether (GAE4E) is the most effective in terms of preventing organic group attachment and particle adhesion to the SiO2 surface, whether it was added to the cleaning solution or post-cleaning rinse water, with or without polystyrene latex particles. Moreover, it was possible to completely prevent particle adhesion to the SiO2 surface with the proper addition of GAE4E in DIO3 solution.

  9. Application of liquid chromatography in polymer non-ionic antistatic additives analysis.

    PubMed

    González-Rodríguez, M Victoria; Dopico-García, M Sonia; Noguerol-Cal, Rosalía; Carballeira-Amarelo, Tania; López-Vilariño, José M; Fernández-Martínez, Gerado

    2010-11-01

    This article investigates the applicability of HPLC-UV, ultra performance LC-evaporative light-scattering detection (UPLC-ELSD), HPLC-ESI(+)-MS and HPLC-hybrid linear ion trap (LTQ) Orbitrap MS for the analysis of different non-ionic antistatic additives, Span 20, Span 60, Span 65, Span 80, Span 85 (sorbitan fatty acid esters), Atmer 129 (glycerol fatty acid ester) and Atmer 163 (ethoxylated alkylamine). Several alkyl chain length or different degrees of esterification of polyol derivatives can be present in commercial mixtures of these polymer additives. Therefore, their identification and quantification is complicated. Qualitative composition of the studied compounds was analysed by MS. HPLC-UV, UPLC-ELSD and HPLC-LTQ Orbitrap MS methods were applied to the quantitative determination of the different Spans, Atmer 129 and Atmer 163, respectively. Quality parameters of these methods were established and no derivatization was necessary.

  10. New tirucallane-type triterpenoid saponins from Sapindus mukorossi Gaetn.

    PubMed

    Ni, Wei; Hua, Yan; Teng, Rong-Wei; Kong, Yun-Cheung; Chen, Chang-Xiang

    2004-09-01

    Two new tirucallane-type triterpenoid saponins, sapimukoside C (1) and sapimukoside D (2), have been isolated from the roots of Sapindus mukorossi Gaetn. Their structures have been determined, on the basis of spectral and chemical analysis, as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L- arabinopyranosyl-(1-->3)]-beta-D-glucopyranosyl (21,23R)-epoxyl tirucalla-7,24-diene-(21S)-ethoxyl-3 beta-ol (1) and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-arabinopyranosyl-(1-->3)]- beta-D-glucopyranosyl (21,23R)-epoxyl tirucall-7,24-diene-(21S)-methoxyl-3 beta-ol (2).

  11. 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.

    PubMed

    Levine, Lanfang H; Garland, Jay L; Johnson, Jodie V

    2005-01-14

    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.

  12. Review on the fate of emerging contaminants during sludge anaerobic digestion.

    PubMed

    Stasinakis, Athanasios S

    2012-10-01

    Several research papers have been published during the last years investigating the occurrence, fate and effects of emerging contaminants (ECs) on sludge anaerobic digestion (AD). Literature review revealed that research has been mainly focused on specific groups of compounds (linear alkylbenzene sulphonates, nonylphenol ethoxylates, some pharmaceuticals, estrogens, phthalates), while there are fewer or no data for others (personal care products, perfluorinated compounds, brominated flame retardants, organotins, benzotriazoles, benzothiazoles, nanoparticles). AD operational parameters (sludge residence time, temperature), sludge characteristics (type of sludge, adaptation on the compound), physicochemical properties of ECs and co-metabolic phenomena seem to affect compounds' biodegradation. The use of sludge pretreatment methods does not seem to enhance ECs removal; whereas encouraging results have been reported when AD was combined with other treatment methods. Future efforts should be focused on better understanding of biotransformation processes and sorption phenomena occurred in anaerobic digesters, as well as on identification of (bio)transformation products.

  13. Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles.

    PubMed

    Fortunati, E; Rinaldi, S; Peltzer, M; Bloise, N; Visai, L; Armentano, I; Jiménez, A; Latterini, L; Kenny, J M

    2014-01-30

    Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

  14. 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.

  15. Nanostructured Gd-CeO2 electrolyte for solid oxide fuel cell by aqueous tape casting

    NASA Astrophysics Data System (ADS)

    Akbari-Fakhrabadi, A.; Mangalaraja, R. V.; Sanhueza, Felipe A.; Avila, Ricardo E.; Ananthakumar, S.; Chan, S. H.

    2012-11-01

    Gadolinia-doped ceria (Ce0.9Gd0.1O1.95, GDC) electrolyte was fabricated by aqueous-based tape casting method for solid oxide fuel cells (SOFCs). The ceramic powder prepared by combustion synthesis was used with poly acrylic acid (PAA), poly vinyl alcohol (PVA), poly ethylene glycol (PEG), Octanol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate and double distilled water as dispersant, binder, plasticizer, defoamer, surfactant and solvent respectively, to prepare stable GDC slurry. The conditions for preparing stable GDC slurries were studied and optimized by sedimentation, zeta potential and viscosity measurements. Green tapes with smooth surface, flexibility, thickness in the range of 0.35-0.4 mm and 45% relative green density were prepared. Conventional and flash sintering techniques were used and compared for densification which demonstrated the possibility of surpassing sintering at high temperatures and retarding related grain growth.

  16. Modeling of water-borne coating: stress relaxation of suspensions of colloids linked by telechelic HEUR polymers

    NASA Astrophysics Data System (ADS)

    Wang, Shihu; Larson, Ronald G.

    In water-borne coatings, the rheology of colloidal suspensions is modified by the presence of rheological modifiers, such as Hydrophobic Ethoxylated Urethane (HEUR) polymers. HEUR is a telechelic polymer with two hydrophobic tails (hydrophobes) and a long hydrophilic interblock consisting of poly(ethylene oxide), and its thickening effect is largely determined by the self-association of hydrophobes as well as their adsorption onto latex particles. Here we describe a model that simulates the complex interactions among latex particles due to the formation of bridges or superbridges via model HEURs. We calculate the stress relaxation of the system and identify different relaxation modes. We explore the relaxation time at different latex volume fractions, HEUR concentrations and energies of association between hydrophobes and latex particles, and discuss its relationship with the bridge or latex cluster formation. These results provide important insights for HEUR adsorption and water-borne coating rheology. We acknowledge the financial support from The Dow Chemical Company.

  17. Substolides A-G, germacrane sesquiterpenoids from Salvia substolonifera.

    PubMed

    Fang, Lianglian; Lin, Weiwei; Qiu, Guanguan; Cai, Yuan; Yan, Pengcheng; Cai, Xiaoqing; Li, Wencan; Tu, Hongfeng; Dong, Jianyong

    2015-12-01

    Chemical investigation of the whole plants of Salvia substolonifera E.Peter yielded seven germacrane sesquiterpenoids, substolides A-G (1-7), an ethoxylated artifact (8), and two known analogues, 6β-tigloyloxyglechomafuran (9) and castanin F (10). Four germacrane 8-acetylation derivatives (1a-4a) were obtained by chemical transformation. Their structures and relative or absolute configurations were elucidated by intensive spectroscopic methods, and single-crystal X-ray diffraction analysis. Compounds 1a-4a, and 5-10 were evaluated for their in vitro anti-angiogenic effects. Compounds 7 and 9 significantly inhibited VEGF-induced human umbilical vein endothelial cell (HUVEC) proliferation in vitro, with IC50 values of 16.15 ± 0.19, and 4.03 ± 0.26 μM, respectively. The structure activity relationship of these compounds is discussed.

  18. Removal of persistent polar pollutants through improved treatment of wastewater effluents (P-THREE).

    PubMed

    Knepper, T P; Barcelo, D; Lindner, K; Seel, P; Reemtsma, T; Ventura, F; De Wever, H; van der Voet, E; Gehringer, P; Schönerklee, M

    2004-01-01

    The EU-project P-THREE started with the establishment of analytical methods for persistent polar pollutants (P3) and quality assurance, followed by screening of P3 in influents and effluents of known wastewater (WW) treatment plants (TP), receiving waters and tap water produced thereof in several European countries. A final selection of analytes for further studies has been performed. Model MBR reactors have been constructed and an optimisation on synthetic wastewater spiked with P3 (linear alkylbenzene sulfonates (LAS), naphthalene sulfonates) has been performed. An initial dynamic modelling of treatment processes has also started. Advanced oxidation process (AOP) treatment has been done in groundwater with isoproturon and nonylphenol ethoxylates (NPEO). The analysis of individual P3 and potential degradation products was also performed. An integrated systeme analysis of the WW treatment processes has also been initiated.

  19. 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

  20. 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.

  1. 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.

  2. Seasonal distribution, source investigation and vertical profile of phenolic endocrine disrupting compounds in Dianchi Lake, China.

    PubMed

    Wang, Bin; Huang, Bin; Jin, Wei; Wang, Yu; Zhao, Shimin; Li, Farong; Hu, Ping; Pan, Xuejun

    2012-04-01

    Phenolic endocrine disrupting compounds, including nonylphenol-di-ethoxylate (NP2EO), nonylphenol-mono-ethoxylate (NP1EO), 4-nonylphenol (4-NP), bisphenol A (BPA), 4-cumylphenol (4-CP) and 4-tert-octylphenol (4-t-OP), were investigated in water, surface sediment and sediment cores in Dianchi Lake to track their seasonal distributions, pollution sources and historical trends. The concentrations of NP2EO, NP1EO, 4-NP, BPA, 4-CP and 4-t-OP were up to 295.14, 448.48, 45.28, 530.33, 8.96 and 21.37 ng L(-1) in water, and up to 297.11, 809.63, 4.58, 166.87, 3.62 and 40.69 ng g(-1) dry weight in surface sediment, respectively. Except BPA in water, concentrations of all the other phenolic compounds in both of the matrices were higher in January than in July, 2011. The concentrations decreased significantly with an increase in distance from the sampling locations which were adjacent to the urban areas (Kunming City, Chenggong City and Jinning City). The pollution of phenolic EDCs came mainly from industry, agriculture and daily life. The relationships between the concentrations of target compounds and the six water quality parameters were evaluated. There were significant positive correlations between concentrations of phenolic compounds in water and in surface sediment. For sediment cores, three clearly separated maxima occurred in segments 0-5 cm (the late 2000s), 5-10 cm (the early and mid of 2000s) and 20-25 cm (the mid of 1980s), respectively. NP2EO, NP1EO and BPA were the three dominant compounds in the lake.

  3. Enhanced oil recovery by CO/sub 2/ foam flooding. Second annual report. [109 references

    SciTech Connect

    Patton, John T.; Spence, Ken

    1980-11-01

    The objective is to identify commercially available additives which are effective in reducing the mobility of carbon dioxide, CO/sub 2/, thereby improving its efficiency in the recovery of tertiary oil, and which are low enough in cost to be economically attractive. During 1980 significant progress has been accomplished on each major contract objective. The apparatus, design and construction phase of this project is essentially complete. Correlation work on dynamic foam stability, in two-phase flow experiments in a linear sandpack, has shown that the most active foaming agents, as identified in static tests, may not necessarily be the best choices for mobility control in the field. The Alipal CD128-Monamid 150AD system, the leading foam generator in the static test, is slightly inferior to an ethoxylated alcohol, Neodol 23-6.5, that produces only a modest amount of foam in the static test. In the dynamic test, Neodol 23-6.5 lowered gas mobility by about a factor of 2 greater than the Alipal system. Both systems are outstanding in their performance, and further comparative tests are scheduled. A third structure which looks promising based on the interpretation of the above test is a Pluronic surfactant whose hydrophobe consists of polypropylene oxide rather than a linear alcohol as used in the Neodol surfactants. Additional tests on the hydrolysis rate of Alipal-type surfactants indicate that molecular breakdown may not be as rapid as at first suspected. Under neutral conditions the half-life of ethoxylated alcohol sulfates appears to be two to three years at a reservoir temperature of 120/sup 0/F. The Neodol and Pluronic structures should be even more stable.

  4. Monodisperse nonionic isoprenoid-type hexahydrofarnesyl ethylene oxide surfactants: high throughput lyotropic liquid crystalline phase determination.

    PubMed

    Fong, Celesta; Weerawardena, Asoka; Sagnella, Sharon M; Mulet, Xavier; Krodkiewska, Irena; Chong, Josephine; Drummond, Calum J

    2011-03-15

    The neat and lyotropic phase behavior of eight new ethylene oxide amphiphiles (EO = 1-8) with a hexahydrofarnesyl chain (3,7,11-trimethyldodecyl) and narrow polydispersity (>98.5% purity) is reported. Below five EO units the behavior of the neat surfactants show only a glass transition, Tg ∼ -90 °C. Above four EO units, crystallization (Tcrys) and crystal-isotropic liquid (Tm) transitions are also observed that increase with degree of ethoxylation of the surfactant headgroup. The lyotropic liquid crystalline phase behavior spans a complex spectrum of surfactant-water interfacial curvatures. Specifically, inverse phases are present below ambient temperatures for EO < 4, with HFarn(EO)2 exhibiting an inverse hexagonal (H(II)) phase stable to dilution. The phase diagram of HFarn(EO)3 displays both the gyroid (Ia3d) and double diamond (Pn3m) inverse bicontinuous cubic phases, with the latter being thermodynamically stable in excess water within the physiological regime. There is a strong preference for planar bilayer structures at intermediate headgroup ethoxylation, with the crossover to normal phases occurring at HFarn(EO)(7-8) which exhibits normal hexagonal (H(I)) and cubic (Q(I)) phases at ambient temperatures. The toxicity of colloidal dispersions of these EO amphiphiles was assayed against normal breast epithelial (HMEpiC) and breast cancer (MCF7) cell lines. The IC50 of the EO amphiphiles was similar in both cell lines with moderate toxicity ranging from ca. <5 to 140 μM in an in vitro cell viability assay. Observations are qualitatively rationalized in terms of the molecular geometry of the surfactant. The physicochemical behavior of the HFarnesyl ethylene oxide amphiphiles is compared to other ethylene oxide surfactants.

  5. Influence of conformational flexibility on self-assembly and luminescence properties of lanthanide coordination polymers with flexible exo-bidentate biphenol derivatives.

    PubMed

    Guo, Yanling; Dou, Wei; Zhou, Xiaoyan; Liu, Weisheng; Qin, Wenwu; Zang, Zhipeng; Zhang, Hongrui; Wang, Daqi

    2009-04-20

    To explore how nonplanar conformational distortions affect supramolecular self-assembly and properties of lanthanide complexes, we have designed and synthesized two new flexible exo-bidentate ligands derived from biphenol featuring two salicylamide pendant arms, 2,2'-bis{[(2'-benzylaminoformyl)phenoxyl]ethoxyl}-1,1'-biphenylene (L(I)) and 5,5'-dibromo-2,2'-bis{[(2'-benzylaminoformyl)phenoxyl]ethoxyl}-1,1'-biphenylene (L(II)). These two structurally related ligands can have different conformations and are used for constructing diverse lanthanide polymers with interesting luminescence properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, X-ray powder diffraction, and IR spectroscopy, four new coordination polymers have been determined using X-ray diffraction analysis. The coordination polymer type {Ln(2)(NO(3))(6)(L(I))(3).3H(2)O}(infinity) (Ln = Nd, Sm, Eu, Gd, Tb or Dy) displays a two-dimensional honeycomb-like framework in the ab plane, which can be regarded as a (6,3) topological network with neodymium atoms acting as "three-connected" centers. In contrast, the coordination polymer types {[Nd(NO(3))(3)(L(II))(CH(3)OH)] x CH(3)OH}(infinity) and [Ln(NO(3))(3)(L(II))(C(2)H(5)OH)](infinity) (Ln = Sm, Eu, Gd, Tb or Dy) possess single-stranded helix chains which can be further connected through intermolecular hydrogen bonds to form two-dimensional supramolecular sheets. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were investigated. The present work substantiates the claim that the supramolecular structure as well as the luminescence properties of the coordination polymer can be tuned by controlling the conformational distortion of a nonplanar flexible ligand in the supramolecular self-assembly.

  6. 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.

  7. Risk characterization of detergent surfactants in the Netherlands

    SciTech Connect

    Feijtel, T.; Plassche, E. van de

    1995-12-31

    The Dutch Soap Association (NVZ) and the Dutch Environmental Ministry (VROM) developed in 1991 an aquatic hazard priority list of all detergent ingredients. The agreed priority list consisted of linear alkylbenzene sulfonate (LAS), alcohol ethoxylates (AE), alcohol ethoxylated sulfates (AES), and soap. A stepwise or tiered risk assessment approach was adopted as the recommended approach to evaluate the risk of these surfactants. This implies that depending on the risk (or PEC/PNEC) ratio, the sequential test program or assessment would proceed further, to ensure adequate protection of the ecosystem. The agreed calculation scheme for the aquatic compartment is based on the comparison of the 90th percentile of Predicted Environmental Concentrations (PEC) in the Netherlands -- at 1,000 meter below the sewage outfall -- to the Predicted No Effect Concentration (PNEC) for ecosystems. The 90th percentile surfactant concentrations at 1,000 meter below the sewage outfall can be calculated using information or data on (1) release, (2) in-sewer removal, (3) treatment efficiency, (4) dilution and (5) instream-removal and/or measured in representative sites in The Netherlands. In addition, all toxicological data was critically reviewed by company experts and experts of RIVM and VROM to present a rationale for a sound database for the derivation of a Predicted No Effect Concentration (PNEC). It was concluded that the risk of LAS, AE and AES and soap for the aquatic environment is low. Also taking the estimated uncertainty into account, the predicted environmental concentrations are always considerably lower that the predicted no effect concentrations.

  8. Comparison of Oleo- vs Petro-Sourcing of Fatty Alcohols via Cradle-to-Gate Life Cycle Assessment.

    PubMed

    Shah, Jignesh; Arslan, Erdem; Cirucci, John; O'Brien, Julie; Moss, Dave

    2016-01-01

    Alcohol ethoxylates surfactants are produced via ethoxylation of fatty alcohol (FA) with ethylene oxide. The source of FA could be either palm kernel oil (PKO) or petrochemicals. The study aimed to compare the potential environmental impacts for PKO-derived FA (PKO-FA) and petrochemicals-derived FA (petro-FA). Cradle-to-gate life cycle assessment has been performed for this purpose because it enables understanding of the impacts across the life cycle and impact categories. The results show that petro-FA has overall lower average greenhouse gas (GHG) emissions (~2.97 kg CO2e) compared to PKO-FA (~5.27 kg CO2e). (1) The practices in land use change for palm plantations, (2) end-of-life treatment for palm oil mill wastewater effluent and (3) end-of-life treatment for empty fruit bunches are the three determining factors for the environmental impacts of PKO-FA. For petro-FA, n-olefin production, ethylene production and thermal energy production are the main factors. We found the judicious decisions on land use change, effluent treatment and solid waste treatment are key to making PKO-FA environmentally sustainable. The sensitivity results show the broad distribution for PKO-FA due to varying practices in palm cultivation. PKO-FA has higher impacts on average for 12 out of 18 impact categories evaluated. For the base case, when accounted for uncertainty and sensitivity analyses results, the study finds that marine eutrophication, agricultural land occupation, natural land occupation, fossil depletion, particulate matter formation, and water depletion are affected by the sourcing decision. The sourcing of FA involves trade-offs and depends on the specific practices through the PKO life cycle from an environmental impact perspective.

  9. Phthalates and nonylphenols in urban runoff: Occurrence, distribution and area emission factors.

    PubMed

    Björklund, Karin; Cousins, Anna Palm; Strömvall, Ann-Margret; Malmqvist, Per-Arne

    2009-08-01

    The urban water system is believed to be an important sink for the nonpoint-source pollutants nonylphenols and phthalates. The presence of nonylphenols (NPs), nonylphenol ethoxylates (NPEOs), and eight phthalates was analyzed in urban stormwater and sediment from three catchment areas in Sweden. Emission loads for these substances were then calculated for a specific urban catchment area. In addition, substance distribution in road runoff passing through a sedimentation facility was modeled using a modified QWASI-model for chemical fate. High concentrations of DEHP, DIDP and DINP (ethoxylate (6.6 and 20 microg/g dw, respectively) were found in the sediment. Aqueous concentrations of the pollutants varied considerably; branched NP was detected in concentrations up to 1.2 microg/L, whereas di(2-ethylhexyl) phthalate (DEHP), diisodecyl phthalate (DIDP), and diisononyl phthalate (DINP) were the most frequently detected phthalates in concentrations up to 5.0, 17 and 85 microg/L, respectively. The fate modeling demonstrated that predicted substance levels in water agreed well with measured levels, whereas the modeled sediment levels were underestimated. Calculation of catchment area emission factors from an urban highway environment revealed that as much as 2.1 kg of total phthalates and 200 g of NP and NPEOs may be emitted per hectare and year. The results indicate that all monitored phthalates, branched NPs and lower NPEOs are present in Swedish urban water systems. The long-chain phthalates DIDP and DINP are believed to occur at higher concentrations than other phthalates because of their higher environmental persistence and their increasing use in Sweden.

  10. 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

  11. 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.

  12. Characterization of biodegradation intermediates of nonionic surfactants by MALDI-MS. 2. Oxidative biodegradation profiles of uniform octylphenol polyethoxylate in 18O-labeled water.

    PubMed

    Sato, Hiroaki; Shibata, Atsushi; Wang, Yang; Yoshikawa, Hiromichi; Tamura, Hiroto

    2003-01-01

    This paper reports the characterization of the biodegradation intermediates of octylphenol octaethoxylate (OP(8)EO) by means of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The biodegradation test study was carried out in a pure culture (Pseudomonas putida S-5) under aerobic conditions using OP(8)EO as the sole carbon source and (18)O-labeled water as an incubation medium. In the MALDI-MS spectra of biodegraded samples, a series of OP(n)EO molecules with n = 2-8 EO units and their corresponding carboxylic acid products (OP(n)EC) were observed. The use of purified OP(8)EO enabled one to distinguish the shortened OPEO molecules as biodegradation intermediates. Furthermore, the formation of OP(8)EC (the oxidized product of OP(8)EO) supported the notion that terminal oxidation is a step in the biodegradation process. When biodegradation study was carried out in (18)O-labeled water, incorporation of (18)O atoms into the carboxyl group was observed for OPEC, while no incorporation was observed for the shortened OPEO products. These results could provide some rationale to the biodegradation mechanism of alkylphenol polyethoxylates.

  13. Effects of Ginkgo biloba constituents on fruit-infesting behavior of codling moth (Cydia pomonella) in apples.

    PubMed

    Pszczolkowski, Maciej A; Durden, Kevin; Sellars, Samantha; Cowell, Brian; Brown, John J

    2011-10-26

    Codling moth, Cydia pomonella (L.), is a cosmopolitan pest of apple, potentially causing severe damage to the fruit. Currently used methods of combating this insect do not warrant full success or are harmful to the environment. The use of plant-derived semiochemicals for manipulation with fruit-infesting behavior is one of the new avenues for controlling this pest. Here, we explore the potential of Ginkgo biloba and its synthetic metabolites for preventing apple feeding and infestation by neonate larvae of C. pomonella. Experiments with crude extracts indicated that deterrent constituents of ginkgo are present among alkylphenols, terpene trilactones, and flavonol glycosides. Further experiments with ginkgo synthetic metabolites of medical importance, ginkgolic acids, kaempferol, quercetin, isorhamnetin, ginkgolides, and bilobalide, indicated that three out of these chemicals have feeding deterrent properties. Ginkgolic acid 15:0 prevented fruit infestation at concentrations as low as 1 mg/mL, bilobalide had deterrent effects at 0.1 mg/mL and higher concentrations, and ginkgolide B at 10 mg/mL. On the other hand, kaempferol and quercetin promoted fruit infestation by codling moth neonates. Ginkgolic acids 13:0, 15:1, and 17:1, isorhamnetin, and ginkgolides A and C had no effects on fruit infestation-related behavior. Our research is the first report showing that ginkgo constituents influence fruit infestation behavior and have potential applications in fruit protection.

  14. Anthropogenic tracers, endocrine disrupting chemicals, and endocrine disruption in Minnesota lakes

    USGS Publications Warehouse

    Writer, J.H.; Barber, L.B.; Brown, G.K.; Taylor, H.E.; Kiesling, R.L.; Ferrey, M.L.; Jahns, N.D.; Bartell, S.E.; Schoenfuss, H.L.

    2010-01-01

    Concentrations of endocrine disrupting chemicals and endocrine disruption in fish were determined in 11 lakes across Minnesota that represent a range of trophic conditions and land uses (urban, agricultural, residential, and forested) and in which wastewater treatment plant discharges were absent. Water, sediment, and passive polar organic integrative samplers (POCIS) were analyzed for steroidal hormones, alkylphenols, bisphenol A, and other organic and inorganic molecular tracers to evaluate potential non-point source inputs into the lakes. Resident fish from the lakes were collected, and caged male fathead minnows were deployed to evaluate endocrine disruption, as indicated by the biological endpoints of plasma vitellogenin and gonadal histology. Endocrine disrupting chemicals, including bisphenol A, 17??-estradiol, estrone, and 4-nonylphenol were detected in 90% of the lakes at part per trillion concentrations. Endocrine disruption was observed in caged fathead minnows and resident fish in 90% of the lakes. The widespread but variable occurrence of anthropogenic chemicals in the lakes and endocrine disruption in fish indicates that potential sources are diverse, not limited to wastewater treatment plant discharges, and not entirely predictable based on trophic status and land use. ?? 2010.

  15. Development of a short-term in situ caging methodology to assess long-term effects of industrial and municipal discharges on salmon smolts.

    PubMed

    Jardine, Timothy D; MacLatchy, Deborah L; Fairchild, Wayne L; Chaput, Gerald; Brown, Scott B

    2005-11-01

    Trial experiments to develop an in situ method for determining effects of short-term exposure to contaminants on salmon during the sensitive smolt stage were carried out. Wild Atlantic salmon (Salmo salar) smolts were caged at various estuarine locations in northeast New Brunswick, Canada at different levels of anthropogenic impact in 2000 and 2001. Survival, growth (weight and K), and feeding (delta(13)C and delta(15)N) parameters were measured following summer grow-out at a hatchery. A summary of distributions of the four parameters indicated that smolts caged at locations receiving lower levels of industrial and municipal discharges feed and grow better than those caged at sites receiving higher levels. The findings, however, were not repeatable between the 2 years studied. The observed inconsistency between years may be a consequence of the relatively low concentrations of alkylphenolic contaminants (putative causative agents) and overall steroidogenic potency in river water at the time of caging. Differences in temperature and salinity from 2000 to 2001 may have further confounded comparisons across treatments and between years. In future studies, caging in closer proximity to industrial and municipal discharges or in systems with higher concentrations of waterborne contaminants or impoundments would help further the assessment and applicability of this methodology and allow a more robust comparison of smolt feeding and growth among reference and exposure sites.

  16. Affinity purification using recombinant PXR as a tool to characterize environmental ligands.

    PubMed

    Dagnino, Sonia; Bellet, Virginie; Grimaldi, Marina; Riu, Anne; Aït-Aïssa, Sélim; Cavaillès, Vincent; Fenet, Hélène; Balaguer, Patrick

    2014-02-01

    Many environmental endocrine disrupting compounds act as ligands for nuclear receptors. The human pregnane X receptor (hPXR), for instance, is activated by a variety of environmental ligands such as steroids, pharmaceutical drugs, pesticides, alkylphenols, polychlorinated biphenyls and polybromo diethylethers. Some of us have previously reported the occurrence of hPXR ligands in environmental samples but failed to identify them. The aim of this study was to test whether a PXR-affinity column, in which recombinant hPXR was immobilized on solid support, could help the purification of these chemicals. Using PXR ligands of different affinity (10 nM < EC50 < 10 μM), we demonstrated that the PXR-affinity preferentially column captured ligands with medium to high affinities (EC50 < 1 μM). Furthermore, by using the PXR-affinity column to analyze an environmental sample containing ERα, AhR, AR, and PXR activities, we show that (i) half of the PXR activity of the sample was due to compounds with medium to high affinity for PXR and (ii) PXR shared ligands with ERα, AR, and AhR. These findings demonstrate that the newly developed PXR-affinity column coupled to reporter cell lines represents a valuable tool for the characterization of the nature of PXR active compounds and should therefore guide and facilitate their further analysis.

  17. Multiresidue analysis of endocrine-disrupting compounds and perfluorinated sulfates and carboxylic acids in sediments by ultra-high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Cavaliere, Chiara; Capriotti, Anna Laura; Ferraris, Francesca; Foglia, Patrizia; Samperi, Roberto; Ventura, Salvatore; Laganà, Aldo

    2016-03-18

    A multiresidue analytical method for the determination of 11 perfluorinated compounds and 22 endocrine-disrupting compounds (ECDs) including 13 natural and synthetic estrogens (free and conjugated forms), 2 alkylphenols, 1 plasticiser, 2 UV-filters, 1 antimicrobial, and 2 organophosphorus compounds in sediments has been developed. Ultrasound-assisted extraction followed by solid phase extraction (SPE) with graphitized carbon black (GCB) cartridge as clean-up step were used. The extraction process yield was optimized in terms of solvent composition. Then, a 3(2) experimental design was used to optimize solvent volume and sonication time by response surface methodology, which simplifies the optimization procedure. The final extract was analyzed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The optimized sample preparation method is simple and robust, and allows recovery of ECDs belonging to different classes in a complex matrix such as sediment. The use of GCB for SPE allowed to obtain with a single clean-up procedure excellent recoveries ranging between 75 and 110% (relative standard deviation <16%). The developed methodology has been successfully applied to the analysis of ECDs in sediments from different rivers and lakes of the Lazio Region (Italy). These analyses have shown the ubiquitous presence of chloro-substituted organophosphorus flame retardants and bisphenol A, while other analyzed compounds were occasionally found at concentration between the limit of detection and quantification.

  18. Occurrence of endocrine disrupting compounds in five estuaries of the northwest coast of Spain: Ecological and human health impact.

    PubMed

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

    2015-07-01

    The occurrence and spatial distribution of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A were examined in five estuaries along the Northwest coastal area of Spain. As far as we know, no previous works about this topic could be found in the literature. A total of 98 seawater samples were collected during May 2011-July 2012 and analyzed by a highly sensitive DLLME-LC-MS/MS methodology recently developed. Results indicated nonylphenol was the most ubiquitous compound with maximal concentration of 0.337 μg L(-1) (Ría de Vigo). The environmental quality standards (EQS) established in Directive 2013/39/EU for 4-tert-octylphenol were slightly exceeded in some sampling points. Fishing harbours, water treatment plant and industrial discharges were supposed as the main sources of contamination. Low and medium ecological risk was determined in all estuaries. Possible endocrine effects on biota and population were estimated in terms of estrogenic activity and daily intake respectively, and no risk was found in any case.

  19. Identification of toxic substances in United Kingdom estuaries

    SciTech Connect

    Thomas, K.V.; Thain, J.E.; Waldock, M.J.

    1999-03-01

    The organic load of bulk water samples, collected from five industrially impacted estuaries, was extracted using solid-phase extraction. Where toxicity was demonstrated using a Tisbe battagliai bioassay, a toxicity directed fractionation scheme was applied to isolate causal compounds. To reduce the complexity of the extracts toxicity profiles were obtained following solid-phase fractionation and reverse-phase HPLC. Candidate toxic contaminants were identified by GC-MS. All procedures were evaluated with a series of reference compounds of widely differing polarity. The method was successful in identifying a number of compounds, which traditionally have not been selected for inclusion in monitoring programs, as the probable cause of detrimental environmental effect. The results suggest that chlorinated phenols are a major contributor to poor water quality in the lower reaches of the river Tyne and alkylphenol surfactant metabolites in the river Tees. Other compounds, as yet unidentified, also contribute to poor water quality. It is suggested that the identified compounds should now be surveyed more widely and considered for inclusion in future monitoring programs.

  20. Sustainable biodegradation of phenolic endocrine-disrupting chemicals by Phragmites australis-rhizosphere bacteria association.

    PubMed

    Toyama, T; Ojima, T; Tanaka, Y; Mori, K; Morikawa, M

    2013-01-01

    The efficacy of two rhizobacteria (Sphingobium fuliginis TIK1 and Sphingobium sp. IT4) of Phragmites australis for the sustainable treatment of water polluted with phenolic endocrine-disrupting chemicals (EDCs) was investigated. Strains TIK1 and IT4 have recently been isolated from Phragmites rhizosphere and shown to degrade various 4-alkylphenols-TIK1 via phenolic ring hydroxylation and meta-cleavage and IT4 via ipso-hydroxylation. The two strains also degraded bisphenol A (BPA), bisphenol B, bisphenol E, bisphenol F, bisphenol P and bisphenol S (BPS). Thus, strains TIK1 and IT4 have wide degradation spectra for phenolic EDCs. The two strains utilized Phragmites root extracts as a sole carbon source and sustainably colonized Phragmites roots, where they degraded phenolic EDCs. In sequencing batch reactor experiments using Phragmites in association with TIK1 or IT4, both associations repeatedly removed phenolic EDCs from polluted secondary effluent water (BPA, BPS, 4-tert-butylphenol, 4-tert-octylphenol and 4-nonylphenol) from polluted secondary effluent water. The results suggest that hydroponic systems using Phragmites-TIK and Phragmites-IT4 associations would be useful for sustainable treatment of polluted waters containing various phenolic EDCs.

  1. Toxics Use Reduction in the Home: Lessons Learned from Household Exposure Studies

    PubMed Central

    Dunagan, Sarah C.; Dodson, Robin E.; Rudel, Ruthann A.; Brody, Julia G.

    2010-01-01

    Workers and fence-line communities have been the first to benefit from the substantial reductions in toxic chemical use and byproducts in industrial production resulting from the Massachusetts Toxics Use Reduction Act (TURA). As TURA motivates reformulation of products as well as retooling of production processes, benefits could extend more broadly to large-scale reductions in everyday exposures for the general population. Household exposure studies, including those conducted by Silent Spring Institute, show that people are exposed to complex mixtures of indoor toxics from building materials and a myriad of consumer products. Pollutants in homes are likely to have multiple health effects because many are classified as endocrine disrupting compounds (EDCs), with the ability to interfere with the body's hormone system. Product-related EDCs measured in homes include phthalates, halogenated flame retardants, and alkylphenols. Silent Spring Institute's chemical analysis of personal care and cleaning products confirms many are potential sources of EDCs, highlighting the need for a more comprehensive toxics use reduction (TUR) approach to reduce those exposures. Toxics use reduction targeted at EDCs in consumer products has the potential to substantially reduce occupational and residential exposures. The lessons that have emerged from household exposure research can inform improved chemicals management policies at the state and national levels, leading to safer products and widespread health and environmental benefits. PMID:21516227

  2. Endocrine-disrupting chemicals in coastal lagoons of the Po River delta: sediment contamination, bioaccumulation and effects on Manila clams.

    PubMed

    Casatta, Nadia; Stefani, Fabrizio; Pozzoni, Fiorenzo; Guzzella, Licia; Marziali, Laura; Mascolo, Giuseppe; Viganò, Luigi

    2016-06-01

    The large estuary that the River Po forms at its confluence into the Adriatic Sea comprises a multitude of transitional environments, including coastal lagoons. This complex system receives the nutrients transported by the River Po but also its load of chemical contaminants, which may pose a substantial (eco)toxicological risk. Despite the high ecological and economic importance of these vulnerable environments, there is a substantial lack of information on this risk. In light of the recent amendments of the European Water Framework Directive (2013/39/EU), the present study investigated the sediment contamination of six coastal lagoons of the Po delta and its effects on Manila clams (Ruditapes philippinarum), exposed in situ for 3 months. Sediment contamination and clam bioaccumulation of a wide range of chemicals, i.e. trace metals (Cd, Cr, Ni, Hg, Pb, As), polybrominated diphenyl ethers (PBDEs), alkylphenols (APs), organochlorine compounds (PCBs, DDTs), polycyclic aromatic hydrocarbons (PAHs) and organotins (TPhT, TBT), suggested a southward increase related to the riverine transports. Where the River Po influence was more direct, the concentrations of contaminants were higher, with nonylphenol and BDE-209 exceeding sediment quality guidelines. Biometric indicators suggested the influence of contamination on organism health; an inverse relationship between PBDEs in sediments and clam condition index has been found, as well as different biota-sediment accumulation factors (BSAFs) in the lagoons.

  3. Stabilization of asphaltenes in aliphatic solvents using alkylbenzene-derived amphiphiles. 2. Study of the asphaltene-amphiphile interactions and structures using Fourier transform infrared spectroscopy and small-angle X-ray scattering techniques

    SciTech Connect

    Chang, C.L.; Fogler, H.S. )

    1994-06-01

    In the preceding paper in this issue, the influence of the chemical structure of a series of alkylbenzene-derived amphiphiles on the stabilization of asphaltenes was described. In this paper, we present the results of using Fourier transform infrared (FTIR) spectroscopy and small-angle X-ray scattering (SAXS) techniques to study the interaction between asphaltenes and two alkylbenzene-derived amphiphiles, p-alkylphenol and p-alkylbenzenesulfonic acid. FTIR spectroscopy was used to characterize and quantify the acid-base interactions between asphaltenes and amphiphiles. It was found that asphaltenes could hydrogen-bond to p-dodecylphenol amphiphiles. The hydrogen-bonding capacity of asphaltenes was estimated to be 1.6-2.0 mmol/g of asphaltene. On the other hand, the FTIR spectroscopic study indicated that asphaltenes had a complicated acid-base interaction with p-dodecylbenzenesulfonic acid (DBSA) amphiphiles with a stoichiometry of about 1.8 mmol of DBSA/g of asphaltene. The UV/vis spectroscopic study suggested that asphaltenes and DBSA could associate into large electronic conjugated complexes. Physical evidence of the association between asphaltenes and amphiphiles was obtained by SAXS measurements. 27 refs., 10 figs.

  4. Stabilization of asphaltenes in aliphatic solvents using alkylbenzene-derived amphiphiles. 1. Effect of the chemical structure of amphiphiles on asphaltene stabilization

    SciTech Connect

    Chang, C.L.; Fogler, H.S. )

    1994-06-01

    Stabilization of crude oil asphaltenes in apolar alkane solvents was investigated using a series of alkylbenzene-derived amphiphiles as the asphaltene stabilizers. In this paper (i.e., part I), we present the study on the influences of the chemical structure of these amphiphiles on the effectiveness of asphaltene solubilization and on the strength of asphaltene-amphiphile interaction using both UV/vis and FTIR spectroscopies. The results showed that the amphiphile's effectiveness of asphaltene stabilization was primarily controlled by the polarity of the amphiphile's head group and the length of the amphiphile's alkyl tail. Increasing the acidity of the amphiphile's head group could promote the amphiphile's ability to stabilize asphaltenes by increasing the acid-base attraction between asphaltenes and amphiphiles. On the other hand, although decreasing the amphiphile's tail length increased the asphaltene-amphiphile attraction slightly, it still required a minimum tail length (six carbons for p-alkylphenol amphiphiles) for amphiphiles to form stable steric layers around asphaltenes. We also found additional acidic side groups of amphiphiles could further improve the amphiphile's ability to stabilize asphaltenes. The effect of the molecular weight of alkane solvents on the amphiphile's ability to stabilize asphaltenes was also studied. 18 refs., 12 figs., 3 tabs.

  5. Combined biological and chemical assessment of estrogenic activities in wastewater treatment plant effluents.

    PubMed

    Aerni, Hans-Rudolf; Kobler, Bernd; Rutishauser, Barbara V; Wettstein, Felix E; Fischer, René; Giger, Walter; Hungerbühler, Andreas; Marazuela, M Dolores; Peter, Armin; Schönenberger, René; Vögeli, A Christiane; Suter, Marc J-F; Eggen, Rik I L

    2004-02-01

    Five wastewater treatment plant effluents were analyzed for known endocrine disrupters and estrogenicity. Estrogenicity was determined by using the yeast estrogen screen (YES) and by measuring the blood plasma vitellogenin (VTG) concentrations in exposed male rainbow trout (Oncorhynchus mykiss). While all wastewater treatment plant effluents contained measurable concentrations of estrogens and gave a positive response with the YES, only at two sites did the male fish have significantly increased VTG blood plasma concentrations after the exposure, compared to pre-exposure concentrations. Estrone (E1) concentrations ranged up to 51 ng L(-1), estradiol (E2) up to 6 ng L(-1), and ethinylestradiol (EE2) up to 2 ng L(-1) in the 90 samples analyzed. Alkylphenols, alkylphenolmonoethoxylates and alkylphenoldiethoxylates, even though found at microg L(-1) concentrations in effluents from wastewater treatment plants with a significant industrial content, did not contribute much to the overall estrogenicity of the samples taken due to their low relative potency. Expected estrogenicities were calculated from the chemical data for each sample by using the principle of concentration additivity and relative potencies of the various chemicals as determined with the yeast estrogen screen. Measured and calculated estradiol equivalents gave the same order of magnitude and correlated rather well (R(2)=0.6).

  6. Demasculinization of male fish by wastewater treatment plant effluent

    USGS Publications Warehouse

    Vajda, A.M.; Barber, L.B.; Gray, J.L.; Lopez, E.M.; Bolden, A.M.; Schoenfuss, H.L.; Norris, D.O.

    2011-01-01

    Adult male fathead minnows (Pimephales promelas) were exposed to effluent from the City of Boulder, Colorado wastewater treatment plant (WWTP) under controlled conditions in the field to determine if the effluent induced reproductive disruption in fish. Gonadal intersex and other evidence of reproductive disruption were previously identified in white suckers (Catostomus commersoni) in Boulder Creek downstream from this WWTP effluent outfall. Fish were exposed within a mobile flow-through exposure laboratory in July 2005 and August 2006 to WWTP effluent (EFF), Boulder Creek water (REF), or mixtures of EFF and REF for up to 28 days. Primary (sperm abundance) and secondary (nuptial tubercles and dorsal fat pads) sex characteristics were demasculinized within 14 days of exposure to 50% and 100% EFF. Vitellogenin was maximally elevated in both 50% and 100% EFF treatments within 7 days and significantly elevated by 25% EFF within 14 days. The steroidal estrogens 17??-estradiol, estrone, estriol, and 17??-ethynylestradiol, as well as estrogenic alkylphenols and bisphenol A were identified within the EFF treatments and not in the REF treatment. These results support the hypothesis that the reproductive disruption observed in this watershed is due to endocrine-active chemicals in the WWTP effluent. ?? 2011 Elsevier B.V.

  7. Distribution and assessment of surface water contamination by application of chemometric and deterministic models

    NASA Astrophysics Data System (ADS)

    Terrado, Marta; Lavigne, Martin-Pierre; Tremblay, Sebastien; Duchesne, Sophie; Villeneuve, Jean-Pierre; Rousseau, Alain N.; Barceló, Damià; Tauler, Romà

    2009-05-01

    SummaryChemometrics and deterministic modelling is proposed to extract useful information from data sets obtained in environmental monitoring studies. Contamination from organic compounds in the Llobregat River basin (Catalunya, NE Spain) was investigated for the period 2003-2006. From the application of Multivariate Curve Resolution using Alternating Least Squares (MCR-ALS), five different patterns of organic compound contamination are identified, explaining nearly 65% of the total variance of data. While pollution from chlorinated pesticides and alkylphenols shows lower levels in recent years, contamination resulting from PAHs has a rather constant distribution in space as well as in time. On the other hand, diffuse pollution from an agricultural pattern with terbutryn and chlorpyrifos increases in the year 2006 as compared to 2005. Dynamics of the products describing this last agricultural pattern are modeled using the modelling system GIBSI. Existing cultures in the studied area as well as possible pesticide usages and application loads are considered for the simulation of pesticide concentrations in water. In this way, the transfer of pesticides applied on soils to the water system is assessed and compared with other possible scenarios involving alternative practices. A new modelling approach based on considering different contamination patterns instead of using individual variables and chemicals is proposed at the end of this work.

  8. Mass-analyzed threshold ionization spectroscopy of p-methylphenol and p-ethylphenol cations and the alkyl substitution effect

    NASA Astrophysics Data System (ADS)

    Lin, Jung Lee; Li, Changyong; Tzeng, Wen Bih

    2004-06-01

    The mass-analyzed threshold ionization (MATI) spectra of p-methylphenol and p-ethylphenol have been recorded by ionizing via various vibronic levels. The adiabatic ionization energies (IEs) of p-methylphenol and p-ethylphenol are determined to be 65918±5 and 65628±5 cm-1, which are less than that of phenol by 2707 and 2997 cm-1, respectively. This redshift indicates that the interaction between the alkyl group and the ring of alkylphenols in the cationic D0 state is greater than that in the neutral S0 state. Moreover, a longer alkyl group gives rise to a greater redshift in the IE. Analysis of the MATI spectra shows that most of the active modes are related to the in-plane ring vibrations of these two cations. However, the length of the alkyl group has an insignificant effect on the frequency of the observed ring vibrations. No band with frequency less than 350 cm-1 is observed for the p-methylphenol cation. In contrast, many low-frequency bands resulting from the characteristic motions (e.g., the C-C2H5 torsion and C-C2H5 and C-OH bending vibrations) appear in the MATI spectra of p-ethylphenol. The present results show that the ethyl group enhances the substituent-sensitive and many large-amplitude vibrations of the cation.

  9. In vitro biomonitoring in polar extracts of solid phase matrices reveals the presence of unknown compounds with estrogenic activity.

    PubMed

    Legler, J; Leonards, P; Spenkelink, A; Murk, A J

    2003-01-01

    Determination of estrogenic activity has so far mainly concentrated on the assessment of compounds in surface water and effluent. This study is one of the first to biomonitor (xeno-)estrogens in sediment, suspended particulate matter and aquatic organisms. The relatively polar acetone extracts from these solid phase matrices do not contain the well-known estrogenic compounds such as hormones, alkylphenols and phthalates. An in vitro 'estrogen receptor-mediated chemical activated luciferase gene expression' (ER-CALUX) assay was applied to samples from various locations in the Netherlands. Estrogenic activity measured in polar fractions of particulate matter and sediment extracts ranged from below detection limit to up to 4.5 pmol estradiol equivalents (EEQ)/g dry weight. Estrogenic activity in freshwater river sediments was up to five times higher compared to sediments from large lakes and coastal locations. Tissue extracts EEQs were determined in bream (Abramis brama), flounder (Platichthysflesus), freshwater mussels (Dreissena polymorpha) and marine mussels (Mytilus edulis). The highest biota EEQ levels were found in the freshwater zebra mussel (30 pmol EEQ/g lipid). One sample site showed greatly elevated EEQs in sediment and biota, which correlated with effects found in the wild populations of bream. The EEQ activity of the unknown compounds in the polar fraction mostly was much higher than the calculated EEQ levels based on known estrogens in the non-polar fraction (previously published data).

  10. Evaluation of the Presence of Endocrine-Disrupting Compounds in Dissolved and Solid Wastewater Treatment Plant Samples of Gran Canaria Island (Spain)

    PubMed Central

    Vega-Morales, T.; Sosa-Ferrera, Z.; Santana-Rodríguez, J. J.

    2013-01-01

    Liquid and solid samples from two wastewater treatment plants (WWTPs) on Gran Canaria Island (Spain) have been tested for the presence of compounds with endocrine-disrupting properties. The selected degradation stages were sampled bimonthly from each WWTP over the 12-month period from July 2010 to July 2011. The analytical methods used for the determination of the endocrine-disrupting compounds (EDCs) were based on on-line solid phase extraction, microwave-assisted extraction (MAE), and ultrasonic-assisted extraction (UAE) coupled to UHPLC-MS/MS. All of the hyphenated methodologies employed in this work showed good recoveries (72–104%) and sensitivities, with LODs lower than 7.0 ng L−1 and 6.3 ng g−1 for the dissolved and solid fractions, respectively. We have also evaluated the estrogenicity of the samples in terms of their estradiol equivalent concentrations (EEQs). The chemical analysis of the selected EDCs revealed fairly low concentrations for both natural and synthetic oestrogens, alkylphenolic compounds, and bisphenol-A in each of the dissolved, particulate, and sludge samples (ng L−1 or ng g−1). However, the estimated estrogenic activity indicated that the majority of samples could represent an important environmental risk, clearly surpassing the threshold to exert deleterious consequences on living beings. PMID:24163820

  11. Heterocyclic aromatic hydrocarbons show estrogenic activity upon metabolization in a recombinant transactivation assay.

    PubMed

    Brinkmann, Markus; Maletz, Sibylle; Krauss, Martin; Bluhm, Kerstin; Schiwy, Sabrina; Kuckelkorn, Jochen; Tiehm, Andreas; Brack, Werner; Hollert, Henner

    2014-05-20

    Heterocyclic aromatic hydrocarbons (hetero-PAHs) are increasingly studied at contaminated sites; especially at former industrial facilities where coal tar-oil was handled, e.g., wood treatment plants, high concentrations of hetero-PAHs are frequently detected in groundwater plumes. In previous studies, fractions of groundwater with high estrogenic activity contained hetero-PAHs and their hydroxylated metabolites. To evaluate this preliminary evidence, selected hetero-PAHs were screened for their estrogenic activity in lyticase yeast estrogen screen (LYES) and ER CALUX. All tested substances were inactive in the LYES. Hetero-PAHs such as acridine, xanthene, indole, 2-methylbenzofuran, 2,3-dimethylbenzofuran, dibenzofuran, dibenzothiophene, quinoline, and 6-methylquinoline were positive in the ER CALUX, with estradiol equivalence factors (EEFs) from 2.85 × 10(-7) to 3.18 × 10(-5). The EEF values of these substances were comparable to those of other xenoestrogens (e.g., alkylphenols or bisphenol A) that are sometimes found in surface water. Chemical analyses revealed that T47Dluc cells could metabolize most of the substances. Among the metabolites (tentatively) identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS) were hydroxides and their keto tautomers, sulfates, sulfoxides, and N-oxides. Because of their high concentrations measured in groundwater, we conclude that hetero-PAHs and metabolites may be a potential risk and should be the subject of further research.

  12. Simultaneous determination of 20 trace organic chemicals in waters by solid-phase extraction (SPE) with triple-quadrupole mass spectrometer (QqQ-MS) and hybrid quadrupole Orbitrap high resolution MS (Q-Orbitrap-HRMS).

    PubMed

    Chen, Wei; Huang, Huanfang; Chen, Chang-Er; Qi, Shihua; Price, Oliver R; Zhang, Hao; Jones, Kevin C; Sweetman, Andrew J

    2016-11-01

    A sensitive method for simultaneous determination of 20 trace organic chemicals (TOrCs, including preservatives, antioxidants, disinfectants, oestrogens, alkyl-phenols and bisphenol-A) in surface water and wastewater has been developed and validated based on the optimisation of solid-phase extraction (SPE) followed by liquid chromatography-mass spectrometry (LC-MS) analysis. 500 mL acidified (pH = 2.5) water samples were pre-concentrated by Supel-Select HLB cartridge (200 mg, 6 mL) and eluted with 12 mL mixture of acetonitrile and ethyl acetate (50:50, v/v). This optimised SPE procedure could provide >75% recoveries for the majority of TOrCs. The instrumental methods were developed using two different LC-MS systems: a triple-quadrupole MS (QqQ-MS) and a hybrid quadrupole Orbitrap high resolution MS (Q-Orbitrap-HRMS). Both showed good performance data, but the former system provided better linearity and method precision, with the latter system providing 2-33 times lower detection limits. Different matrix effects were observed for both systems: No remarkable matrix effects were observed for Q-Orbitrap-HRMS but significant matrix effects were found in influent and river water samples for the QqQ-MS. This analytical method was subsequently employed to analyse the TOrCs in river waters and wastewaters from China successfully, which confirmed its applicability to environmental samples.

  13. Transport and release of chemicals from plastics to the environment and to wildlife.

    PubMed

    Teuten, Emma L; Saquing, Jovita M; Knappe, Detlef R U; Barlaz, Morton A; Jonsson, Susanne; Björn, Annika; Rowland, Steven J; Thompson, Richard C; Galloway, Tamara S; Yamashita, Rei; Ochi, Daisuke; Watanuki, Yutaka; Moore, Charles; Viet, Pham Hung; Tana, Touch Seang; Prudente, Maricar; Boonyatumanond, Ruchaya; Zakaria, Mohamad P; Akkhavong, Kongsap; Ogata, Yuko; Hirai, Hisashi; Iwasa, Satoru; Mizukawa, Kaoruko; Hagino, Yuki; Imamura, Ayako; Saha, Mahua; Takada, Hideshige

    2009-07-27

    Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2'-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g(-1) to microg g(-1). Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub microg l(-1) to mg l(-1) and were correlated with the level of economic development.

  14. Transport and release of chemicals from plastics to the environment and to wildlife

    PubMed Central

    Teuten, Emma L.; Saquing, Jovita M.; Knappe, Detlef R. U.; Barlaz, Morton A.; Jonsson, Susanne; Björn, Annika; Rowland, Steven J.; Thompson, Richard C.; Galloway, Tamara S.; Yamashita, Rei; Ochi, Daisuke; Watanuki, Yutaka; Moore, Charles; Viet, Pham Hung; Tana, Touch Seang; Prudente, Maricar; Boonyatumanond, Ruchaya; Zakaria, Mohamad P.; Akkhavong, Kongsap; Ogata, Yuko; Hirai, Hisashi; Iwasa, Satoru; Mizukawa, Kaoruko; Hagino, Yuki; Imamura, Ayako; Saha, Mahua; Takada, Hideshige

    2009-01-01

    Plastics debris in the marine environment, including resin pellets, fragments and microscopic plastic fragments, contain organic contaminants, including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons, petroleum hydrocarbons, organochlorine pesticides (2,2′-bis(p-chlorophenyl)-1,1,1-trichloroethane, hexachlorinated hexanes), polybrominated diphenylethers, alkylphenols and bisphenol A, at concentrations from sub ng g–1 to µg g–1. Some of these compounds are added during plastics manufacture, while others adsorb from the surrounding seawater. Concentrations of hydrophobic contaminants adsorbed on plastics showed distinct spatial variations reflecting global pollution patterns. Model calculations and experimental observations consistently show that polyethylene accumulates more organic contaminants than other plastics such as polypropylene and polyvinyl chloride. Both a mathematical model using equilibrium partitioning and experimental data have demonstrated the transfer of contaminants from plastic to organisms. A feeding experiment indicated that PCBs could transfer from contaminated plastics to streaked shearwater chicks. Plasticizers, other plastics additives and constitutional monomers also present potential threats in terrestrial environments because they can leach from waste disposal sites into groundwater and/or surface waters. Leaching and degradation of plasticizers and polymers are complex phenomena dependent on environmental conditions in the landfill and the chemical properties of each additive. Bisphenol A concentrations in leachates from municipal waste disposal sites in tropical Asia ranged from sub µg l–1 to mg l–1 and were correlated with the level of economic development. PMID:19528054

  15. Embryotoxic effects of nonylphenol and octylphenol in sea urchin Arbacia lixula.

    PubMed

    Cakal Arslan, O; Parlak, H

    2007-08-01

    Nonylphenol (NP) and octylphenol (OP), both of which are biodegradation products of alkylphenols, are widely used in industrial applications and in some domestic products. These chemicals are found widely in surface water and aquatic sediments. We have carried out a comparative embryotoxicity analysis of the effects of increasing concentrations of NP (seven concentrations ranging from 0.937 to 18.74 microg/l) and OP (six concentrations ranging from 5 to 160 microg/l) on embryos of the sea urchin Arbacia lixula. The indicators evaluated were larval malformations, developmental arrest and embryonic/larval mortality. The results revealed that low concentrations of these chemicals (NP, OP) generally caused malformations in the skeletal system. High concentrations (18.74 microg NP/l, 160 microg OP/l) were found to inhibit the growth of embryos in the early life stages by preventing mitosis. We conclude that NP and OP present a major risk to the normal development of A. lixula at the low concentrations that have been recorded in the environment. These chemicals are therefore most likely to represent an ecological hazard at the population level given the cumulative effects of other environmental pollutants.

  16. Micropollutants removal in an anaerobic membrane bioreactor and in an aerobic conventional treatment plant.

    PubMed

    Abargues, M R; Robles, A; Bouzas, A; Seco, A

    2012-01-01

    The paper expresses an attempt to tackle the problem due to the presence of micropollutants in wastewater which may be able to disrupt the endocrine system of some organisms. These kinds of compounds are ubiquitously present in municipal wastewater treatment plant (WWTP) effluents. The aim of this paper is to compare the fate of the alkylphenols-APs (4-(tert-octyl)) phenol, t-nonylphenol and 4-p-nonylphenol and the hormones (estrone, 17β-estradiol and 17α-ethinylestradiol) in a submerged anaerobic membrane bioreactor (SAMBR) pilot plant and in a conventional activated sludge wastewater treatment plant (CTP). The obtained results are also compared with the results obtained in a previous study carried out in an aerobic MBR pilot plant. The results showed that the APs soluble concentrations in the SAMBR effluent were always significantly higher than the CTP ones. Moreover, the analyses of the suspended fraction revealed that the AP concentrations in the SAMBR reactor were usually higher than in the CTP reactor, indicating that under anaerobic conditions the APs were accumulated in the digested sludge. The aerobic conditions maintained both in the CTP system and in the aerobic MBR favoured the APs and hormones degradation, and gave rise to lower concentrations in the effluent and in the reactor of these systems. Furthermore, the results also indicated that the degradation of APs under aerobic conditions was enhanced working at high solid retention time (SRT) and hydraulic retention time (HRT) values.

  17. Preliminary studies of bio-oil from fast pyrolysis of coconut fibers.

    PubMed

    Almeida, Tarciana M; Bispo, Mozart D; Cardoso, Anne R T; Migliorini, Marcelo V; Schena, Tiago; de Campos, Maria Cecilia V; Machado, Maria Elisabete; López, Jorge A; Krause, Laiza C; Caramão, Elina B

    2013-07-17

    This work studied fast pyrolysis as a way to use the residual fiber obtained from the shells of coconut ( Cocos nucifera L. var. Dwarf, from Aracaju, northeastern Brazil). The bio-oil produced by fast pyrolysis and the aqueous phase (formed during the pyrolysis) were characterized by GC/qMS and GC×GC/TOF-MS. Many oxygenated compounds such as phenols, aldehydes, and ketones were identified in the extracts obtained in both phases, with a high predominance of phenolic compounds, mainly alkylphenols. Eighty-one compounds were identified in the bio-oil and 42 in the aqueous phase using GC/qMS, and 95 and 68 in the same samples were identified by GC×GC/TOF-MS. The better performance of GC×GC/TOF-MS was due to the possibility of resolving some coeluted peaks in the one-dimension gas chromatography. Semiquantitative analysis of the samples verified that 59% of the area on the chromatogram of bio-oil is composed by phenols and 12% by aldehydes, mainly furfural. Using the same criterion, 77% of the organic compounds in the aqueous phase are phenols. Therefore, this preliminary assessment indicates that coconut fibers have the potential to be a cost-effective and promising alternative to obtain new products and minimize environmental impact.

  18. Occurrence of 4-tert-butylphenol (4-t-BP) biodegradation in an aquatic sample caused by the presence of Spirodela polyrrhiza and isolation of a 4-t-BP-utilizing bacterium.

    PubMed

    Ogata, Yuka; Toyama, Tadashi; Yu, Ning; Wang, Xuan; Sei, Kazunari; Ike, Michihiko

    2013-04-01

    Although 4-tert-butylphenol (4-t-BP) is a serious aquatic pollutant, its biodegradation in aquatic environments has not been well documented. In this study, 4-t-BP was obviously and repeatedly removed from water from four different environments in the presence of Spirodela polyrrhiza, giant duckweed, but 4-t-BP persisted in the environmental waters in the absence of S. polyrrhiza. Also, 4-t-BP was not removed from autoclaved pond water with sterilized S. polyrrhiza. These results suggest that the 4-t-BP removal from the environmental waters was caused by biodegradation stimulated by the presence of S. polyrrhiza rather than by uptake by the plant. Moreover, Sphingobium fuliginis OMI capable of utilizing 4-t-BP as a sole carbon and energy source was isolated from the S. polyrrhiza rhizosphere. Strain OMI degraded 4-t-BP via a meta-cleavage pathway, and also degraded a broad range of alkylphenols with linear or branched alkyl side chains containing two to nine carbon atoms. Root exudates of S. polyrrhiza stimulated 4-t-BP degradation and cell growth of strain OMI. Thus, the stimulating effects of S. polyrrhiza root exudates on 4-t-BP-degrading bacteria might have contributed to 4-t-BP removal in the environmental waters with S. polyrrhiza. These results demonstrate that the S. polyrrhiza-bacteria association may be applicable to the removal of highly persistent 4-t-BP from wastewaters or polluted aquatic environments.

  19. Determination of 13 endocrine disrupting chemicals in environmental solid samples using microwave-assisted solvent extraction and continuous solid-phase extraction followed by gas chromatography-mass spectrometry.

    PubMed

    Azzouz, Abdelmonaim; Ballesteros, Evaristo

    2016-01-01

    Soil can contain large numbers of endocrine disrupting chemicals (EDCs). The varied physicochemical properties of EDCs constitute a great challenge to their determination in this type of environmental matrix. In this work, an analytical method was developed for the simultaneous determination of various classes of EDCs, including parabens, alkylphenols, phenylphenols, bisphenol A, and triclosan, in soils, sediments, and sewage sludge. The method uses microwave-assisted extraction (MAE) in combination with continuous solid-phase extraction for determination by gas chromatography-mass spectrometry. A systematic comparison of the MAE results with those of ultrasound-assisted and Soxhlet extraction showed MAE to provide the highest extraction efficiency (close to 100%) in the shortest extraction time (3 min). The proposed method provides a linear response over the range 2.0 - 5000 ng kg(-1) and features limits of detection from 0.5 to 4.5 ng kg(-1) depending on the properties of the EDC. The method was successfully applied to the determination of target compounds in agricultural soils, pond and river sediments, and sewage sludge. The sewage sludge samples were found to contain all target compounds except benzylparaben at concentration levels from 36 to 164 ng kg(-1). By contrast, the other types of samples contained fewer EDCs and at lower concentrations (5.6 - 84 ng kg(-1)).

  20. Chronic toxicity of nonylphenol and ethinylestradiol: haematological and histopathological effects in juvenile Common carp (Cyprinus carpio).

    PubMed

    Schwaiger, J; Spieser, O H; Bauer, C; Ferling, H; Mallow, U; Kalbfus, W; Negele, R D

    2000-11-01

    In recent ecotoxicological research, there is an increasing concern about alkylphenolic industrial chemicals, such as nonylphenol (NP), because of their estrogenic properties. Data on the general fish toxicity of these wide spread aquatic pollutants are scarce. In order to evaluate sublethal toxic effects of environmentally relevant concentrations of NP, juvenile Common carp (Cyprinus carpio) were exposed to NP concentrations ranging from 1 to 15 microg NP/l over a 70-day period. Classical toxicological endpoints, such as various haematological parameters and histopathological alterations were investigated. In a comprehensive protocol, besides NP-induced effects also alterations due to a treatment with the synthetic estrogen ethinylestradiol (EE2) were evaluated. After both the NP-exposure as well as the EE2-treatment, the predominant haematological finding was a severe anaemia. Histopathological alterations in the kidney, the liver and the spleen occurred exclusively after treatment with EE2, whereas NP-exposed fish did not show any tissue lesions. Depending on the haematological parameter examined, a NOEC between 1 and 5 microg NP/l could be established. From the present findings, it is assumed, that under field conditions, the NP-induced, general toxic effects, might outbalance the relatively weak estrogenic effects of this compound and possibly might disturb ecologically relevant processes such as fish reproduction.

  1. Environmental impacts of produced water and drilling waste discharges from the Norwegian offshore petroleum industry.

    PubMed

    Bakke, Torgeir; Klungsøyr, Jarle; Sanni, Steinar

    2013-12-01

    Operational discharges of produced water and drill cuttings from offshore oil and gas platforms are a continuous source of contaminants to continental shelf ecosystems. This paper reviews recent research on the biological effects of such discharges with focus on the Norwegian Continental Shelf. The greatest concern is linked to effects of produced water. Alkylphenols (AP) and polyaromatic hydrocarbons (PAH) from produced water accumulate in cod and blue mussel caged near outlets, but are rapidly metabolized in cod. APs, naphtenic acids, and PAHs may disturb reproductive functions, and affect several chemical, biochemical and genetic biomarkers. Toxic concentrations seem restricted to <2 km distance. At the peak of discharge of oil-contaminated cuttings fauna disturbance was found at more than 5 km from some platforms, but is now seldom detected beyond 500 m. Water-based cuttings may seriously affect biomarkers in filter feeding bivalves, and cause elevated sediment oxygen consumption and mortality in benthic fauna. Effects levels occur within 0.5-1 km distance. The stress is mainly physical. The risk of widespread, long term impact from the operational discharges on populations and the ecosystem is presently considered low, but this cannot be verified from the published literature.

  2. Ecological risk assessment of substances with suspected estrogenic activity using standard laboratory fish tests

    SciTech Connect

    Gimeno, S.; Bowmer, C.T.

    1999-07-01

    The assessment of risks to the aquatic environment in the European Union is generally based on a comparison of Predicted Environmental Concentrations (PEC) with Predicted No Effect Concentrations (PNEC) for surrogate, or representative, organisms of the receiving waters. Such risk assessments are required for new and priority existing chemicals, pesticides, and, in the near future, biocides; they are dependent on robust in vivo test data. Current strategies for ecological risk assessment were not designed to assess the risk of endocrine disrupters. The selection of suitable fish species and practical in vivo end points for determining endocrine disruption in fish are discussed, including the adaptation of some existing guidelines. This paper is partly based on a series of experiments conducted at the laboratory to look at the effects of a model alkylphenol (4-tert-pentylphenol), an industrial chemical intermediate, acting as a pseudo-estrogen on an all-male population of the common carp, Cyprinus carpio. Exposure to the test substance occurred at critical life stages for endocrine disruption. Biochemical parameters as well as histological parameters were applied, and their suitability to be used in ecological risk assessment is discussed.

  3. A national reconnaissance for selected organic micropollutants in sediments on French territory.

    PubMed

    Vulliet, Emmanuelle; Berlioz-Barbier, Alexandra; Lafay, Florent; Baudot, Robert; Wiest, Laure; Vauchez, Antoine; Lestremau, François; Botta, Fabrizio; Cren-Olivé, Cécile

    2014-10-01

    To collect a large data set regarding the occurrence of organic substances in sediment, this study presents the examination of 20 micropollutants, as a national survey. The list of target compounds contains two alkylphenols, three polycyclic aromatic hydrocarbons (PAHs) not commonly included in monitoring programmes, six pesticides or metabolites, five pharmaceutical compounds, two hormones, one UV filter and bisphenol A. The selective and sensitive analytical methods, based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) or gas chromatography-time-of-flight mass spectrometry (GC-ToF-MS), allow the quantification at limits comprised between 0.5 and 23 ng/g, depending on the compound. The paper summarizes the analytical results from 154 sampling points. Of the 20 target compounds, 9 were determined at least once, and the sediments contained a maximum of 7 substances. The most frequently detected were PAHs (frequency, 77 %; max., 1,400 ng/g). The pharmaceutical compounds, hormones and pesticides were rarely detected in the samples; the most frequently detected was carbamazepine (frequency, 6 %; max., 31 ng/g). In some cases, the levels of PAHs and bisphenol A exceed the predicted no-effect concentration (PNEC) values.

  4. Effect of bottling and storage on the migration of plastic constituents in Spanish bottled waters.

    PubMed

    Guart, Albert; Bono-Blay, Francisco; Borrell, Antonio; Lacorte, Silvia

    2014-08-01

    Bottled water is packaged in either glass or, to a large extent, in plastic bottles with metallic or plastic caps of different material, shape and colour. Plastic materials are made of one or more monomers and several additives that can eventually migrate into water, either during bottle manufacturing, water filling or storage. The main objective of the present study was to carry out a comprehensive assessment of the quality of the Spanish bottled water market in terms of (i) migration of plastic components or additives during bottling and during storage and (ii) evaluation of the effect of the packaging material and bottle format on the migration potential. The compounds investigated were 5 phthalates, diethylhexyl adipate, alkylphenols and bisphenol A. A set of 362 bottled water samples corresponding to 131 natural mineral waters and spring waters sources and 3 treated waters of several commercial brands were analysed immediately after bottling and after one-year storage (a total of 724 samples). Target compounds were detected in 5.6% of the data values, with diethyl hexyl phthalate and bisphenol A being the most ubiquitous compounds detected. The total daily intake was estimated and a comparison with reference values was indicated.

  5. Spatial and temporal patterns of endocrine active chemicals in small streams indicate differential exposure to aquatic organisms

    USGS Publications Warehouse

    Lee, K.E.; Barber, L.B.; Schoenfuss, H.L.

    2014-01-01

    Alkylphenolic chemicals (APCs) and hormones were measured six times from February through October 2007 in three Minnesota streams receiving wastewater to identify spatial and temporal patterns in concentrations and in estrogen equivalency. Fish were collected once during the study to evaluate endpoints indicative of endocrine disruption. The most commonly detected APCs were 4-tert-octylphenol and 4-nonylphenol and the most commonly detected hormones were estrone and androstenedione. Chemical concentrations were greatest for nonylphenol ethoxycarboxylates (NPECs) (5,000-140,000 ng/l), followed by 4-nonlylphenol and 4-nonylphenolethoxylates (50-880 ng/l), 4-tert-octylphenol and 4-tert-octylphenolethoxylates with concentrations as great as 130 ng/l, and hormones (0.1-54 ng/l). Patterns in chemicals and estrogen equivalency indicated that wastewater effluent is a pathway of APCs and hormones to downstream locations in this study. However, upstream contributions can be equally or more important indicating alternative sources. This study indicates that aquatic organisms experience both spatially and temporally variable exposures in the number of compounds, total concentrations, and estrogenicity. This variability was evident in fish collected from the three rivers as no clear upstream to downstream pattern of endocrine disruption endpoints emerged.

  6. ZnCl 2 induced catalytic conversion of softwood lignin to aromatics and hydrocarbons

    SciTech Connect

    Wang, Hongliang; Zhang, Libing; Deng, Tiansheng; Ruan, Hao; Hou, Xianglin; Cort, John R.; Yang, Bin

    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. Results 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.

  7. Toxics Use Reduction in the Home: Lessons Learned from Household Exposure Studies.

    PubMed

    Dunagan, Sarah C; Dodson, Robin E; Rudel, Ruthann A; Brody, Julia G

    2011-03-01

    Workers and fence-line communities have been the first to benefit from the substantial reductions in toxic chemical use and byproducts in industrial production resulting from the Massachusetts Toxics Use Reduction Act (TURA). As TURA motivates reformulation of products as well as retooling of production processes, benefits could extend more broadly to large-scale reductions in everyday exposures for the general population. Household exposure studies, including those conducted by Silent Spring Institute, show that people are exposed to complex mixtures of indoor toxics from building materials and a myriad of consumer products. Pollutants in homes are likely to have multiple health effects because many are classified as endocrine disrupting compounds (EDCs), with the ability to interfere with the body's hormone system. Product-related EDCs measured in homes include phthalates, halogenated flame retardants, and alkylphenols. Silent Spring Institute's chemical analysis of personal care and cleaning products confirms many are potential sources of EDCs, highlighting the need for a more comprehensive toxics use reduction (TUR) approach to reduce those exposures. Toxics use reduction targeted at EDCs in consumer products has the potential to substantially reduce occupational and residential exposures. The lessons that have emerged from household exposure research can inform improved chemicals management policies at the state and national levels, leading to safer products and widespread health and environmental benefits.

  8. Towards the determination of an optimal scale for stormwater quality management: micropollutants in a small residential catchment.

    PubMed

    Bressy, A; Gromaire, M-C; Lorgeoux, C; Saad, M; Leroy, F; Chebbo, G

    2012-12-15

    Stormwater and atmospheric deposits were collected on a small residential urban catchment (0.8 ha) near Paris in order to determine the levels of certain micropollutants (using a preliminary scan of 69 contaminants, followed by a more detailed quantification of PAHs, PCBs, alkylphenols and metals). Atmospheric inputs accounted for only 10%-38% of the stormwater contamination (except for PCBs), thus indicating substantial release within the catchment. On this small upstream catchment however, stormwater contamination is significantly lower than that observed downstream in storm sewers on larger adjacent urban catchments with similar land uses. These results likely stem from cross-contamination activity during transfers inside the sewer system and underscore the advantages of runoff management strategies at the source for controlling stormwater pollutant loads. Moreover, it has been shown that both contamination levels and contaminant speciation evolve with the scale of the catchment, in correlation with a large fraction of dissolved contaminants in upstream runoff, which differs from what has been traditionally assumed for stormwater. Consequently, the choice of treatment device/protocol must be adapted to the management scale as well as to the targeted type of contaminant.

  9. Risk assessment based prioritization of 200 organic micropollutants in 4 Iberian rivers.

    PubMed

    Kuzmanović, Maja; Ginebreda, Antoni; Petrović, Mira; Barceló, Damia

    2015-01-15

    The use of chemicals is continuously growing both in total amount as well as in a number of different substances, among which organic chemicals play a major role. Owing to the growing public awareness on the need of protecting both ecosystems and human health from the risks related to chemical pollution, an increasing attention has been drowned to risk assessment and prioritization of organic pollutants. In this context, the aims of this study were (a) to perform an environmental risk assessment for 200 organic micropollutants including both regulated and emerging contaminants (pesticides, alkylphenols, pharmaceuticals, hormones, personal care products, perflourinated compounds and various industrial organic chemicals) monitored in four rivers located in the Mediterranean side of the Iberian Peninsula, namely, the Ebro, Llobregat, Júcar and Guadalquivir rivers; and (b) to prioritize them for each of the four river basins studied, taking into account their observed concentration levels together with their ecotoxicological potential. For this purpose, a prioritization approach has been developed and a resulting ranking index (RI) associated with each compound. Ranking index is based on the measured concentrations of the chemical in each river and its ecotoxicological potential (EC50 values for algae, Daphnia sp. and fish). Ten compounds were identified as most important for the studied rivers: pesticides chlorpyriphos, chlorfenvinphos, diazinon, dichlofenthion, prochloraz, ethion carbofuran and diuron and the industrial organic chemicals nonylphenol and octylphenol that result from the biodegration of polyethoxylated alkyphenol surfactants. Also, further research into chronic toxicity of emerging contaminants is advocated.

  10. Cognitive effects of endocrine-disrupting chemicals in animals.

    PubMed Central

    Schantz, S L; Widholm, J J

    2001-01-01

    A large number of chemical pollutants including phthalates, alkylphenolic compounds, polychlorinated biphenyls and polychlorinated dibenzodioxins, organochlorine pesticides, bisphenol A, and metals including lead, mercury, and cadmium have the ability to disrupt endocrine function in animals. Some of these same chemicals have been shown to alter cognitive function in animals and humans. Because hormonally mediated events play a central role in central nervous system development and function, a number of researchers have speculated that the changes in cognitive function are mediated by the endocrine-like actions of these chemicals. In this paper we review the evidence that cognitive effects of chemicals classified as environmental endocrine disruptors are mediated by changes in hormonal function. We begin by briefly reviewing the role of gonadal steroids, thyroid hormones, and glucocorticoids in brain development and brain function. We then review the endocrine changes and cognitive effects that have been reported for selected endocrine-disrupting chemicals, discuss the evidence for causal relationships between endocrine disruption and cognitive effects, and suggest directions for future research. PMID:11748026

  11. Zero-valent iron-activated persulfate oxidation of a commercial alkyl phenol polyethoxylate.

    PubMed

    Temiz, Kubra; Olmez-Hanci, Tugba; Arslan-Alaton, Idil

    2016-01-01

    Aqueous Triton X-45 (TX-45; 20 mg/L; original total organic carbon (TOC) = 14 mg/L), a representative, commercially important alkylphenol polyethoxylate, was subjected to persulfate (PS) oxidation activated with zero-valent iron (ZVI) nanoparticles. After optimization of the ZVI/PS treatment combination (1 g/L ZVI; 2.5 mM PS at pH5) in terms of pH (3-9), ZVI (0.5-5 g/L) and PS (0.5-5.0 mM) concentrations, TX-45 could be efficiently (>90%) degraded within short treatment periods (<60 min) accompanied with significant (>40%) TOC removals. The degree of PS consumption and Fe release was also followed during the experiments and a positive correlation existed between enhanced TX-45 removals and ZVI-activated PS consumption rates accompanied with a parallel Fe release. Acute toxicity tests were conducted using two different bioassays to examine the toxicological safety of the ZVI/PS oxidation system. Acute toxicity profiles significantly decreased from an original value of 66% relative inhibition to 21% and from 16% relative inhibition to non-toxic values according to Vibrio fischeri and Pseudokirchneriella subcapitata bioassays, respectively. The photobacterium V. fischeri appeared to be more sensitive to TX-45 and its degradation products than the microalgae P. subcapitata.

  12. Multiresidue analysis of environmental pollutants in edible vegetable oils by gas chromatography-tandem mass spectrometry.

    PubMed

    Zhou, Rui-Ze; Jiang, Jie; Mao, Ting; Zhao, Ya-Song; Lu, Yong

    2016-09-15

    A novel multiresidue determination of polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PAEs) and alkylphenols (APs) in edible vegetable oils was developed. The samples were extracted with hexane-saturated acetonitrile, and after concentration, the extract was directly qualitatively and quantitatively analyzed by gas chromatography-tandem mass spectrometry (GC-MS/MS) with multiple reaction monitoring (MRM) in positive ion mode. The calibration curve displayed good linearity in the range of 2-100 μg/L, with correlation coefficients greater than 0.99. The mean recoveries were 70.0-110.8% by analysis of spiked oil, and the relative standard deviations (RSDs) were 2.1-10.2% (n=6), respectively. The limits of detection (LODs) for the 23 PAHs, 17 PAEs and 3 APs were 0.1-1.0 μg/kg, 0.1-4.0 μg/kg and 1.2-3.0 μg/kg, respectively. The established method effectively avoided interference from large amounts of lipids and pigments. It was applied to real sample and shown to be a rapid and reliable alternative for determination and confirmation in routine analysis.

  13. Toxicity identification fractionation of environmental estrogens in waste water and sludge using gas and liquid chromatography coupled to mass spectrometry and recombinant yeast assay.

    PubMed

    Fernandez, Marc P; Noguerol, Tania-Noelia; Lacorte, Silvia; Buchanan, Ian; Piña, Benjamin

    2009-02-01

    We developed a toxicity identification fractionation (TIF) procedure to determine estrogenic compounds in wastewaters and sludge. The procedure consisted in fractionation of samples through a C(18) solid-phase extraction cartridge, in which Fraction I contained nonylphenol (NP) and its mono (NPEO(1)) and diethoxylate (NPEO(2)) and the markers of faecal exposure, Fraction II contained bisphenol A (BPA) and synthetic and natural hormones, and Fraction III contained the hormone conjugates. These three fractions were analyzed in parallel using gas or liquid chromatography coupled to mass spectrometry and recombinant yeast assay (RYA). Water samples collected daily throughout a whole week contained from 0.45 to 7.22 microg L(-1) of NP > NPEO(1) > NPEO(2) and were responsible for the estrogenicity of these samples. Fractions II and III were not estrogenic and that was due to the low ng L(-1) level of hormones and hormone conjugates found, respectively. The biological treatment sewage treatment plant (STP) was capable to eliminate from 52 to 100% of the compounds, with bisphenol A being the least removed. Only alkylphenols were accumulated in sludge with concentrations from 8.69 to 26.3 mg kg(-1) dw of NPEO(1) > NPEO(2) > NP. The integrated procedure herein proposed can be used as a screening method to evaluate estrogenic compounds in STPs and to survey faecal elimination.

  14. New alkenyl derivative from Piper malacophyllum and analogues: Antiparasitic activity against Trypanosoma cruzi and Leishmania infantum.

    PubMed

    Varela, Marina T; Lima, Marta L; Galuppo, Mariana K; Tempone, Andre G; de Oliveira, Alberto; Lago, João Henrique G; Fernandes, João Paulo S

    2017-03-29

    Alkylphenols isolated from Piper malacophyllum (Piperaceae), gibbilimbols A and B, showed interesting activity against the parasites Trypanosoma cruzi and Leishmania infantum. In continuation to our previous work, a new natural product from the essential oil of the leaves of P. malacophyllum was isolated, the 5-[(3E)-oct-3-en-1-il]-1,3-benzodioxole, and also a new set of five compounds was prepared. The antiparasitic activity of the natural product was evaluated in vitro against these parasites, indicating potential against the promastigote/trypomastigote/amastigote forms (IC50 32-83 μM) of the parasites and low toxicity (CC50 >200 μM) to mammalian cells. The results obtained to the synthetic compounds indicated that the new derivatives maintained the promising antiparasitic activity, but the cytotoxicity was considerably lowered The amine derivative LINS03011 displayed the most potent IC50 values (13.3 and 16.7 μM) against amastigotes of T. cruzi and L. infantum, respectively, indicating comparable activity to the phenolic prototype LINS03003, with 3-fold decreased (CC50 73.5 μM) cytotoxicity, leading the selectivity index (SI) towards the parasites up to 24.5. In counterpart, LINS03011 has not shown membrane disruptor activity in Sytox Green model. In summary, this new set showed the hydroxyl is not essential for the antiparasitic activity, and its substitution could decrease the toxicity to mammalian cells. This article is protected by copyright. All rights reserved.

  15. A Portable Liquid Chromatograph with a Battery-operated Compact Electroosmotic Pump and a Microfluidic Chip Device with a Reversed Phase Packed Column.

    PubMed

    Ishida, Akihiko; Fujii, Mitsutaka; Fujimoto, Takehiro; Sasaki, Shunsuke; Yanagisawa, Ichiro; Tani, Hirofumi; Tokeshi, Manabu

    2015-01-01

    A compact and lightweight liquid chromatography system is presented with overall dimensions of 26 cm width × 18 cm length × 21 cm height and weight of 2 kg. This system comprises a battery-operated compact electroosmotic pump, a manual injector, a microfluidic chip device containing a packed column and an electrochemical detector, and a USB bus-powered potentiostat. The pumping system was designed for microfluidic-based reversed-phase liquid chromatography in which an electroosmotically generated water stream pushes the mobile phase via a diaphragm for the output. The flow rate ranged from 0 to 10 μL/min and had a high degree of precision. The pumping system operated continuously for over 24 h with dry batteries. The column formed in the microfluidic device was packed with 3-μm ODS particles with a length of 30 mm and a diameter of 0.8 mm. The results presented herein demonstrate the performance of the pumping system and the column using alkylphenols, catecholamine, catechin, and amino acids.

  16. Occurrence and Removal of Organic Micropollutants in Landfill Leachates Treated by Electrochemical Advanced Oxidation Processes.

    PubMed

    Oturan, Nihal; van Hullebusch, Eric D; Zhang, Hui; Mazeas, Laurent; Budzinski, Hélène; Le Menach, Karyn; Oturan, Mehmet A

    2015-10-20

    In recent years, electrochemical advanced oxidation processes have been shown to be an effective alternative for the removal of refractory organic compounds from water. This study is focused on the effective removal of recalcitrant organic matter (micropollutants, humic substances, etc.) present in municipal solid waste landfill leachates. A mixture of eight landfill leachates has been studied by the electro-Fenton process using a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode or by the anodic oxidation process with a BDD anode. These processes exhibit great oxidation ability due to the in situ production of hydroxyl radicals ((•)OH), a highly powerful oxidizing species. Both electrochemical processes were shown to be efficient in the removal of dissolved total organic carbon (TOC) from landfill leachates. Regarding the electro-Fenton process, the replacement of the classical anode Pt by the anode BDD allows better performance in terms of dissolved TOC removal. The occurrence and removal yield of 19 polycyclic aromatic hydrocarbons, 15 volatile organic compounds, 7 alkylphenols, 7 polychlorobiphenyls, 5 organochlorine pesticides, and 2 polybrominated diphenyl ethers in landfill leachate were also investigated. Both electrochemical processes allow one to reach a quasicomplete removal (about 98%) of these organic micropollutants.

  17. Identification of persistent anionic surfactant-derived chemicals in sewage effluent and groundwater

    USGS Publications Warehouse

    Field, Jennifer A.; Leenheer, Jerry A.; Thorn, Kevin A.; Barber, Larry B.; Rostad, Colleen; Macalady, Donald L.; Daniel, Stephen R.

    1992-01-01

    Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3–10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F300-50 groundwater have a minimum residence time in the range of 2.7–4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50–500 half lives.

  18. Identification of persisten anionic surfactant-derived chemicals in sewage effluent and groundwater

    USGS Publications Warehouse

    Field, J.A.; Leenheer, J.A.; Thorn, K.A.; Barber, L.B.; Rostad, C.; Macalady, D.L.; Daniel, S.R.

    1992-01-01

    Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3-10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F300-50 groundwater have a minimum residence time in the range of 2.7-4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50-500 half lives.

  19. Estrogen receptor (ER) agonists and androgen receptor (AR) antagonists in effluents from Norwegian North Sea oil production platforms.

    PubMed

    Tollefsen, Knut-Erik; Harman, Christopher; Smith, Andy; Thomas, Kevin V

    2007-03-01

    The in vitro estrogen receptor (ER) agonist and androgen receptor (AR) antagonist potencies of offshore produced water effluents collected from the Norwegian Sector were determined using recombinant yeast estrogen and androgen screens. Solid phase extraction (SPE) concentrates of the effluents showed E2 agonist activities similar to those previously reported for the United Kingdom (UK) Continental Shelf (<0.1-4 ng E2 L(-1)). No activity was detected in the filtered oil droplets suggesting that produced water ER activity is primarily associated with the dissolved phase. Targeted analysis for methyl- to nonyl-substituted alkylphenol isomers show the occurrence of known ER agonists in the analysed samples. For the first time, AR antagonists were detected in both the dissolved and oil associated phase at concentrations of between 20 and 8000 microg of flutamide equivalents L(-1). The identity of the AR antagonists is unknown, however this represents a significant input into the marine environment of unknown compounds that exert a known biological effect. It is recommended that further analysis using techniques such as bioassay-directed analysis is performed to identify the compounds/groups of compounds that are responsible in order to improve the assessment of the risk posed by produced water discharges to the marine environment.

  20. May organic pollutants affect fish populations in the North Sea?

    PubMed

    Hylland, Ketil; Beyer, Jonny; Berntssen, Marc; Klungsøyr, Jarle; Lang, Thomas; Balk, Lennart

    2006-01-08

    The North Sea is a highly productive area with large fish populations that have been extensively harvested over the past century. North Sea fisheries remain important to the surrounding countries despite declining fish stocks over the past decades. The main reason for declining fish stocks is nearly certainly overfishing, but other environmental pressures also affect fish populations, such as eutrophication, climate change, and exposure to metals and organic pollutants, including polyaromatic hydrocarbons (PAHs), alkylphenols, and organochlorine compounds. There are three main sources of organic pollutants in the North Sea: atmospheric, land-based sources, and inputs from offshore gas and oil installations. All three sources contribute to elevated concentrations of organic pollutants in the North Sea compared to the Norwegian Sea. There is evidence that chlorinated organic contaminants were present in sufficiently high concentrations in the southern North Sea two decades ago, to alter embryonal development in fish. The results from extensive, long-term monitoring programs show that some diseases decreased whereas other increased in the southern North Sea and that, among other factors, contaminants may play a role in the temporal changes recorded in disease prevalence. Recent studies demonstrated that components in offshore effluents may affect fish reproduction and that tissues of fish near oil rigs are structurally different to tissues of fish from reference areas. Data on effluents from offshore activities have recently become available through an international workshop (BECPELAG) and follow-up studies.

  1. [Acute toxicity of different type pesticide surfactants to Daphnia magna].

    PubMed

    Li, Xiu-huan; Li, Hua; Chen, Cheng-yu; Li, Jian-tao; Liu, Feng

    2013-08-01

    By using the standard test methods in Experimental Guideline for Environmental Safety Evaluation of Chemical Pesticide to aquatic organisms, a comparative study was conducted on the acute toxicity of 39 nonionic, 6 anionic, and 3 cationic surfactants to Daphnia magna. The acute toxicity of three cationic surfactants 1427, 1227 and C8-10 to D. magna belonged to virulent level, and the toxicity of 1427 was the highest, with the EC50 value being 0.97 x 10(-2) mg x L(-1). The acute toxicity of nonionic surfactants polyoxyethylene ether castor oil EL, Tween, and Span emulsifiers belonged to low level, but the toxicity of alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether surfactants was relatively high, of which, AEO-7 and AEO-5 displayed high toxicity, with the EC50 value being 0.82 and 0.97 mg x L(-1), respectively. In these surfactants, the more liposolubility, the higher the toxicity was. Most of the anionic surfactants were medium in toxicity, but the acute toxicity of NNO belonged to high toxicity, with the EC50 value being 0.17 mg x L(-1).

  2. Tracing endocrine disrupting chemicals in a coastal lagoon (Sacca di Goro, Italy): sediment contamination and bioaccumulation in Manila clams.

    PubMed

    Casatta, Nadia; Mascolo, Giuseppe; Roscioli, Claudio; Viganò, Luigi

    2015-04-01

    The Water Framework Directive, recently amended with new priority substances (2013/39/EU), is meant to regulate the health status of European aquatic environments, including transitional waters. Despite the ecological and economic importance of transitional water bodies and, in particular, of coastal lagoons, a relevant example of this type of environments, little is known about their contamination by priority substances, particularly by endocrine disrupting chemicals (EDCs). In this study, a wide array of priority substances, all with recognised disrupting properties, was investigated in the Sacca di Goro Lagoon (Adriatic Sea, Italy), which receives freshwater from the Po River after draining the most urbanised and industrialised Italian regions. Flame retardants, alkylphenols, bisphenol A, natural and synthetic steroids, personal care products and legacy pollutants were investigated both in sediments and in the clam Ruditapes philippinarum collected from three sites in the lagoon. Sediments showed that most of the chemicals analysed could reach the lagoon ecosystem but their concentrations were below existing quality guidelines. Clams essentially reflected this condition although some concern was raised by polybrominated diphenyl ethers (PBDEs): the limit for the sum of six congeners set for biota in the European Directive (2013/39/EU) to protect human health was exceeded 4-5 times. No significant biota-sediment accumulation factors (BSAFs) were calculated. Nonylphenol, tonalide, PBDE, polychlorinated biphenyls and bisphenol A were the most abundant chemicals in clam tissues.

  3. Distributions of persistent organic contaminants in sediments and their potential impact on macrobenthic faunal community of the Geum River Estuary and Saemangeum Coast, Korea.

    PubMed

    Yoon, Seo Joon; Hong, Seongjin; Kwon, Bong-Oh; Ryu, Jongseong; Lee, Chang-Hee; Nam, Jungho; Khim, Jong Seong

    2017-04-01

    Over the last 30 years, the Geum River Estuary and Saemangeum Coast have been subject to major environmental changes, including dike construction, reclamation, and development of industrial complexes. This study aimed to: 1) investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs), alkylphenols (APs), and styrene oligomers (SOs), 2) identify the sources of sedimentary organic matter, and 3) determine key environmental factors controlling the macrozoobenthos community structure. A total of 58 surface sediments were collected from the estuary and coastal area in 2014. Specific persistent organic contaminants (POCs), including 24 PAHs, 6 APs, and 10 SOs were measured. PAHs, APs, and SOs were detected in the sediments at all sites, with concentrations varying among sites. Although POCs concentrations were generally below the Canadian sediment quality guidelines, relatively greater concentrations of POCs were found at some sites adjacent to industrial complexes and the estuarine area. Sediment organic carbon, total nitrogen, and the stable carbon isotope ratio (δ(13)C) were determined. Some sites near watergate had about 2-3‰ lighter δ(13)C values compared to other areas, indicating that these sites are affected by terrestrial organic matter. The number of species in the macrofaunal community was significantly correlated with δ(13)C values (p < 0.001), positively, suggesting that the origin of sedimentary organic matter is important for controlling the macrozoobenthos distribution. Overall, this research provides information about the level and sources of sediment pollution, the origins of organic matter, and the relationships with the macrofaunal community.

  4. Methods development for separation of inorganic anions, organic acids and bases, and neutral organic compounds by ion chromatography and capillary electrophoresis

    SciTech Connect

    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 different 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.

  5. In vitro effects of diethylstilbestrol, genistein, 4-tert-butylphenol, and 4-tert-octylphenol on steroidogenic activity of isolated immature rat ovarian follicles

    SciTech Connect

    Myllymaeki, Sari . E-mail: saanmy@utu.fi; Haavisto, Tapio; Vainio, Minna; Toppari, Jorma; Paranko, Jorma

    2005-04-01

    Isolated rat ovarian follicles grow and produce steroid hormones in vitro and so provide a good model for studying the effects of hormonally active compounds on follicular steroidogenesis. We have evaluated the effects of diethylstilbestrol (DES), genistein (GEN) and two alkylphenols, 4-tert-butylphenol (BP) and 4-tert-octylphenol (OP) on the growth, survival, and steroid hormone and cAMP production by isolated 14-day-old rat (Sprague-Dawley) ovarian follicles. During a 5-day culture, FSH was obligatory for follicle growth and increased estradiol and testosterone secretion in a dose-dependent manner. DES (10{sup -6} M) caused the strongest decline in estradiol and testosterone levels but did not have detectable effects on either cAMP production or aromatase enzyme activity. GEN caused a prominent decrease in cAMP and testosterone levels without significant changes in secreted estradiol. The latter, apparently, was due to a dose-dependent stimulation of aromatase enzyme activity in the presence of genistein. Both BP and OP decreased estradiol and testosterone secretion in a dose-dependent manner while no effect on aromatase activity was observed. OP, unlike BP, decreased forskolin-induced cAMP levels. Xenoestrogens at the used concentrations did not interfere with the growth and survival of the follicles. The results indicate that isolated ovarian follicles representing intact morphological and functional units offer a sensitive model system for elucidating the female-specific reproductive effects of environmental chemicals.

  6. Gas purge microsyringe extraction for quantitative direct gas chromatographic-mass spectrometric analysis of volatile and semivolatile chemicals.

    PubMed

    Yang, Cui; Piao, Xiangfan; Qiu, Jinxue; Wang, Xiaoping; Ren, Chunyan; Li, Donghao

    2011-03-25

    Sample pretreatment before chromatographic analysis is the most time consuming and error prone part of analytical procedures, yet it is a key factor in the final success of the analysis. A quantitative and fast liquid phase microextraction technique termed as gas purge microsyringe extraction (GP-MSE) has been developed for simultaneous direct gas chromatography-mass spectrometry (GC-MS) analysis of volatile and semivolatile chemicals without cleanup process. Use of a gas flowing system, temperature control and a conventional microsyringe greatly increased the surface area of the liquid phase micro solvent, and led to quantitative recoveries of both volatile and semivolatile chemicals within short extraction time of only 2 min. Recoveries of polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and alkylphenols (APs) determined were 85-107%, and reproducibility was between 2.8% and 8.5%. In particular, the technique shows high sensitivity for semivolatile chemicals which is difficult to achieve in other sample pretreatment techniques such as headspace-liquid phase microextraction. The variables affecting extraction efficiency such as gas flow rate, extraction time, extracting solvent type, temperature of sample and extracting solvent were investigated. Finally, the technique was evaluated to determine PAHs, APs and OCPs from plant and soil samples. The experimental results demonstrated that the technique is economic, sensitive to both volatile and semivolatile chemicals, is fast, simple to operate, and allows quantitative extraction. On-site monitoring of volatile and semivolatile chemicals is now possible using this technique due to the simplification and speed of sample treatment.

  7. The immune response of juvenile Atlantic cod (Gadus morhua L.) to chronic exposure to produced water.

    PubMed

    Pérez-Casanova, Juan C; Hamoutene, Dounia; Samuelson, Stephanie; Burt, Kimberly; King, Thomas L; Lee, Kenneth

    2010-07-01

    Produced water (PW) is the main discharge from the offshore oil industry and contains oil-derived compounds such as poly-aromatic hydrocarbons, phenols, alkylphenols, and heavy metals. Studies suggest that PW discharges may affect the biota over larger areas from the oil drilling sites at sea than originally predicted. We investigated the effects of chronic exposure to PW on some aspects of juvenile Atlantic cod immunity, stress response and growth by intermittently exposing fish to 0, 100 or 200 ppm of PW for 22 weeks. No significant effects of PW were observed on growth, hepatosomatic index, condition factor or plasma cortisol. The respiratory burst (RB) of circulating leukocytes was significantly elevated in the 100 ppm group only, while the RB of head-kidney leukocytes was significantly decreased in both the 100 and 200 ppm groups. Significant up-regulation of the mRNA expression of beta-2-microglobulin, immunoglobulin-M light chain and interleukins-1beta and -8 was observed in the 200 ppm group, while the down-regulation of interferon stimulated gene 15 was obvious for both the 100 and 200 ppm groups. The results suggest that chronic exposure to environmentally relevant concentrations of PW causes modulations of the immune system of juvenile Atlantic cod with most immune parameters being stimulated, potentially resulting in an energetic cost that may be detrimental to the fish.

  8. In vivo effects of environmental concentrations of produced water on the reproductive function of polar cod (Boreogadus saida).

    PubMed

    Geraudie, P; Nahrgang, J; Forget-Leray, J; Minier, C; Camus, L

    2014-01-01

    Offshore oil and gas drilling processes generate operational discharges such as produced water (PW), a complex mixture of seawater with polycyclic aromatic hydrocarbons (PAH) and alkylphenols (AP). Some of these compounds may interact with the endocrine system of marine organisms and alter reproductive functions. In this study, polar cod were exposed for up to 28 d to a mixture of PAH, alkylated PAH, and AP simulating the composition of North Sea PW, at low and high concentrations (1:2000 and 1:1000 dilution of the original concentrate, respectively). Potential adverse effects of PW on polar cod physiology were investigated through biomarkers of biotransformation (hepatic ethoxyresorufin O-deethylase [EROD] activity and bile PAH metabolites), endocrine disruption (plasma vitellogenin [VTG] levels and sex steroid concentrations), and gonad histology. Plasma sexual steroid levels in fish were not markedly affected by PW exposure, while higher plasma VTG concentrations were measured in females exposed to the high PW treatment for 7 and 28 d. In males exposed to the higher PW concentration, inhibition of spermatogenesis was observed after 28 d in addition to increase of melano-macrophage occurrence in testis. Females exposed to the high PW treatment for 21 d showed a significant increase of atresia incidence. Finally, a significant decrease in oocyte number was observed in high PW exposed female ovaries after 28 d of exposure.

  9. Negative impact of endocrine-disrupting compounds on human reproductive health.

    PubMed

    Balabanič, Damjan; Rupnik, Marjan; Klemenčič, Aleksandra Krivograd

    2011-01-01

    There is increasing concern about chemical pollutants that are able to mimic hormones, the so-called endocrine-disrupting compounds (EDCs), because of their structural similarity to endogenous hormones, their ability to interact with hormone transport proteins or because of their potential to disrupt hormone metabolic pathways. Thus, the effects of endogenous hormones can be mimicked or, in some cases, completely blocked. A substantial number of environmental pollutants, such as polychlorinated biphenyls, dioxins, polycyclic aromatic hydrocarbons, phthalates, bisphenol A, pesticides, alkylphenols and heavy metals (arsenic, cadmium, lead, mercury), have been shown to disrupt endocrine function. These compounds can cause reproductive problems by decreasing sperm count and quality, increasing the number of testicular germ cells and causing male breast cancer, cryptorchidism, hypospadias, miscarriages, endometriosis, impaired fertility, irregularities of the menstrual cycle, and infertility. Although EDCs may be released into the environment in different ways, the main sources is industrial waste water. The present paper critically reviews the current knowledge of the impact of EDCs on reproductive disorders in humans.

  10. 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.

  11. Cognitive effects of endocrine-disrupting chemicals in animals.

    PubMed

    Schantz, S L; Widholm, J J

    2001-12-01

    A large number of chemical pollutants including phthalates, alkylphenolic compounds, polychlorinated biphenyls and polychlorinated dibenzodioxins, organochlorine pesticides, bisphenol A, and metals including lead, mercury, and cadmium have the ability to disrupt endocrine function in animals. Some of these same chemicals have been shown to alter cognitive function in animals and humans. Because hormonally mediated events play a central role in central nervous system development and function, a number of researchers have speculated that the changes in cognitive function are mediated by the endocrine-like actions of these chemicals. In this paper we review the evidence that cognitive effects of chemicals classified as environmental endocrine disruptors are mediated by changes in hormonal function. We begin by briefly reviewing the role of gonadal steroids, thyroid hormones, and glucocorticoids in brain development and brain function. We then review the endocrine changes and cognitive effects that have been reported for selected endocrine-disrupting chemicals, discuss the evidence for causal relationships between endocrine disruption and cognitive effects, and suggest directions for future research.

  12. Endocrine disrupting compounds in the atmosphere of the urban area of Thessaloniki, Greece

    NASA Astrophysics Data System (ADS)

    Salapasidou, M.; Samara, C.; Voutsa, D.

    2011-07-01

    The aim of this study was to investigate the occurrence of endocrine disrupting compounds (EDCs) in a complex urban atmosphere. Target compounds were alkylphenols (NP, tOP, nOP), nonylphenol monoethoxylate (NP1EO), bisphenol A (BPA), tetrabromobisphenol A (TBBPA), and phthalates (DMP, DEP, DBP, BBP, DEHP, DNOP). EDCs were determined in ambient PM10 from two sampling sites, one urban-traffic and one urban-industrial, located in the city of Thessaloniki, northern Greece. At both sites, DEHP and NP were found to be the predominant EDCs in airborne PM10. Concentrations of NP did not exhibit any spatial difference, whereas concentrations of DEHP were significantly higher at the urban-traffic site. Wind direction was not found to have any significant effect on ambient EDCs concentrations suggesting impact from local sources rather than transport; however some peak concentrations might be attributed to short-distance sources. The gas/particle partition coefficient, Kp, and the gaseous phase of EDCs were calculated by employing two approaches based on literature data (a) for the subcooled liquid vapor pressure ( PL0) and (b) the octanol-air partition coefficient ( KOA). It appeared that the g/ p partition of phthalates estimated by the KOA approach is in better agreement with experimental partition data reported by other investigators. Absorption in organic matter was found to be significant partition mechanism at the urban-traffic site.

  13. The endocrine disruptor nonylphenol induces sublethal toxicity in vascular plant development at environmental concentrations: A risk for riparian plants and irrigated crops?

    PubMed

    Esteban, S; Llamas, P M; García-Cortés, H; Catalá, M

    2016-09-01

    In recent years, there is a growing concern among the scientific community about the presence of the so-called emergent pollutants in waters of different countries, especially endocrine-disrupting compounds (EDCs) that have the ability to alter the hormonal system. One of the substances found almost ubiquitously and in higher concentrations is the alkylphenol nonylphenol. Albeit this compound is included in priority lists as a probable risk for human health and the environment, little is known about its effects on developing plants. The aim of this work is to assess the acute and sub-chronic toxicity of environmental concentrations of nonylphenol in riparian vascular plant development using spores of the fern Polystichum setiferum and a biomarker-based approach: mitochondrial activity (cell viability), chlorophyll (plant physiology) and DNA content (growth). Mitochondrial activity and DNA content show that nonylphenol induces acute and sub-chronic toxicity at 48 h and after 1 week, respectively. Significant effects are observed in both parameters in fern spores at ng L(-1) but chlorophyll autofluorescence shows little changes. The inhibition of germination by natural allelochemicals has been reported to be related with the active hydroxyl group of phenolic compounds and largely independent of the structural nucleus to which it is attached. Results presented in this study suggest that environmental concentrations of nonylphenol could interfere with higher plant germination development by mimicking natural allelochemicals and/or phytohormones acting as a "phytoendocrine disruptor" likely posing ecophysiological risks.

  14. Anthropogenic tracers, endocrine disrupting chemicals, and endocrine disruption in Minnesota lakes.

    PubMed

    Writer, Jeffrey H; Barber, Larry B; Brown, Greg K; Taylor, Howard E; Kiesling, Richard L; Ferrey, Mark L; Jahns, Nathan D; Bartell, Steve E; Schoenfuss, Heiko L

    2010-12-01

    Concentrations of endocrine disrupting chemicals and endocrine disruption in fish were determined in 11 lakes across Minnesota that represent a range of trophic conditions and land uses (urban, agricultural, residential, and forested) and in which wastewater treatment plant discharges were absent. Water, sediment, and passive polar organic integrative samplers (POCIS) were analyzed for steroidal hormones, alkylphenols, bisphenol A, and other organic and inorganic molecular tracers to evaluate potential non-point source inputs into the lakes. Resident fish from the lakes were collected, and caged male fathead minnows were deployed to evaluate endocrine disruption, as indicated by the biological endpoints of plasma vitellogenin and gonadal histology. Endocrine disrupting chemicals, including bisphenol A, 17β-estradiol, estrone, and 4-nonylphenol were detected in 90% of the lakes at part per trillion concentrations. Endocrine disruption was observed in caged fathead minnows and resident fish in 90% of the lakes. The widespread but variable occurrence of anthropogenic chemicals in the lakes and endocrine disruption in fish indicates that potential sources are diverse, not limited to wastewater treatment plant discharges, and not entirely predictable based on trophic status and land use.

  15. Toxicological and chemical investigation of untreated municipal wastewater: Fraction- and species-specific toxicity.

    PubMed

    Hrubik, Jelena; Glisic, Branka; Tubic, Aleksandra; Ivancev-Tumbas, Ivana; Kovacevic, Radmila; Samardzija, Dragana; Andric, Nebojsa; Kaisarevic, Sonja

    2016-05-01

    Absence of a municipal wastewater (WW) treatment plant results in the untreated WW discharge into the recipient. The present study investigated toxic effects and chemical composition of water extracts and fractions from untreated WW and recipient Danube River (DR). Samples were prepared by solid-phase extraction and silica gel fractionation and screened for EROD activity and cytotoxicity using aquatic models, comprising of fish liver cells (PLHC-1) and a model of the early development of zebrafish embryos, while rat (H4IIE) and human (HepG2) hepatoma cells served as mammalian models. Polar fraction caused cytotoxicity and increased the EROD activity in PLHC-1 cells, and increased mortality and developmental abnormalities in developing zebrafish embryos. In H4IIE, polar fraction induced inhibition of cell growth and increased EROD activity, whereas HepG2 exerted low or no response to the exposure. Non-polar and medium-polar fractions were ineffective. Tentative identification by GC/MS showed that WW is characterized by the hydrocarbons, alkylphenols, plasticizers, and a certain number of benzene derivatives and organic acids. In DR, smaller number of organic compounds was identified and toxicity was less pronounced than in WW treatments. The present study revealed the potent toxic effect of polar fraction of untreated WW, with biological responses varying in sensitivity across organisms. Obtained results confirmed that fraction- and species-specific toxicity should be considered when assessing health risk of environmental pollution.

  16. Purification and characterization of hydroquinone dioxygenase from Sphingomonas sp. strain TTNP3

    PubMed Central

    2011-01-01

    Hydroquinone-1,2-dioxygenase, an enzyme involved in the degradation of alkylphenols in Sphingomonas sp. strain TTNP3 was purified to apparent homogeneity. The extradiol dioxygenase catalyzed the ring fission of hydroquinone to 4-hydroxymuconic semialdehyde and the degradation of chlorinated and several alkylated hydroquinones. The activity of 1 mg of the purified enzyme with unsubstituted hydroquinone was 6.1 μmol per minute, the apparent Km 2.2 μM. ICP-MS analysis revealed an iron content of 1.4 moles per mole enzyme. The enzyme lost activity upon exposure to oxygen, but could be reactivated by Fe(II) in presence of ascorbate. SDS-PAGE analysis of the purified enzyme yielded two bands of an apparent size of 38 kDa and 19 kDa, respectively. Data from MALDI-TOF analyses of peptides of the respective bands matched with the deduced amino acid sequences of two neighboring open reading frames found in genomic DNA of Sphingomonas sp strain TTNP3. The deduced amino acid sequences showed 62% and 47% identity to the large and small subunit of hydroquinone dioxygenase from Pseudomonas fluorescens strain ACB, respectively. This heterotetrameric enzyme is the first of its kind found in a strain of the genus Sphingomonas sensu latu. PMID:21906340

  17. Physical and metabolic interactions of Pseudomonas sp. strain JA5-B45 and Rhodococcus sp. strain F9-D79 during growth on crude oil and effect of a chemical surfactant on them.

    PubMed

    Van Hamme, J D; Ward, O P

    2001-10-01

    Methods to enhance crude oil biodegradation by mixed bacterial cultures, for example, (bio)surfactant addition, are complicated by the diversity of microbial populations within a given culture. The physical and metabolic interactions between Rhodococcus sp. strain F9-D79 and Pseudomonas sp. strain JA5-B45 were examined during growth on Bow River crude oil. The effects of a nonionic chemical surfactant, Igepal CO-630 (nonylphenol ethoxylate), also were evaluated. Strain F9-D79 grew attached to the oil-water interface and produced a mycolic acid-containing capsule. Crude oil emulsification and surface activity were associated with the cellular fraction. Strain JA5-B45 grew in the aqueous phase and was unable to emulsify oil, but cell-free supernatants mediated kerosene-water emulsion formation. In coculture, stable emulsions were formed and strain JA5-B45 had an affinity for the capsule produced by strain F9-D79. Igepal CO-630 inhibited F9-D79 cells from adhering to the interface, and cells grew dispersed in the aqueous phase as 0.5-microm cocci rather than 2.5-microm rods. The surfactant increased total petroleum hydrocarbon removal by strain JA5-B45 from 4 to 22% and included both saturated compounds and aromatics. In coculture, TPH removal increased from 13 to 40% following surfactant addition. The culture pH normally increased from 7.0 to between 7.5 and 8.5, although addition of Igepal CO-630 to F9-D79 cultures resulted in a drop to pH 5.5. We suggest a dual role for the nonylphenol ethoxylate surfactant in the coculture: (i) to improve hydrocarbon uptake by strain JA5-B45 through emulsification and (ii) to prevent strain F9-D79 from adhering to the oil-water interface, indirectly increasing hydrocarbon availability. These varied effects on hydrocarbon biodegradation could explain some of the known diversity of surfactant effects.

  18. Physical and Metabolic Interactions of Pseudomonas sp. Strain JA5-B45 and Rhodococcus sp. Strain F9-D79 during Growth on Crude Oil and Effect of a Chemical Surfactant on Them

    PubMed Central

    Van Hamme, Jonathan D.; Ward, Owen P.

    2001-01-01

    Methods to enhance crude oil biodegradation by mixed bacterial cultures, for example, (bio)surfactant addition, are complicated by the diversity of microbial populations within a given culture. The physical and metabolic interactions between Rhodococcus sp. strain F9-D79 and Pseudomonas sp. strain JA5-B45 were examined during growth on Bow River crude oil. The effects of a nonionic chemical surfactant, Igepal CO-630 (nonylphenol ethoxylate), also were evaluated. Strain F9-D79 grew attached to the oil-water interface and produced a mycolic acid-containing capsule. Crude oil emulsification and surface activity were associated with the cellular fraction. Strain JA5-B45 grew in the aqueous phase and was unable to emulsify oil, but cell-free supernatants mediated kerosene-water emulsion formation. In coculture, stable emulsions were formed and strain JA5-B45 had an affinity for the capsule produced by strain F9-D79. Igepal CO-630 inhibited F9-D79 cells from adhering to the interface, and cells grew dispersed in the aqueous phase as 0.5-μm cocci rather than 2.5-μm rods. The surfactant increased total petroleum hydrocarbon removal by strain JA5-B45 from 4 to 22% and included both saturated compounds and aromatics. In coculture, TPH removal increased from 13 to 40% following surfactant addition. The culture pH normally increased from 7.0 to between 7.5 and 8.5, although addition of Igepal CO-630 to F9-D79 cultures resulted in a drop to pH 5.5. We suggest a dual role for the nonylphenol ethoxylate surfactant in the coculture: (i) to improve hydrocarbon uptake by strain JA5-B45 through emulsification and (ii) to prevent strain F9-D79 from adhering to the oil-water interface, indirectly increasing hydrocarbon availability. These varied effects on hydrocarbon biodegradation could explain some of the known diversity of surfactant effects. PMID:11571196

  19. 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

  20. Reticence vs. Responsibility: Why Climate Scientists Sometimes Need to Think Like Emergency Room Doctors

    NASA Astrophysics Data System (ADS)

    Peacock, K.

    2013-12-01

    require innovation, but in a conservative way because experimentation is not allowed---something may have to be done that no one has done before, but it has to be done right the first time. (I will briefly comment on the relevance of this point to geoengineering.) It is the duty of professionals to tell the truth 'without fear or favour' (APEO) but it is also the duty of professionals to make decisions, often without what Hansen (2007) called 'the comfort of waiting for incontrovertible confirmations.' In short, scientists may have to train themselves to think like emergency room doctors. It may seem that I am threatening to impose impossibly severe expectations on climate scientists, but I believe that they may find it comforting and steadying, in these very uncertain times, to place themselves within the long and honourable tradition of professional practice.