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Sample records for alkylphenol polyethoxylates apeos

  1. Behavior of alkylphenol polyethoxylate metabolites during soil aquifer treatment.

    PubMed

    Montgomery-Brown, John; Drewes, Jörg E; Fox, Peter; Reinhard, Martin

    2003-09-01

    The attenuation of alkylphenol polyethoxylates (APEOs) metabolites was studied at a soil aquifer treatment (SAT) site located in Arizona, USA. Two parcels of water were monitored during infiltration; one parcel was predominantly oxic while the other was predominantly anoxic. In this study, only alkylphenol ethoxycarboxylates (APECs) and carboxyalkylphenol ethoxycarboxylates (CAPECs) were detected, no short-chained APEOs were observed-even under anoxic conditions. APEO metabolites were rapidly (<7 days) removed under both aerobic and anoxic conditions. In general, the length of the ethoxycarboxylate chain decreases with depth--at depths greater than 3m, only alkylphenoxy acetic acids (AP1ECs), carboxyalkylphenoxy acetic acids (CAP1ECs), and alkylphenols (APs) remain. Under aerobic conditions, octylphenol and nonylphenol concentrations decreased by approximately 80% (w/w) within 3m of the ground surface. Under anoxic conditions however, alkylphenol concentrations increased by approximately 200% during the first 1.5m and then decreased during the next 1.5m; overall, under anoxic conditions, alkylphenol concentrations increased by approximately 38% within 3m. During infiltration, APEC and CAPEC concentrations decrease by more than 95% within 3m of SAT. Alternate flooding and drying cycles appear to enhance overall APEO metabolite removal efficiencies. PMID:12867334

  2. 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.

  3. A sensitive and robust method for the determination of alkylphenol polyethoxylates and their carboxylic acids and their transformation in a trickling filter wastewater treatment plant.

    PubMed

    Koh, Yoong K K; Chiu, Tze Y; Boobis, Alan R; Cartmell, Elise; Pollard, Simon J T; Scrimshaw, Mark D; Lester, John N

    2008-09-01

    This paper presents a method for the determination of alkylphenols, alkylphenol polyethoxylates (APEO) and alkylphenol ethoxycarboxylates (APEC) in the aqueous and particulate phase of wastewater samples. Quantification was achieved by liquid chromatography-tandem mass spectrometry. The sensitivity of the method is demonstrated by low detection limits, in the dissolved phase 1.2-9.6ngl(-1) for alkylphenol, AP1-3EO and APEC and 0.1-4.1ngl(-1) for longer chain alkylphenol polyethoxylates. The method detection limit for particulate phase samples ranged from 6 to 60ngg(-1) for AP, AP1-3EO and APEC; with the longer chain APEO being from 0.5 to 20ngg(-1). Matrix effects were noted in complex matrix rich samples. There was a distinct change in the distribution of alkylphenol ethoxylates during biological treatment of the wastewater, with the major biotransformation products observed being carboxylated derivatives at concentrations of up to 1768ngl(-1). Shorter chain APEO were present in higher proportions in the suspended solids, due to their higher affinity to particulate matter compared to the long-chain oligomers. PMID:18657288

  4. Alkylphenol Polyethoxylate Metabolite Behavior During Short-Term Soil Aquifer Treatment

    NASA Astrophysics Data System (ADS)

    Reinhard, M.

    2002-12-01

    The attenuation of alkylphenol polyethoxylate (APEO) metabolites was studied at a soil aquifer treatment (SAT) facility located in Mesa, Arizona, USA. SAT is a technique commonly used in arid environments to augment groundwater supplies. In SAT, municipal wastewater is discharged into basins and allowed to infiltrate into the subsurface; the basins are most often filled for several days and then allowed to dry out. During SAT the quality of the recharged water is substantially improved. Because this water may eventually be used to augment drinking water supplies, there is a concern whether organic contaminants survive SAT. APEO metabolites are among the most frequently detected anthropogenic contaminants in the environment. The ubiquitous presence of these compounds may be of concern because they are relatively recalcitrant, can sorb and accumulate in soils and sediments, can bioaccumulate in plants and animals, and can be estrogenic to wildlife at low concentrations. In this study, two parcels of water were monitored during SAT -- one aerobic, the other anaerobic. During infiltration, under aerobic and anaerobic conditions, both alkylphenol ethoxycarboxylates (APECs) and carboxyalkylphenol ethoxycarboxylates (CAPECs) were substantially attenuated (> 90%) within 3 m. As expected, nonylphenol was removed under aerobic conditions, but produced under anaerobic conditions. Interestingly, no short-chained APEOs were detected. The rapid attenuation of CAPECs was surprising, as other researchers have found these metabolites to be very persistent. During infiltration, APEO metabolites with the longest ethoxycarboxylate side chain are attenuated fastest. Unlike several recent studies, alkylphenoxyacetic acids (AP1ECs) and carboxyalkylphenoxyacetic acids (CAP1ECs) were almost twice as abundant as alkylphenoxyethoxyacetic acids (AP2ECs) and carboxyalkylphenoxyethoxyacetic acids (CAP2ECs). Nonylphenol concentrations in both the wastewater and effluent SAT water were > 10

  5. Natural attenuation of pharmaceuticals and alkylphenol polyethoxylate metabolites during river transport: photochemical and biological transformation.

    PubMed

    Lin, Angela Yu-Chen; Plumlee, Megan H; Reinhard, Martin

    2006-06-01

    The capacity of rivers to naturally attenuate trace organic compounds is an important but poorly understood process because the many factors that control attenuation are interrelated and difficult to study in isolation. To better understand the relative importance of chemical (photolysis and sorption) and biological attenuation processes, contaminant removal along a 12-km stretch of the Santa Ana River (SAR) was determined as a function of travel time, distance, and irradiance. Target contaminants included three pharmaceuticals (gemfibrozil, ibuprofen, and naproxen) and their metabolites, and the metabolites of alkylphenol polyethoxylates (APEMs). The APEMs included alkylphenols (APs), short-chain alkylphenol polyethoxylates (APEOs), alkylphenol polyethoxycarboxylates (APECs), and carboxyalkylphenol polyethoxycarboxylates (CAPECs). Overall removals ranged from 50% for APs to 100% for naproxen and increased with distance and time, in many cases following first-order kinetics. For naproxen, which is photolabile, average removals were 20 to 30% more during the day than at night; the nighttime and daytime half-lives were 3 h and 1.7 to 1.9 h, respectively. Comparison of field and laboratory data suggests that approximately 40% of the daytime naproxen removal can be attributed to photolysis with the remainder due to other processes, most likely sorption. For ibuprofen and gemfibrozil, half-lives were 5.4 and 2.7 h, respectively, and laboratory data suggest that biotransformation is the principal attenuating process. The APEM attenuation might be due to sorption and biotransformation; phototransformation may also play a minor role. These data demonstrate that travel times on the order of hours can significantly mitigate the impact of effluent discharge on the water quality of shallow rivers. PMID:16764462

  6. Direct spectrophotometric determination of alkylphenol polyethoxylate nonionic surfactants in wastewater.

    PubMed

    Zhu, Zhenzhong; Li, Zaijun; Hao, Zhuoli; Chen, Jian

    2003-11-01

    A new spectrophotometric method is proposed for direct determination of alkylphenol polyethoxylate, RO(CH(2)CH(2)O)(n)H (where R is alkylphenyl and n is the degree of polymerization), in wastewater. The method is based on the formation of ternary complex, Pb(II)-meso-tetra-(3,5-dibromo-4-hydrooxyphenyl)-Porphyrin (T(DBHP)P)-alkylphenol polyethoxylate (APE). Under optimum reaction conditions, T(DBHP)P reacts with lead(II) and APE to form a yellow ternary complex with the maximum absorption peak at 479 nm. The color reaction is rapidly completed and the absorbance remains stable for at least 24h under room temperature. The apparent molar absorption coefficients were 0.4-4.3 x 10(4) L mol(-1) cm(-1) for n=5-50. As little as 0.02 microg mL(-1) of APE can be detected. The effects of various substances on the determination of APE were also investigated in detail. It was found that all the studied co-existing substances, especially cationic and anionic surfactants, which always seriously interfere in some reported methods, could be tolerated in considerable amounts. The method offered the advantages of simplicity, rapidity, sensitivity and selectivity without any prior separation or extraction. PMID:14511721

  7. Strategies for selecting optimal sampling and work-up procedures for analysing alkylphenol polyethoxylates in effluents from non-activated sludge biofilm reactors.

    PubMed

    Stenholm, Ake; Holmström, Sara; Hjärthag, Sandra; Lind, Ola

    2012-01-01

    Trace-level analysis of alkylphenol polyethoxylates (APEOs) in wastewater containing sludge requires the prior removal of contaminants and preconcentration. In this study, the effects on optimal work-up procedures of the types of alkylphenols present, their degree of ethoxylation, the biofilm wastewater treatment and the sample matrix were investigated for these purposes. The sampling spot for APEO-containing specimens from an industrial wastewater treatment plant was optimized, including a box that surrounded the tubing outlet carrying the wastewater, to prevent sedimented sludge contaminating the collected samples. Following these changes, the sampling precision (in terms of dry matter content) at a point just under the tubing leading from the biofilm reactors was 0.7% RSD. The findings were applied to develop a work-up procedure for use prior to a high-performance liquid chromatography-fluorescence detection analysis method capable of quantifying nonylphenol polyethoxylates (NPEOs) and poorly investigated dinonylphenol polyethoxylates (DNPEOs) at low microg L(-1) concentrations in effluents from non-activated sludge biofilm reactors. The selected multi-step work-up procedure includes lyophilization and pressurized fluid extraction (PFE) followed by strong ion exchange solid phase extraction (SPE). The yields of the combined procedure, according to tests with NP10EO-spiked effluent from a wastewater treatment plant, were in the 62-78% range. PMID:22519096

  8. Occurrence of alkylphenol polyethoxylates in the St. Lawrence River and their bioconcentration by mussels (Elliptio complanata).

    PubMed

    Sabik, H; Gagné, F; Blaise, C; Marcogliese, D J; Jeannot, R

    2003-05-01

    A study was conducted in 1999 to determine the occurrence of alkylphenol polyethoxylates in the St. Lawrence River and their bioconcentration by mussels (Elliptio complanata). Concentrations of selected contaminants were measured in surface water, municipal effluent, sediments and mussels. Analyses were performed on 4-tert-octylphenol (4-t-OP), 4-n-nonylphenol (4-n-NP), nonylphenol polyethoxylates (NP(1-16)EO), nonylphenol-mono and di-ethoxycarboxylic acids (NP(1)EC and NP(2)EC), and octylphenol-mono and di-ethoxycarboxylic acids (OP(1)EC and OP(2)EC). Mussels (Elliptio complanata) taken from a reference lake were placed in cages and submerged for 62 days at two sites in the St. Lawrence River, 1.5 km upstream and 5 km downstream of the outfall of a municipal wastewater treatment plant. The results showed that many of the target chemicals were present in all matrices studied: in water, at ppt and ppb levels, and reaching ppm levels in sediments and mussels. Concentrations of these contaminants were higher in matrices sampled at the downstream site than in those drawn at the site upstream of the Montreal effluent outfall, especially in sediments. Likewise, the slight, but not significant, bioconcentration of certain alkylphenol polyethoxylates (AP(n)EO) in the mussels was more noticeable at the downstream site than at the upstream site. PMID:12598000

  9. Adsorption and recovery of alkylphenol polyethoxylates from synthetic wastewater using hexagonal mesoporous silicate.

    PubMed

    Punyapalakul, P; Takizawa, S

    2006-01-01

    A large amount of alkylphenol polyethoxylate (APnEOs), one of endocrine disrupters, is disposed of directly to biological wastewater treatment plants. But microbial oxidation processes cannot completely degrade these molecules to nontoxic forms. Adsorption and recovery efficiency of APnEOs was investigated using four different types of Hexagonal Mesoporous Silicate (HMSs) and powdered activated carbon (PAC). HMSs were synthesized by surfactant-templating methods, and two of them were subsequently grafted with surface functional groups. The two types of organic functional groups grafted on the surface were n-octyldimethyl- and 3-mercaptopropyl- groups. Titanium substituted HMS was also made in the same way as HMS. Adsorption of APnEOs on synthesized HMSs was higher than that on PAC. Larger pore sizes of HMS and Ti-HMS enhanced accessibility of APnEOs to active surface sites in mesopores, which realized higher adsorption capacities and L-shape (Langmuir) adsorption isotherms. Adsorption capacities of APnEOs are influenced by water solubility of APnEOs. APnEOs adsorbed on HMSs can be completely recovered by a mixture of alcohol and water at 5:5 ratio, which is more effective than the recovery from PAC. PMID:16749450

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

    PubMed

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

    2014-10-01

    Four different pellicular stationary phases (i.e. octadecylsilane, octasilane, Phenyl-Hexyl and pentafluorophenyl) were investigated for the chromatographic resolution of alkylphenols (APs), alkylphenols polyethoxylates (APnEOs) and alkylphenoxy carboxylates (APECs) using mixtures of water and organic solvents (i.e. methanol, acetonitrile and tetrahydrofuran) as eluents, in order to obtain their determination by a single LC-MS/MS run. In fact, alkylphenols and alkylphenoxy carboxylates must be analysed in negative ion mode, whereas alkylphenols polyethoxylates undergo ionisation only in positive ion mode, and therefore, two distinct LC-MS/MS analysis are commonly adopted. The best resolution among the aforementioned target analytes was achieved on the pentafluorophenyl column, eluting with an acidified water-acetonitrile-tetrahydrofuran mixture and using the post column addition of an ammonia solution in methanol for the detection of positively ionisable compounds. Under these optimized chromatographic conditions the investigated compounds were determined via a single chromatographic run, with only one polarity switch, in 15min, achieving the following instrumental detection limits: 600pg for AP1EOs, 0.8-14pg for AP2EOs, 10.4-150pg for APs and 4.4-4.8pg for APECs. The chromatographic method was coupled with solid-phase extraction and clean-up procedures and successfully applied to the analysis of wastewater and surface water samples, highlighting mean concentration ranging from 6ng/L for 4-t-OP1EC to 1434ng/L for 4-NP1121EC, depending on the sample analysed. PMID:25171944

  11. 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. PMID:20025273

  12. Determination of degradation products of alkylphenol polyethoxylates in municipal wastewaters and rivers in Tokyo, Japan.

    PubMed

    Isobe, Tomohiko; Takada, Hideshige

    2004-03-01

    An analytical method for the simultaneous determination of nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol (NP), octylphenol (OP), and nonylphenol monoethoxylate (NP1EO) was developed. The method was applied to environmental samples to demonstrate the distribution and behavior of nonylphenol polyethoxylates and their degradation intermediates in aquatic environments in Tokyo, Japan. In sewage treatment plants, more than 85% of NP, OP, and NP1EO were removed, whereas NP1EC and NP2EC were generated during the treatment. Concentrations of NP1EC and NP2EC in secondary effluents (1.9-2.9 microg/L) were higher than those of NP and NPIEO (0.12-0.63 microg/L). In river waters. NPIEC and NP2EC concentrations (0.11-2.8 microg/L) were higher than NP and NP1EO concentrations (<0.015-3.4 microg/L). with some exceptions. In surface sediments, neither NPIEC nor NP2EC was detectable (<0.01 microg/g dry wt) whereas NP and NPIEO were detected significantly (0.03-1.82 microg/g dry wt and 0.04-0.46 microg/g dry wt, respectively). PMID:15285351

  13. Fate of alkylphenolic compounds during activated sludge treatment: impact of loading and organic composition.

    PubMed

    McAdam, Ewan J; Bagnall, John P; Soares, Ana; Koh, Yoong K K; Chiu, Tze Y; Scrimshaw, Mark D; Lester, John N; Cartmell, Elise

    2011-01-01

    The impact of loading and organic composition on the fate of alkylphenolic compounds in the activated sludge plant (ASP) has been studied. Three ASP designs comprising carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification treatment were examined to demonstrate the impact of increasing levels of process complexity and to incorporate a spectrum of loading conditions. Based on mass balance, overall biodegradation efficiencies for nonylphenol ethoxylates (NPEOs), short chain carboxylates (NP(1-3)EC) and nonylphenol (NP) were 37%, 59%, and 27% for the carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification ASP, respectively. The presence of a rich community of ammonia oxidizing bacteria does not necessarily facilitate effective alkylphenolic compound degradation. However, a clear correlation between alkylphenolic compound loading and long chain ethoxylate compound biodegradation was determined at the three ASPs, indicating that at higher initial alkylphenolic compound concentrations (or load), greater ethoxylate biotransformation can occur. In addition, the impact of settled sewage organic composition on alkylphenolic compound removal was evaluated. A correlation between the ratio of chemical oxygen demand (COD) to alkylphenolic compound concentration and biomass activity was determined, demonstrating the inhibiting effect of bulk organic matter on alkylphenol polyethoxylate transformation activity. At all three ASPs the biodegradation pathway proposed involves the preferential biodegradation of the amphiphilic ethoxylated compounds, after which the preferential attack of the lipophilic akylphenol moiety occurs. The extent of ethoxylate biodegradation is driven by the initial alkylphenolic compound concentration and the proportion of COD constituted by the alkylphenol polyethoxylates (APEOs) and their metabolites relative to the bulk organic concentration of the sewage composed of proteins, acids, fats

  14. Occurrence and fate of pharmaceuticals and alkylphenol ethoxylate metabolites in an effluent-dominated river and wetland.

    PubMed

    Gross, Birgit; Montgomery-Brown, John; Naumann, Anneke; Reinhard, Martin

    2004-09-01

    The occurrence of pharmaceuticals, nonylphenol ethoxylate metabolites, and other wastewater-derived contaminants in surface waters is a potential environmental concern, especially since the discovery of contaminants with endocrine-disrupting properties. The present study investigated the discharge of emerging contaminants into the Santa Ana River (CA, USA) and their attenuation during river transport and passage through a constructed wetland. Contaminants studied included pharmaceuticals (gemfibrozil, ibuprofen, naproxen, ketoprofen, and carbamazepine) and their metabolites, hormones, the metabolites of alkylphenol polyethoxylates (APEMs), N-butyl benzenesulfonamide (NBBS), and chlorinated tris-propylphosphates (TCPPs). The APEMs included alkylphenols (APs), short-chain AP polyethoxylates (APEOs), AP polyethoxycarboxylates (APECs), and carboxylated APECs (CAPECs). In wastewater treatment plant effluent, APECs and CAPECs represented the dominant APEM fraction (1.8-18.7 microg/L), whereas APEOs and APs contributed only small amounts to the overall APEM concentrations (0.10-0.92 and < or =0.1 microg/L, respectively) except where the effluent was infiltrated into soil (5.2 microg/L). In effluents, ibuprofen and its metabolites, TCPPs, and NBBS were detected regularly (<0.5 microg/L), and the other pharmaceuticals were detected occasionally. Transport in the Santa Ana River for 11 km resulted in the significant attenuation of all contaminants, from 67% for gemfibrozil to 100% for others. Wetland treatment (residence time, 2-4 d) resulted in partial removal of ibuprofen, gemfibrozil, and TCPPs and transformed APEOs to APECs. PMID:15378981

  15. Alkylphenol polyethoxylate removal in a pilot-scale reed bed and phenotypic characterization of the aerobic heterotrophic community.

    PubMed

    Sacco, Cristiana; Pizzo, Anna Maria; Tiscione, Emilia; Burrini, Daniela; Messeri, Luca; Lepri, Luciano; Del Bubba, Massimo

    2006-07-01

    The removal of the non-ionic surfactant Triton X-100, dosed at 30 and 300 mg/L in a pilot-scale subsurface horizontal flow reed bed, and the aerobic heterotrophic cultivable community associated with the roots and with the substrate gravel in both absence and presence of Triton X-100 were investigated. t-Octylphenol (OP) and its mono-, di- and tri-ethoxyl derivatives, among others, were found in the outlet. A mass balance allowed us to calculate that approximately 40% of the Triton X-100 metabolites OP and octylphenol polyethoxylate derivatives flowed out of the reed bed during the dosage and postdosage experiments. More aerobic heterotrophic microorganisms adhered to the roots than to the gravel. The appearance of new strains (Aeromonas, Flavobacterium, and Aquaspirillum) and the increased presence of others (Pseudomonas) during the dosage of Triton may be linked to the capacity of these bacteria to adapt to the presence of the surfactant or to use it as a nourishment. PMID:16929647

  16. 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. PMID:25618638

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

    PubMed

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

    2013-12-15

    An organic thin film photodiode (OPD) was successfully employed as a portable photodetector in a competitive enzyme-linked immunosorbent assay (ELISA) of a class of nonionic surfactants, namely alkylphenol polyethoxylates (APnEOs) which are an environmental pollutant. Microbeads that were chemically immobilized with an anti-APnEOs antibody were used in the assay. The OPD consisted of a layer of copper phthalocyanine (CuPc), C60 and a second layer of bathocuproine (BCP) with a bulk heterojunction composed of CuPc and C60 prepared by a vapor deposition method on an indium-tin oxide coated glass substrate. The OPD showed an incident photon-current efficiency (IPCE) of approximately 19% for light at a wavelength of 585 nm. This relatively high IPCE at 585 nm makes it suitable for detecting the fluorescence of resorufin (λem=585 nm), the product of the competitive ELISA, produced through the enzymatic reaction of Amplex Red with horseradish peroxidase (HRP) and H2O2. A fluorometric detector was assembled on a microchip by combining the fabricated OPD and a commercial LED as a photodetector and a light source, respectively. The photocurrent of the OPD due to the fluorescence of resorufin was proportional to the concentration of resorufin in the concentration range from 0 to 8 μM. When the fabricated OPD was used as a portable photodetector, the competitive ELISA of APnEOs using HRP labeled APnEOs (HRP-APnEOs) was performed on magnetic microbeads on which surface an anti-APnEOs antibody had been immobilized. A typical sigmoidal calibration curve was obtained and the data were in good agreement with a numerical simulation, where the photocurrent of the OPD was plotted against the concentration of APnEOs, determined via the competitive ELISA. The detection limit of the immunoassay for APnEOs was approximately 2 and 4 ppb in batch and flow system, respectively. PMID:24209322

  18. 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. PMID:17306341

  19. 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...

  20. Fully automated on-line solid phase extraction coupled to liquid chromatography-tandem mass spectrometry for the simultaneous analysis of alkylphenol polyethoxylates and their carboxylic and phenolic metabolites in wastewater samples.

    PubMed

    Ciofi, Lorenzo; Ancillotti, Claudia; Chiuminatto, Ugo; Fibbi, Donatella; Pasquini, Benedetta; Bruzzoniti, Maria Concetta; Rivoira, Luca; Del Bubba, Massimo

    2016-05-01

    Three different sorbents (i.e. endcapped octadecylsilane, octasilane and styrene-N-vinylpiperidinone co-polymer) were investigated in order to develop an on-line solid phase extraction-liquid chromatographic tandem mass spectrometric method (on-line SPE-LC-MS/MS) for the simultaneous analysis of alkylphenols polyethoxylate (AP(n)EOs, n = 1-8) and corresponding monocarboxylate (AP1ECs) and phenolic (APs) metabolites. The endcapped octadecylsilane was selected due to its full compatibility with a chromatographic approach, which allowed the elution of positively and negatively ionisable compounds in two distinct retention time windows, using a water-acetonitrile-tetrahydrofuran ternary gradient and a pellicular pentafluorophenyl column. On this SPE sorbent, the composition of the loading/clean-up solution was then optimized in order to achieve the best recoveries of target analytes. Under the best experimental conditions, the total analysis time per sample was 25 min and method detection limits (MDLs) were in the sub-nanograms per litre to nanograms per litre range (0.0081-1.0 ng L(-1)) for AP(n)EOs with n = 2-8, AP1ECs and APs, whereas for AP1EOs, an MDL of about 50 ng L(-1) was found. Using the mass-labelled compound spiking technique, the method performance was tested on inlet and outlet wastewater samples from three activated sludge treatment plants managing domestic and industrial sewages of the urban areas and the textile district of Prato and Bisenzio valley (Tuscany, Italy); in most cases, apparent recovery percentages approximately in the ranges of 50-110% and 80-120% were found for inlet and outlet samples, respectively. The on-line SPE-LC-MS/MS analysis of wastewater samples highlighted the presence of target analytes at concentrations ranging from few nanograms per litre to thousands nanograms per litre, depending on the compound and matrix analysed. AP2ECs were also tentatively identified in outlet samples. PMID:26897380

  1. Alkylphenols in marine environments: distribution monitoring strategies and detection considerations.

    PubMed

    David, Arthur; Fenet, Hélène; Gomez, Elena

    2009-07-01

    The presence of alkylphenols (APs) in coastal and marine ecosystems is not as well-documented as it is in freshwater ecosystems. This paper reviews reported concentrations of alkylphenol ethoxylates (APEOs) and APs in seawater, sediments and organisms of marine environments such as estuaries, coastal lagoons, bights, harbours or deep sea in order to study their distribution. Overall contamination of marine aquatic compartments by APs and APEOs has been observed, while coastal areas in the vicinity of wastewater discharges are more impacted than deep sea environments, but to a lesser extent than freshwater sites. Sediments act as sinks for APs and APEOs, especially around wastewater discharge sites. Reported AP concentrations in marine organisms are higher in bivalves and gastropods than in fishes. As nonylphenols and octylphenols are estrogenomimetic, biological responses induced in marine organisms are discussed. Finally, we describe the cell bioassay approach for the biodetection of APs. PMID:19476957

  2. Synergistic ecotoxicity of APEOs-PAHs in rivers and sediments: is there a potential health risk?

    PubMed

    Zoller, Uri; Hushan, Marwan

    2010-01-01

    The occurrence and persistence of anthropogenic pollutants in the environment showing estrogenic-endocrine modulating effects in aquatic organisms is a 'hot' issue of major health- and environment-related concern worldwide. The population growth and the increasing scarcity of water in many regions of the world have led to a comprehensive reuse of treated wastewater that, ultimately, may cause a long-term concentration buildup of many toxic persistent organic pollutants (POPs) in the closed cycle of water supply and wastewater treatment and reuse. The endocrinic/mutagenic potencies of the EDCs-branched chain alkylphenol ethoxylates (APEOs), polycyclic aromatic hydrocarbons (PAHs), and their metabolites are well-documented. From approximately 5.5 x 108 m3/y of sewage produced in Israel, approximately 70% are reused, following a conventional, or advanced, activated sludge or sand aquifer treatment (SAT). A major related question is: Does this practice conform to sustainability? Our studies reveal that (a) the concentrations of APEOs and PAHs in Israel rivers and sediments do pose a potential health risk problem; and (b) the synergistic ecotoxicologic impact of environmentally relevant mixtures of these POPs, in WWTP effluents, constitutes an inconsistency, healthwise, with sustainability practice. PMID:21268449

  3. Determination of nineteen 4-alkylphenol endocrine disrupters in Geneva municipal sewage wastewater.

    PubMed

    Espejo, Ramon; Valter, Karel; Simona, Marco; Janin, Yves; Arrizabalaga, Phillipe

    2002-11-01

    A method for the determination of 18 isomeric 4-nonylphenols and 4-tert.-octylphenol in wastewater using GC-MS and LC-MS has been developed. This procedure has been applied to the determination of the free allylphenols and the analysis of these substances in the form of 4-alkylphenol polyethoxylates, their various hydrosoluble metabolites and other hydrosoluble 4-alkylphenol containing degradation products ("bonded" alkylphenols) after their cleavage with hydroiodic acid. In the environment, the final degradation products of 4-alkylphenol polyethoxylates and their metabolites are the long-chain free 4-alkylphenols, which are responsible of endocrine disruption in various animal species. The average concentration of free alkylphenols in the wastewater of the sewage plant in Aïre, Geneva (Switzerland) ranges from 1.0 to 6.8 microg/l (average 2.5 microg/l). The concentration of "bonded" 4-alkylphenols can reach about 0.66 mg/l. The precision of the method and its accuracy are satisfactory with recovery rates for the free 4-alkylphenols and "bonded" 4-nonylphenols ranging from 74 to 79% and 80 to 87%, respectively. The relative standard deviation is lower than 6% for all analyzed compounds. The detection limits are in the range of 0.4 to 6 ng/l (typically 2 ng/l) and quantification limits are between 2 to 22 ng/l (typically 10 ng/l) for all individual isomeric alkylphenols. PMID:12462626

  4. Advanced oxidation of alkylphenol ethoxylates in aqueous systems.

    PubMed

    Nagarnaik, Pranav M; Boulanger, Bryan

    2011-10-01

    Alkylphenols and alkylphenol ethoxylates are ubiquitous wastewater contaminants. In this study the oxidation of nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (OPEO) by oxidant systems generating hydroxide radicals was evaluated. The reaction of each oxidant with a technical mixture of NPEO (Tergitol™) and OPEO (Triton X-100™) in ultrapure laboratory water and four aqueous environmental matrices was carried out in order to develop an understanding of reaction kinetics. The oxidation of APEOs was evaluated by hydroxyl radical generated by (1) hydrogen peroxide in the presence of ultraviolet light, (2) Fenton's reagent, and (3) a photo-Fenton's process. The second order kinetic rate constant for both NPEO and OPEO with hydroxyl radical was calculated to be 1.1×10¹⁰ M⁻¹ s⁻¹. The efficacy of the AOPs within an aqueous environmental matrix was dependent on the rate of formation of hydroxyl radical and the scavenging capacity of the matrix. A model based on the hydroxyl radical formation, scavenging capacity and the kinetic rate constant of target APEO was developed from the existing literature and applied to predict the concentration of APEOs in solution during advanced oxidation in different aqueous environmental matrices. PMID:21784502

  5. Biodegradation of polyethoxylated nonylphenols.

    PubMed

    Ruiz, Yassellis; Medina, Luis; Borusiak, Margarita; Ramos, Nairalith; Pinto, Gilberto; Valbuena, Oscar

    2013-01-01

    Polyethoxylated nonylphenols, with different ethoxylation degrees (NPEO x ), are incorporated into many commercial and industrial products such as detergents, domestic disinfectants, emulsifiers, cosmetics, and pesticides. However, the toxic effects exerted by their degradation products, which are persistent in natural environments, have been demonstrated in several animal and invertebrate aquatic species. Therefore, it seems appropriate to look for indigenous bacteria capable of degrading native NPEO x and its derivatives. In this paper, the isolation of five bacterial strains, capable of using NPEO 15 , as unique carbon source, is described. The most efficient NPEO 15 degrader bacterial strains were identified as Pseudomonas fluorescens (strain Yas2) and Klebsiella pneumoniae (strain Yas1). Maximal growth rates were reached at pH 8, 27°C in a 5% NPEO 15 medium. The NPEO 15 degradation extension, followed by viscometry assays, reached 65% after 54.5 h and 134 h incubation times, while the COD values decreased by 95% and 85% after 24 h for the Yas1 and Yas2 systems, respectively. The BOD was reduced by 99% and 99.9% levels in 24 h and 48 h incubations. The viscosity data indicated that the NPEO 15 biodegradation by Yas2 follows first-order kinetics. Kinetic rate constant (k) and half life time (τ) for this biotransformation were estimated to be 0.0072 h(-1) and 96.3 h, respectively. PMID:23936727

  6. Biodegradation of Polyethoxylated Nonylphenols

    PubMed Central

    Ruiz, Yassellis; Medina, Luis; Borusiak, Margarita; Ramos, Nairalith; Pinto, Gilberto; Valbuena, Oscar

    2013-01-01

    Polyethoxylated nonylphenols, with different ethoxylation degrees (NPEOx), are incorporated into many commercial and industrial products such as detergents, domestic disinfectants, emulsifiers, cosmetics, and pesticides. However, the toxic effects exerted by their degradation products, which are persistent in natural environments, have been demonstrated in several animal and invertebrate aquatic species. Therefore, it seems appropriate to look for indigenous bacteria capable of degrading native NPEOx and its derivatives. In this paper, the isolation of five bacterial strains, capable of using NPEO15, as unique carbon source, is described. The most efficient NPEO15 degrader bacterial strains were identified as Pseudomonas fluorescens (strain Yas2) and Klebsiella pneumoniae (strain Yas1). Maximal growth rates were reached at pH 8, 27°C in a 5% NPEO15 medium. The NPEO15 degradation extension, followed by viscometry assays, reached 65% after 54.5 h and 134 h incubation times, while the COD values decreased by 95% and 85% after 24 h for the Yas1 and Yas2 systems, respectively. The BOD was reduced by 99% and 99.9% levels in 24 h and 48 h incubations. The viscosity data indicated that the NPEO15 biodegradation by Yas2 follows first-order kinetics. Kinetic rate constant (k) and half life time (τ) for this biotransformation were estimated to be 0.0072 h−1 and 96.3 h, respectively. PMID:23936727

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

    PubMed

    Zoller, U; Plaut, I; Hushan, M

    2004-01-01

    The concentration profiles of the potential endocrine disrupting nonionic alkylphenol ethoxylate (APEO) surfactants in Israel's rivers, groundwaters and coastal water of the eastern Mediterranean Sea, were found to be within the range of 12.5-74.6, trace - 20.2 and 4.2-25.0 microg/L respectively. Determination of the APEO's homologic distribution revealed "skewing" towards the more toxic shorter-chain ethoxylates. Egg production of zebrafish, Danio rerio, exposed to these actually found the environmental concentrations range of the APEOs decreased, after 20 days, to 89.6+/-2.1, 84.7+/-3.9 and 76.9+/-2.2% of the baseline levels, compared with control, in concentrations of 10, 25 and 75 microg/L respectively. These results suggest that, (a) there is a potential health problem, particularly in countries in which the "hard"/environmentally persistent APEOs are still in use; and (b) the related health-risk is seasonally-dependent, particularly in semi-arid regions where the fluctuations in the water quantities in surface- and groundwater are substantial. PMID:15497833

  8. 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. PMID:16225920

  9. Inhibition of testicular growth in rainbow trout (Oncorhynchus mykiss) exposed to estrogenic alkylphenolic chemicals

    SciTech Connect

    Jobling, S.; Sumpter, J.P.; Sheahan, D.; Osborne, J.A.; Matthiessen, P.

    1996-02-01

    It is becoming evident that an increasing number of widely used industrial and agricultural chemicals are estrogenic. The biodegradation products of a major group of nonionic surfactants, the alkylphenol polyethoxylates, are one such group. Some of these chemicals are widespread aquatic pollutants, and bioconcentrate in aquatic biota. Exposure of male rainbow trout (Oncorhynchus mykiss) to four different alkylphenolic chemicals caused synthesis of vitellogenin, a process normally dependent on endogenous estrogens, and a concomitant inhibition of testicular growth. The magnitude of these estrogenic effects was dependent on the estrogenic potency of the chemical, the stage of reproductive development of the fish, and the concentration of the chemical in the water. These results support the contention that exposure of wildlife to environmentally persistent estrogenic chemicals can result in deleterious reproductive consequences.

  10. Determination of non-ionic polyethoxylated surfactants in sewage sludge by coacervative extraction and ion trap liquid chromatography-mass spectrometry.

    PubMed

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

    2004-08-13

    Alkylphenol polyethoxylates (APE, nonyl and octyl) and alcohol ethoxylates (AE, C12-C16) were analysed in sewage sludge by extraction with sodium dodecane sulphonate (SDoS), that undergoes coacervation under acid conditions, followed by quantitation with liquid chromatography/atmospheric pressure chemical ionisation ion/trap mass spectrometry, in positive ion mode. Coacervative extraction was optimised using an aged, fortified dehydrated sludge. Recoveries ranged from 78 to nearly 100% irrespective of the sludge matrix analysed. The method provided good agreement between the ethoxamer distribution of surfactants after extraction from sludge and that in the original surfactant. Detection limits for polyethoxylated surfactants in the sludge were 0.09-0.38 mg/kg. The procedure was used to assess the concentrations of APE and AE in activated and dehydrated sludge from two sewage treatment plants. Polyethoxylates were found in all samples in the concentration ranges 11-151, 100-138 and 23-141 mg/kg for octylphenol, nonylphenol and individual AE homologues, respectively. The method did not require clean-up or preconcentration steps. PMID:15387183

  11. 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. PMID:26946030

  12. Rapid liquid chromatography-tandem mass spectrometry-based method for the analysis of alcohol ethoxylates and alkylphenol ethoxylates in environmental samples.

    PubMed

    DeArmond, Patrick D; DiGoregorio, Amanda L

    2013-08-30

    A sensitive and selective method for the determination of alcohol ethoxylates (AEOs) and alkylphenol ethoxylates (APEOs) using solid-phase extraction (SPE) and LC-MS/MS was developed and applied to the analysis of water samples. All AEO and APEO homologues, a total of 152 analytes, were analyzed within a run time of 11min, and the MS allowed for the detection of ethoxymers containing 2-20 ethoxy units (nEO=2-20). The limits of detection (LOD) were as low as 0.1pg injected, which generally increased as nEO increased (e.g., as high as 300pg for nEO=20). Additionally, the responses of the various ethoxymers varied by orders of magnitude, with ethoxymers with nEO=3-5 being the most sensitive and those with nEO>15 producing the least response in the MS. Absolute extraction recoveries of the analytes ranged from 37% to 69% in ultrapure water (RSD≤20%), with the recovery depending on the length of the alkyl chain. Abiotic stability studies were performed, and C14-18 ethoxylates showed significant degrees of degradation. Water samples from the Colorado River were then analyzed for AEOs and APEOs, with absolute extraction recoveries ranging from 33% to 45% (RSD≤12%). The predominant species observed in most samples were the octylphenol (OP) and nonylphenol (NP) ethoxylates, which contained total concentrations that were greater than 100ng/L APEOs in a couple samples. Other AEO homologues were identified in the river water samples, including C13, C15, C16, and C18 ethoxylates, but these compounds were generally present at much lower levels (i.e., <50ng/L total concentration). PMID:23891378

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

    PubMed

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

    2016-07-01

    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. PMID:26797469

  14. Determination of alkylphenols and alkylphenol carboxylates in wastewater and river samples by hemimicelle-based extraction and liquid chromatography-ion trap mass spectrometry.

    PubMed

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

    2006-07-01

    Sodium dodecyl sulfate (SDS)-coated alumina and cetylpyridinium chloride (CPC)-coated silica were investigated as new sorbents for the concentration of alkylphenol polyethoxylate (APE) biodegradation products from wastewater and river water samples. Octylphenol (OP), nonylphenol (NP), octylphenol carboxylic acid (OPC) and nonylphenol carboxylic acid (NPC) were quantitatively retained on both supramolecular sorbents on the basis of the formation of mixed hemimicelles and admicelles. SDS hemimicelles-based SPE was proposed for the extraction/concentration of the target compounds prior to their separation and quantitation by liquid chromatography/electrospray ionization in negative mode, ion trap mass spectrometry. No clean-up steps or evaporation of the eluent were required. The recovery of APE metabolites from sewage and river water ranged between 87 and 100%. Concentration factors of about 500, using sample volumes of 1 l, were achieved. Detection limits were between 75 and 193 ng/l. The approach developed was applied to the determination of alklylphenols and alkylphenol carboxylic acids in raw and treated sewage and river samples. The concentrations of APE metabolites found ranged between 0.8 and 78 microg/l. PMID:16412449

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

    PubMed

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

    2009-12-01

    An analytical method has been developed and applied to determine the concentrations of the nonionic alkylphenol polyethoxylate surfactants and their metabolites, alkylphenoxy carboxylates and alkyphenols, in sewage sludges. The compounds were extracted with methanol/acetone (1:1 v/v) from sludge, and concentrated extracts were cleaned by silica solid-phase extraction prior to determination by liquid chromatography tandem mass spectrometry. The recoveries, determined by spiking sewage sludge at two concentrations, ranged from 51% to 89% with method detection limits from 6 microg kg(-1) to 60 microg kg(-1). The methodology was subsequently applied to sludge samples obtained from a carbonaceous activated sludge plant, a nitrifying/denitrifying activated sludge plant and a nitrifying/ denitrifying activated sludge plant with phosphorus removal. Concentrations of nonylphenolic compounds were two to three times higher than their octyl analogues. Long-chain nonylphenol polyethoxylates (NP3-12EO) ranged from 16 microg kg(-1) to 11754 microg kg(-1). The estrogenic metabolite nonylphenol was present at concentrations ranging from 33 microg kg(-1) to 6696 microg kg(-1). PMID:20088206

  16. Estrogenic activity measured in a sewage treatment works treating industrial inputs containing high concentrations of alkylphenolic compounds--a case study.

    PubMed

    Sheahan, David A; Brighty, Geoff C; Daniel, Mic; Kirby, Sonia J; Hurst, Mark R; Kennedy, Joe; Morris, Steven; Routledge, Edwin J; Sumpter, John P; Waldock, Michael J

    2002-03-01

    Chemical analyses were combined with a biological assay to investigate the main estrogenic chemicals as they passed through a sewage treatment works (STW) and entered a river. The STW studied was unusual in that it received wastewater from the textile trade. This wastewater was shown to contain high concentrations of alkylphenol polyethoxylates and their degradation products, such as nonylphenol. High-performance liquid chromatography fractionation, combined with biological assay, showed that the majority of the estrogenic activity was contributed by the alkylphenolic chemicals and the natural estrogens 17beta-estradiol and estrone. Despite removal of a high proportion of the alkylphenolic chemicals by the various treatment processes within the STW, concentrations in the final effluent were still high compared to most other STW effluents in the United Kingdom. The effluent was very estrogenic to caged fish, as was the river water 2 and 5 km downstream of the STW, even though less so. Using various approaches, attempts were made to determine which group of chemicals contributed most to the estrogenic activity of the effluent. The analysis suggested that, in this unusual situation, the alkylphenolic chemicals may contribute the majority of the estrogenic activity of the effluent. However, this conclusion was based on a number of uncertainties that are presently unresolved and hence can be considered only tentative. PMID:11878463

  17. Analytical methods for the determination of alkylphenolic surfactants and polybrominated diphenyl ethers in wastewaters and sewage sludges. I a review of methodologies.

    PubMed

    Scrimshaw, M D; Langford, K H; Lester, J N

    2004-08-01

    Alkylphenolic surfactants (alkylphenol polyethoxylates) and the polybrominated diphenyl ether flame retardants are important environmental contaminants and have been implicated as endocrine disrupters. Both groups of compounds have come under increasing scrutiny from legislators and there are proposals to curb their use. However, these compounds continue to enter the environment and there is a need to determine their occurrence, fate and behaviour throughout the hydrosphere and in wastewater treatment processes to determine mass fluxes and sources. This paper reviews analytical methods for their determination in the aqueous and solid (sediment / sludge) phase. Extraction, cleanup and quantification by gas and liquid chromatographic (GC and LC) techniques linked to mass spectrometric (MS) detectors are considered. The literature indicates that for the alkylphenols research papers favour the use of LC/MS which is more amenable to determination of more highly ethoxylated oligomers, however, standard methods focus on GC/MS and the less ethoxylated oligomers and parent alkylphenols. The use of GC with negative chemical ionisation MS techniques predominates for the analysis of polybrominated diphenyl ethers. PMID:15366564

  18. Rapid identification of microorganisms for biodegradation of alkylphenols and alkylphenol ethercarboxylates

    SciTech Connect

    Hemming, B.; Williams, J.B.

    1995-12-31

    Alkylphenols, especially nonylphenol and octylphenol, are used in a wide variety of applications. These compounds, and alkylphenol ethercarboxylates, are also believed to be formed during the biodegradation of alkylphenol ethoxylates in activated sludge wastewater treatment systems. Microbe Inotech Laboratories has developed a rapid assay to identify the microorganisms present in activated sludge wastewater treatment systems (GC-FAME) and a screening assay to measure the biodegradation of compounds. These assays were used to show that alkylphenols and their corresponding ethercarboxylates were degraded aerobically even when these compounds were the sole carbon source.

  19. Environmental fate of alkylphenols and alkylphenol ethoxylates--a review.

    PubMed

    Ying, Guang-Guo; Williams, Brian; Kookana, Rai

    2002-07-01

    Alkylphenol ethoxylates (APEs) are widely used surfactants in domestic and industrial products, which are commonly found in wastewater discharges and in sewage treatment plant (STP) effluents. Degradation of APEs in wastewater treatment plants or in the environment generates more persistent shorter-chain APEs and alkylphenols (APs) such as nonylphenol (NP), octylphenol (OP) and AP mono- to triethoxylates (NPE1, NPE2 and NPE3). There is concern that APE metabolites (NP, OP, NPE1-3) can mimic natural hormones and that the levels present in the environment may be sufficient to disrupt endocrine function in wildlife and humans. The physicochemical properties of the APE metabolites (NP, NPE1-4, OP, OPE1-4), in particular the high K(ow) values, indicate that they will partition effectively into sediments following discharge from STPs. The aqueous solubility data for the APE metabolites indicate that the concentration in water combined with the high partition coefficients will provide a significant reservoir (load) in various environmental compartments. Data from studies conducted in many regions across the world have shown significant levels in samples of every environmental compartment examined. In the US, levels of NP in air ranged from 0.01 to 81 ng/m3, with seasonal trends observed. Concentrations of APE metabolites in treated wastewater effluents in the US ranged from < 0.1 to 369 microg/l, in Spain they were between 6 and 343 microg/l and concentrations up to 330 microg/l were found in the UK. Levels in sediments reflected the high partition coefficients with concentrations reported ranging from < 0.1 to 13,700 microg/kg for sediments in the US. Fish in the UK were found to contain up to 0.8 microg/kg NP in muscle tissue. APEs degraded faster in the water column than in sediment. Aerobic conditions facilitate easier further biotransformation of APE metabolites than anaerobic conditions. PMID:12222618

  20. Simultaneous determination of halogenated derivatives of alkylphenol ethoxylates and their metabolites in sludges, river sediments, and surface, drinking, and wastewaters by liquid chromatography-mass spectrometry.

    PubMed

    Petrovic, M; Diaz, A; Ventura, F; Barceló, D

    2001-12-15

    A quantitative solid-phase extraction-liquid chromatography/mass spectrometry (SPE-LC/MS) method is described for the simultaneous analysis of halogenated byproducts of alkylphenolic compounds and their degradation products formed during chlorine disinfection in the presence of bromide ions. Compounds analyzed include brominated and chlorinated nonylphenol ethoxylates (XN-PEOs); octylphenol ethoxylates (XOPEOs); nonylphenols (XNP); nonylphenoxycarboxylates (XNPECs) and their precursors nonionic surfactants, alkylphenol ethoxylates (APEOs); and their metabolites formed during sewage treatment, alkylphenoxycarboxylates (APECs) and alkylphenols (APs). Target compounds were concentrated from water samples using a C18 SPE procedure. Extracts were analyzed using reversed phase LC/MS. The performances of both atmospheric pressure chemical ionization (APCI) and electrospray (ESI) interfaces were compared. ESI offered better sensitivity and specificity for a higher range of oligomers. Detection limits (LODs) for water samples were from 20 to 100 ng/L; and for sediment samples, from 2 to 10 microg/kg. Slightly higher LODs were obtained for sludge samples (5-25 microg/kg). Halogenated byproducts were found in sludge from Barcelona drinking water treatment plant in concentrations of 220 microg/kg for BrNP, 430 microg/kg for BrNPEOs (nEO = 1 - 2), and 1600 microg/kg for BrNPEOs (nEO = 3 - 15). The concentration of ClNPEOs was estimated to be in the order of 660 microg/kg (assuming the same response as BrNPEOs). Halogenated OPEOs were also identified, and their concentration was approximately 50 times lower than the concentration of NPEOs analogues. To our knowledge, this is the first method described that allows simultaneous determination of alkyphenol ethoxylates and halogenated derivatives, including degradation products. PMID:11791557

  1. 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. PMID:12523845

  2. 40 CFR 721.4700 - Metalated alkylphenol copolymer (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Metalated alkylphenol copolymer (generic name). 721.4700 Section 721.4700 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4700 Metalated alkylphenol copolymer (generic name). (a)...

  3. 40 CFR 721.4700 - Metalated alkylphenol copolymer (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Metalated alkylphenol copolymer (generic name). 721.4700 Section 721.4700 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4700 Metalated alkylphenol copolymer (generic name). (a)...

  4. 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. PMID:24784502

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

    PubMed

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

    2013-01-01

    Alkylphenols and their precursors, alkylphenol etoxylates, are a group of manmade chemicals used mainly as surfactants in domestic and industrial applications worldwide. It has been well established that they have endocrine disruption activity, hepatotoxic, genotoxic and other negative effects on animal and human health. In spite of the effort to reduce their use, they persist in the environment not only in industrial but also in remote regions, and were detected in the variety of natural matrices including air, water, soil as well as food products, and human blood and urine worldwide. This article summarizes their occurrence, fate in natural conditions, and toxicity including mode of action. A subject of our concern was the aquatic environment as the most important reservoir and target of their deleterious impact. PMID:24597317

  6. Macroscopic and Macromolecular Specificity of Alkylphenol Anesthetics for Neuronal Substrates

    PubMed Central

    Weiser, Brian P.; Hall, Michael A.; Weinbren, Nathan L.; Woll, Kellie A.; Dailey, William P.; Eckenhoff, Maryellen F.; Eckenhoff, Roderic G.

    2015-01-01

    We used a photoactive general anesthetic called meta-azi-propofol (AziPm) to test the selectivity and specificity of alkylphenol anesthetic binding in mammalian brain. Photolabeling of rat brain sections with [3H]AziPm revealed widespread but heterogeneous ligand distribution, with [3H]AziPm preferentially binding to synapse-dense areas compared to areas composed largely of cell bodies or myelin. With [3H]AziPm and propofol, we determined that alkylphenol general anesthetics bind selectively and specifically to multiple synaptic protein targets. In contrast, the alkylphenol anesthetics do not bind to specific sites on abundant phospholipids or cholesterol, although [3H]AziPm shows selectivity for photolabeling phosphatidylethanolamines. Together, our experiments suggest that alkylphenol anesthetic substrates are widespread in number and distribution, similar to those of volatile general anesthetics, and that multi-target mechanisms likely underlie their pharmacology. PMID:25853337

  7. 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...

  8. 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...

  9. 40 CFR 721.10443 - Ethoxylated alkylphenol sulfate, ammonium salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 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 to... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethoxylated alkylphenol...

  10. Alkylphenols in atmospheric depositions and urban runoff.

    PubMed

    Bressy, A; Gromaire, M-C; Lorgeoux, C; Chebbo, G

    2011-01-01

    A sampling campaign was conducted in order to determine alkylphenol (AP) concentrations in stormwater as well as potential AP sources in suburban environments. An analytical procedure was developed to quantify APs in bulk atmospheric deposition, building runoff, road runoff and stormwater. Both nonylphenols and octylphenols could be quantified in each sample. Median stormwater concentrations amounted to: 470 ng/l for nonylphenols, and 36 ng/l for octylphenols. These concentrations are 3 times higher than those found in atmospheric deposition, thus proving that local human activity constitutes a significant source of contamination. The contributions of the various sources to stormwater have been assessed from mass balances at the catchment scale. 70% of AP mass in stormwater originates from building and road emissions. Annual AP fluxes have been extrapolated from the total AP mass measured over our sampling periods for atmospheric depositions (44 to 84 µgNP/m(2)/yr) and stormwater (100 to 190 µgNP/m(2)/yr). Moreover, since APs were mainly found in the dissolved fraction, runoff treatment devices based on settling are unlikely to be very efficient. PMID:21330713

  11. 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

  12. 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...

  13. RELATIVE BINDING AFFINITY OF ALKYLPHENOLS TO RAINBOW TROUT ESTROGEN RECEPTOR

    EPA Science Inventory

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

  14. Determination of nonylphenol ethoxylates and octylphenol ethoxylates in environmental samples using 13C-labeled surrogate compounds.

    PubMed

    Yoshida, Yasuko; Ito, Azusa; Murakami, Masashi; Murakami, Takayuki; Fujimoto, Hideharu; Takeda, Kikuo; Suzuki, Shigeru; Hori, Masahiro

    2007-10-01

    Alkylphenol polyethoxylates (APEOs) have been widely used as nonionic surfactants in a variety of industrial and commercial products. Typical compounds are nonylphenol polyethoxylates (NPEOs) and octylphenol polyethoxylates (OPEOs), which serve as precursors to nonylphenol (NP) and octylphenol (OP), respectively. NP and 4-t-OP are known to have endocrine disrupting effects on fish (medaka, Oryzias latipes), so it is important to know the concentrations of APEOs in the environment. Because the analytical characteristics of these compounds depend on the length of the ethoxy chain, it is necessary to use appropriate compounds as internal standards or surrogates. We synthesized two 13C-labeled surrogate compounds and used these compounds as internal standards to determine NPEOs and OPEOs by high-performance liquid chromatography (LC)-mass spectrometry. Method detection limits were 0.015 microg/L for NP (2)EO to 0.037 microg/L for NP(12)EO, and 0.011 microg/L for OP(3,6)EO to 0.024 microg/L for OP (4)EO. NPEO concentrations in water from a sewage treatment plant were less than 0.05-0.52 microg/L for final effluent and 1.2-15 microg/L for influent. OPEO concentrations were less than 0.05-0.15 microg/L for the final effluent and less than 0.05-1.1 microg/L for influent. PMID:17972761

  15. Determination of alkylphenols and alkylphenol ethoxylates in sewage sludge: effect of sample pre-treatment.

    PubMed

    Fernández-Sanjuan, María; Rigol, Anna; Sahuquillo, Angels; Rodríguez-Cruz, Sonia; Lacorte, Silvia

    2009-07-01

    A complete characterization of sewage sludge collected from five biological waste water treatment plants was done to determine physico-chemical parameters, heavy metals and alkylphenols, making special emphasis on sampling, homogenization, and sample pre-treatment. Ultrasonic extraction followed by gas chromatrography coupled with mass spectrometry was used to evaluate the effect of sample pre-treatment (untreated sample, freeze-drying, drying at 40 degrees C or drying at 100 degrees C) on the concentration of octylphenol (OP), nonylphenol (NP) and nonylphenol ethoxylates (NP1EO, NP2EO). Untreated samples and samples dried at 100 degrees C gave concentration levels up to 62% and 89% lower, respectively, than freeze-dried samples. In 50% of cases, freeze-dried samples led to significantly higher concentrations than those obtained by drying at 40 degrees C. Thus, freeze-drying is the recommended sample pre-treatment to prevent possible losses of OP, NP, and NP1EO. Using this methodology, concentrations detected were from 3.2 to 199 mg kg(-1) being NP followed by NP1EO found in highest concentration. The total concentration of NP and NP1EO exceeded the limit of 50 mg kg(-1) proposed by the draft European directive on sewage sludge in three out of five samples studied. Contrarily, heavy metals were below the legislated values. PMID:19305980

  16. Certification of reference materials for the determination of alkylphenols.

    PubMed

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

    2015-04-01

    Certified reference materials (CRMs) are playing an increasingly important role in national and international standardizing activities. In Japan, primary standard solutions for analyses of endocrine disrupters are supplied under the national standards dissemination system named the Japan Calibration Service System (JCSS). For the traceability on reference materials used for preparation of the primary standard solutions based on the JCSS, the National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) has developed and certified high-purity reference materials of alkylphenols as NMIJ CRMs, such as 4-n-nonylphenol, 4-tert-octylphenol, 4-n-heptylphenol, 4-tert-butylphenol, and 2,4-dichlorophenol. Thereafter, it is essential to determine the alkylphenols by using these solutions based on the JCSS for environmental monitoring and risk assessments because analytical values obtained by using the solutions can ensure the reliability and traceability of the chemical analyses. PMID:25656848

  17. 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.

  18. 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... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  19. 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... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  20. 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... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  1. 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... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  2. 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... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  3. 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...

  4. Identification of estrogen-like alkylphenols in produced water from offshore oil installations.

    PubMed

    Boitsov, Stepan; Mjøs, Svein A; Meier, Sonnich

    2007-12-01

    Produced water released into the sea from oil installations contains a vast number of organic compounds. This work focuses on the analysis and identification of phenols in produced water, in particular long-chain para-substituted alkylphenols, which act as endocrine disruptors for marine biota. Some alkylphenol standards, unavailable commercially, have been synthesised and some compounds of interest identified. However, a complete identification is not possible since conventional GC techniques cannot achieve the desired degree of separation. An overview of the levels of the 52 known alkylphenols in produced water from nine oil installations in the North and Norwegian Seas has been made. The previously unidentified alkylphenols in produced water have been characterised by means of alkylphenol retention indices (APRI) and mass spectrometry, and their total amounts estimated for the same nine locations. Our results confirm the presence of naphthols and other as yet unidentified compounds in produced water, while thiophenols were not detected by the used technique. PMID:17714776

  5. Meta-analysis of environmental contamination by alkylphenols.

    PubMed

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

    2012-11-01

    Alkylphenols and alkylphenol ethoxylates (APE) are toxics classified as endocrine-disrupting compounds; they are used in detergents, paints, herbicides, pesticides, emulsifiers, wetting and dispersing agents, antistatic agents, demulsifiers, and solubilizers. Many studies have reported the occurrence of alkylphenols in different environmental matrices, though none of these studies have yet to establish a comprehensive overview of such compounds in the water cycle within an urban environment. This review summarizes APE concentrations for all environmental media throughout the water cycle, from the atmosphere to receiving waters. Once the occurrence of compounds has been assessed for each environmental compartment (urban wastewater, wastewater treatment plants [WWTP], atmosphere, and the natural environment), data are examined in order to understand the fate of APE in the environment and establish their geographical and historical trends. From this database, it is clear that the environment in Europe is much more contaminated by APE compared to North America and developing countries, although these APE levels have been decreasing in the last decade. APE concentrations in the WWTP effluent of developed countries have decreased by a factor of 100 over the past 30 years. This study is aimed at identifying both the correlations existing between environmental compartments and the processes that influence the fate and transport of these contaminants in the environment. In industrial countries, the concentrations observed in waterways now represent the background level of contamination, which provides evidence of a past diffuse pollution in these countries, whereas sediment analyses conducted in developing countries show an increase in APE content over the last several years. Finally, similar trends have been observed in samples drawn from Europe and North America. PMID:22864754

  6. Degradation of alkylphenol ethoxylates by Pseudomonas sp. strain TR01.

    PubMed

    Maki, H; Masuda, N; Fujiwara, Y; Ike, M; Fujita, M

    1994-07-01

    An alkylphenol ethoxylate-degrading bacterium was isolated from activated sludge of a municipal sewage treatment plant by enrichment culture. This organism was found to belong to the genus Pseudomonas; since no corresponding species was identified, we designated it as Pseudomonas sp. strain TR01. This strain had an optimal temperature and pH of 30 degrees C and 7, respectively, for both growth and the degradation of Triton N-101 (a nonylphenol ethoxylate in which the average number of ethylene oxide [EO] units is 9.5). The strain was unable to mineralize Triton N-101 but was able to degrade its EO chain exclusively. The resulting dominant intermediate was identified by normal-phase high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry as a nonylphenol ethoxylate with 2 mol of EO units. A carboxylated metabolite, [(nonylphenoxy)ethoxy]acetic acid, was detected by gas chromatography-mass spectrometry. This bacterium also metabolized alcohol ethoxylates with various numbers of EO units but not polyethylene glycols whatever their degree of polymerization. By oxygen consumption assay, the alkyl group or arene corresponding to the hydrophobic part of alcohol ethoxylates or alkylphenol ethoxylates was shown to contribute to the induction of the metabolic system of the EO chain of Triton N-101, instead of the EO chain itself, which corresponds to its hydrophilic part. Thus, the isolated pseudomonad bacterium has unique substrate assimilability: it metabolizes the EO chain only when the chain linked to bulky hydrophobic groups. PMID:8074508

  7. Degradation of alkylphenol ethoxylates by Pseudomonas sp. strain TR01.

    PubMed Central

    Maki, H; Masuda, N; Fujiwara, Y; Ike, M; Fujita, M

    1994-01-01

    An alkylphenol ethoxylate-degrading bacterium was isolated from activated sludge of a municipal sewage treatment plant by enrichment culture. This organism was found to belong to the genus Pseudomonas; since no corresponding species was identified, we designated it as Pseudomonas sp. strain TR01. This strain had an optimal temperature and pH of 30 degrees C and 7, respectively, for both growth and the degradation of Triton N-101 (a nonylphenol ethoxylate in which the average number of ethylene oxide [EO] units is 9.5). The strain was unable to mineralize Triton N-101 but was able to degrade its EO chain exclusively. The resulting dominant intermediate was identified by normal-phase high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry as a nonylphenol ethoxylate with 2 mol of EO units. A carboxylated metabolite, [(nonylphenoxy)ethoxy]acetic acid, was detected by gas chromatography-mass spectrometry. This bacterium also metabolized alcohol ethoxylates with various numbers of EO units but not polyethylene glycols whatever their degree of polymerization. By oxygen consumption assay, the alkyl group or arene corresponding to the hydrophobic part of alcohol ethoxylates or alkylphenol ethoxylates was shown to contribute to the induction of the metabolic system of the EO chain of Triton N-101, instead of the EO chain itself, which corresponds to its hydrophilic part. Thus, the isolated pseudomonad bacterium has unique substrate assimilability: it metabolizes the EO chain only when the chain linked to bulky hydrophobic groups. PMID:8074508

  8. 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

  9. Sequential injection immunoassay for environmental measurements.

    PubMed

    Soh, Nobuaki; Tanaka, Mayumi; Hirakawa, Koji; Zhang, RuiQi; Nakajima, Hizuru; Nakano, Koji; Imato, Toshihiko

    2011-01-01

    Sequential injection immunoassay systems for environmental measurements based on the selective immunoreaction between antigen and antibody were described. A sequential injection analysis (SIA) technique is suitable to be applied for the procedure of enzyme-linked immunosorbent assay (ELISA), because the washing and the addition of reagent solutions can be automated by using a computer-controlled syringe pump and switching valve. We selected vitellogenin (Vg), which is a biomarker for evaluating environmental risk caused by endocrine-disrupting chemicals in the hydrosphere, and linear alkylbenzene sulfonates (LAS) and alkylphenol polyethoxylates (APEO), which are versatile surfactants, as target analytes in the flow immunoassay systems. For Vg monitoring, SIA systems based on spectrophotometric, chemiluminescence, and electrochemical determinations were constructed. On the other hand, chemiluminescence determination was applied to the detection of LAS and APEO. For APEO, an SIA system combined with surface plasmon resonance (SPR) sensor was also developed. These new sequential injection immunoassay systems are expected to be useful systems for environmental analysis. PMID:22076332

  10. Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain).

    PubMed

    Céspedes, Raquel; Lacorte, Sílvia; Ginebreda, Antonio; Barceló, Damià

    2008-05-01

    The partitioning of alkylphenols in the dissolved and particulate matter of influents, effluents, accumulation onto sludge and the impact of sewage treatment plant upon receiving waters was studied along the Ter River basin (Catalonia, NE Spain). A solid-phase extraction or pressurized liquid extraction followed by liquid chromatography-mass spectrometry was developed and permitted to determine target compounds with high efficiency in waters, particulate material and sludge. Nonylphenol mono- and diethoxylate, nonylphenol and octylphenol partitioned preferably upon particulate matter and sludge, whereas long chain NPE(3-15)O prevailed in the dissolved phase and was released by effluents. Within the treatment process, a net accumulation of alkylphenols in sludge was found, producing up to 148g/t/month. The removal efficiency of alkylphenols was of 37-90% and depended on the treatment. Assessment on the fate of these contaminants within STPs is discussed in terms of flow rates, biological oxygen demand and tons of sludge produced. PMID:18262317

  11. Sediment-porewater partition of nonylphenol polyethoxylates: field measurements from Lanzhou Reach of Yellow River, China.

    PubMed

    Yu, Yong; Xu, Jian; Sun, Hongwen; Dai, Shugui

    2008-08-01

    Nonylphenol polyethoxylates (NPnEO) and nonylphenol (NP) have drawn much environmental concern because of their weak estrogenic activities. The present study focused on the spatial distribution of NPnEO and NP in surface sediments and their corresponding porewaters along Lanzhou Reach of Yellow River, China. Long EO chain NPnEO analogs with n > 2 were not measurable in most sediment and porewater samples, so only NP, nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) were discussed in this study. Concentrations of NP, NP1EO, and NP2EO in the sediments ranged from 61.3 to 113.9, 31.1 to 55.9, and 47.9 to 74.1 ng/g dry weight, respectively. A significant correlation (R2= 0.56, p < 0.01) was observed between NP levels and organic carbon content of the sediments, whereas no correlation was found for the more hydrophilic NP1EO and NP2EO. The concentrations of NP, NP1EO, and NP2EO in the porewaters ranged from 0.35 to 1.95, 0.06 to 0.63, and 0.08 to 0.38 microg/L. The mean in situ log K(oc) values (n = 13, S1 excluded) of NP, NP1EO, and NP2EO were 4.48, 4.94, and 5.06, respectively, which were lower than those measured in batch adsorption experiments. PMID:18213479

  12. The Bioconcentration and Degradation of Nonylphenol and Nonylphenol Polyethoxylates by Chlorella vulgaris

    PubMed Central

    Sun, Hong-Wen; Hu, Hong-Wei; Wang, Lei; Yang, Ying; Huang, Guo-Lan

    2014-01-01

    Nonylphenol polyethoxylates (NPnEOs), a major class of nonionic surfactants, can easily enter into aquatic environments through various pathways due to their wide applications, which leads to the extensive existence of their relative stable metabolites, namely nonylphenol (NP) and mono- to tri-ethoxylates. This study investigated the bioconcentration and degradation of NP and NPnEO oligomers (n = 1–12) by a green algae, Chlorella vulgaris. Experimental results showed that C. vulgaris can remove NP from water phase efficiently, and bioconcentration and degradation accounted for approximately half of its loss, respectively, with a 48 h BCF (bioconcentration factor) of 2.42 × 103. Moreover, C. vulgaris could concentrate and degrade NPnEOs, distribution profiles of the series homologues of the NPnEOs in algae and water phase were quite different from the initial homologue profile. The 48 h BCF of the NPnEO homologues increased with the length of the EO chain. Degradation extent of total NPnEOs by C. vulgaris was 95.7%, and only 1.1% remained in water phase, and the other 3.2% remained in the algal cells. The algae removed the NPnEOs mainly through degradation. Due to rapid degradation, concentrations of the long chain NPnEO homologous in both water (n ≥ 2) and the algal phase (n ≥ 5) was quite low at the end of a 48 h experiment. PMID:24445260

  13. Sites and functional consequence of VDAC-alkylphenol anesthetic interactions.

    PubMed

    Weiser, Brian P; Bu, Weiming; Wong, David; Eckenhoff, Roderic G

    2014-11-28

    General anesthetics have previously been shown to bind mitochondrial VDAC. Here, using a photoactive analog of the anesthetic propofol, we determined that alkylphenol anesthetics bind to Gly56 and Val184 on rat VDAC1. By reconstituting rat VDAC into planar bilayers, we determined that propofol potentiates VDAC gating with asymmetry at the voltage polarities; in contrast, propofol does not affect the conductance of open VDAC. Additional experiments showed that propofol also does not affect gramicidin A properties that are sensitive to lipid bilayer mechanics. Together, this suggests propofol affects VDAC function through direct protein binding, likely at the lipid-exposed channel surface, and that gating can be modulated by ligand binding to the distal ends of VDAC β-strands where Gly56 and Val184 are located. PMID:25448677

  14. Regio- and stereospecific conversion of 4-alkylphenols by the covalent flavoprotein vanillyl-alcohol oxidase.

    PubMed

    van den Heuvel, R H; Fraaije, M W; Laane, C; van Berkel, W J

    1998-11-01

    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

  15. 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. PMID:20044249

  16. 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. PMID:27343574

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

    SciTech Connect

    Ahel, M.; Giger, W.

    1985-07-01

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

  18. Sequential solid phase extraction protocol followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry for the trace determination of non ionic polyethoxylated surfactants in tannery wastewaters

    SciTech Connect

    Castillo, M.; Barcelo, D.; Ventura, F.

    1999-06-01

    Automated solid-phase extraction (SPE) with C18 and styrene-divinylbenzene cartridges in series was used for the preconcentration of non ionic polyethoxylated surfactants in tannery wastewater. Fractionated extracts were analyzed by LC-MS using Atmospheric Pressure Chemical Ionization (APCI) in the Positive and Negative Ion modes. Recoveries for nonionic surfactants were approximately of 72, 90 and 80% for polyethylene glycols, nonylphenol and alcohol ethoxylates in the polar, aromatic and medium polarity fractions, respectively. Data acquisition in the selected ion monitoring mode afforded limits of quantification from 0.1 to 0.8 {micro}g/l for tridecylic polyethoxylated alcohol and polyethoxylated glycol, respectively, in the complex tannery wastewaters. The tannery effluents investigated contained between 0.03 to 3.0 mg/l of polyethylene glycol and nonylphenol polyethoxylate, respectively.

  19. Differential protein expression in the estuarine copepod Eurytemora affinis after diuron and alkylphenol exposures.

    PubMed

    Boulangé-Lecomte, Céline; Rocher, Béatrice; Cailleaud, Kévin; Cosette, Pascal; Legrand, Eléna; Devreker, David; Budzinski, Hélène; Souissi, Sami; Forget-Leray, Joëlle

    2016-07-01

    Proteomics was used in the calanoid copepod Eurytemora affinis for screening of protein expression modifications induced by organic contaminants. The copepods were exposed in a continuous flow-through system for 86 h to environmentally relevant concentrations of contaminants representative of the pollution in the Seine Estuary (Haute-Normandie, France; diuron, 500 ng L(-1) ; alkylphenol mixture, 1000 ng L(-1) ). Proteome analysis of whole-body copepod extracts by 2-dimensional gel electrophoresis revealed that the contaminants induced modifications in protein expression, with the highest quantitative variations occurring after diuron exposure. Specifically, 88 and 41 proteins were differentially expressed after diuron and alkylphenol treatments, respectively. After mass spectrometry analysis, 51 (diuron exposure) and 15 (alkylphenol exposure) proteins were identified. The identified proteins were potentially related to energy metabolism, cell growth, nervous signal conductivity, excitotoxicity, oxidative stress response, and antioxidant defense. The data suggest a massive general disturbance of physiological functions of E. affinis after diuron exposure, whereas alkylphenols induced an alteration of a few targeted physiological functions. The protein expression signatures identified after contaminant exposure deserve further investigation in terms of the development of novel potential biomarkers for water quality assessment. Environ Toxicol Chem 2016;35:1860-1871. © 2015 SETAC. PMID:26677818

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

    PubMed

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

    2014-01-01

    The widespread use of alkylphenols in European industry has led to their presence in the environment and the living organisms of the Baltic Sea. The present study (2011-2012) was designed to determine the concentrations of alkylphenols, 4-nonylphenol (NP) and 4-tert-octylphenol (OP), in surface sediments of the Gulf of Gdansk, a section of the Baltic that lies in close proximity to industrial and agricultural areas and borders with an agglomeration of nearly one million inhabitants. It is also where the Vistula, the largest Polish river, ends its course. In spring, large concentrations of 4-nonylphenol and 4-tert-octylphenol were washed off into the coastal zone with meltwater. In summertime, sediments near the beach had the highest alkylphenol concentrations (NP-2.31 ng g(-1) dw, OP-13.09 ng g(-1) dw), which was related to tourism and recreational activity. In silt sediments located off the coast, the highest NP (1.46 ng g(-1) dw) and OP (6.56 ng g(-1) dw) amounts were observed in autumn. The origin of OP and NP at those test stations was linked to atmospheric transport of black carbon along with adsorbed alkylphenols. PMID:25132692

  1. 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

  2. Determination of alkylphenol polyethoxylates, bisphenol-A, 17α-ethynylestradiol and 17β-estradiol and its metabolites in sewage samples by SPE and LC/MS/MS.

    PubMed

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

    2010-11-15

    Recently, many chemicals released into the environment have been shown to mimic endogenous hormones such as estradiol. It has been demonstrated that these compounds cause several adverse effects on wildlife and humans, such as the feminization of animal species, development of physical abnormalities and birth defects, and reproductive failure. In an effort to model the behaviour of some endocrine-disrupting chemicals (EDCs) and to establish the level of contamination in sewage samples, a quantitative method for the simultaneous determination of nonylphenol, octylphenol and corresponding ethoxylates (1-12), 17α-ethynylestradiol, bisphenol-A, and 17β-estradiol and two of its metabolites have been developed. Identification and quantification were achieved by high performance liquid chromatography-tandem mass spectrometry (LC-ESI-MS/MS). Satisfactory detection limits (between 0.5-6 ng L(-1) in the dissolved phase and 1.4-12.7 ng g(-1) in the particulate phase) and analyte recoveries (between 60% and 108%) were achieved for target compounds. The optimised method was applied to the determination of EDCs in liquid sewage samples collected from a wastewater treatment plant (WWTP) in Las Palmas de Gran Canaria (Spain). Concentrations of EDCs ranged from <10 ng L(-1) to nearly 1200 ng L(-1) in the dissolved phase, and from 0.005 μg g(-1) to 2.8 μg g(-1) in the suspended particulate matter. PMID:20724070

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

    PubMed

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

    2016-05-15

    Wild mussels (Mytilus galloprovincialis) were selected as bioindicators of chemical pollution to evaluate the occurrence and spatial distribution of five endocrine disrupting compounds in the Spanish Atlantic coast and Bay of Biscay. A total of 24 samples were collected in May, 2011 and analysed by selective pressurized liquid extraction followed by liquid chromatography tandem mass spectrometry determination. Branched alkylphenols (4-tert-octylphenol and nonylphenol) were determined in more than 90% of the analysed samples whereas the presence of linear alkylphenols (4-n-octylphenol and 4-n-nonylphenol) was scarcely detected (<12% of the samples). Wastewater treatment plants discharges and nautical, fishing and shipping activities were considered the primary sources of contamination by alkylphenols. Bisphenol A was found in 16% of the analysed samples associated to punctual industrial discharges. A total endocrine disrupting compound (alkylphenols and bisphenol A) average concentration of 604ngg(-1) dw was calculated and nonylphenol was the main contributor in almost all sampling points. PMID:27001713

  4. 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.

  5. Isolation and characterization of Sphingomonas sp. Y2 capable of high-efficiency degradation of nonylphenol polyethoxylates in wastewater.

    PubMed

    Bai, Naling; Wang, Sheng; Abuduaini, Rexiding; Zhu, Xufen; Zhao, Yuhua

    2016-06-01

    Nonylphenol polyethoxylates (NPEOs), although banned for decades, are still widely used in manufactories and thus affect human lives. In this study, a highly efficient NPEO-degrading bacterium, Sphingomonas sp. Y2, was isolated from sewage sludge by enrichment culture. Strain Y2 ensured the complete removal of NPEO in 48 h and degraded 99.2 % NPEO (1,000 mg L(-1)) within 30 h at a specific growth rate of 0.73 h(-1) in minimum salt medium. To date, this degradation efficiency is the highest reported for NPEO metabolism by a pure bacterium under this condition. Furthermore, the application of this bacterium to wastewater treatment demonstrated that it metabolized 98.5 % NPEO (1,000 mg L(-1)) within 5 days with a specific growth rate of 2.03 day(-1). The degradation intermediates, identified as nonylphenol, short-chain NPEOs and short-chain nonylphenol polyethoxycarboxylates by high-performance liquid chromatography and gas chromatography-mass spectrometry, indicated the sequential exo-cleavage of the EO chain. Additionally, the enzymes involved in the biodegradation were inducible rather than constitutive. Considering that strain Y2 exhibits prominent biodegradation advantages in industrial wastewater treatment, it might serve as a promising potential candidate for in situ bioremediation of contamination by NPEOs and other structurally similar compounds. PMID:26961533

  6. Effects of polyethoxylate lauryl ether (Brij 35) addition on phenanthrene biodegradation in a soil/water system.

    PubMed

    Chang, Yi-T; Hung, Chun-H; Chou, Hsi-L

    2014-01-01

    Non-ionic surfactants usually are often selected for use in surfactant flushing technology, which is a process that can be used as part of PAH-contaminated soil bioremediation. Phenanthrene (PHE) biodegradation in the presence of polyethoxylate lauryl ether (Brij 35) was studied in two soil/water systems. The natural soil organic matter content (SOM) and the present of Brij 35, both above the critical micelle concentration (CMC) and below the CMC, changed the rate of PHE biodegradation in the presence of Brij 35. PHE biodegradation is different in the two different soil/water systems: PHE > PHE-Brij 35-Micelle > PHE-Brij 35-Monomer in the clay/water system; PHE-Brij 35-Micelle > PHE-Brij 35-Monomer > PHE in the natural soil/water system. Among the free-living species associated with PHE-Brij 35 biodegradation, Brevundimonas diminuta, Caulobacter spp., Mycoplana bullata, Acidovorax spp. and Pseudomonas aeruginosa accounted for 90.72% to 99.90% of the bacteria present. Specific hydrolytic enzymes, including esterases, glycosol-hydrolases and phosphatases, are expressed during PHE biodegradation. The information presented here will help the engineering design of more effective PAH bioremediation systems that use Brij 35 series flushing technology. In particular, micelles of Brij 35 can be used to accelerate the rate of remediation of PAH-contaminated soil in natural soil/water systems. PMID:25320854

  7. Influence of sediment on the fate and toxicity of a polyethoxylated tallowamine surfactant system (MON 0818) in aquatic microcosms

    USGS Publications Warehouse

    Wang, N.; Besser, J.M.; Buckler, D.R.; Honegger, J.L.; Ingersoll, C.G.; Johnson, B.T.; Kurtzweil, M.L.; MacGregor, J.; McKee, M.J.

    2005-01-01

    The fate and toxicity of a polyethoxylated tallowamine (POEA) surfactant system, MON 0818, was evaluated in water-sediment microcosms during a 4-d laboratory study. A surfactant solution of 8 mg l-1 nominal concentration was added to each of nine 72-l aquaria with or without a 3-cm layer of one of two natural sediments (total organic carbon (TOC) 1.5% or 3.0%). Control well water was added to each of nine additional 72-l aquaria with or without sediment. Water samples were collected from the microcosms after 2, 6, 24, 48, 72, and 96 h of aging to conduct 48-h toxicity tests with Daphnia magna and to determine surfactant concentrations. Elevated mortality of D. magna (43-83%) was observed in overlying water sampled from water-only microcosms throughout the 96-h aging period, whereas elevated mortality (23-97%) was only observed in overlying water sampled from water-sediment microcosms during the first 24 h of aging. Measured concentrations of MON 0818 in water-only microcosms remained relatively constant (4-6 mg l-1) during the 96-h period, whereas the concentrations in overlying water from microcosms containing either of the two types of sediment dissipated rapidly, with half-lives of 13 h in the 3.0% TOC sediment and 18 h in the 1.5% TOC sediment. Both toxicity and the concentration of MON 0818 in overlying water decreased more rapidly in microcosms containing sediment with the higher percent TOC and clay and with a higher microbial biomass. Mortality of D. magna was significantly correlated with surfactant concentrations in the overlying water. These results indicate that the toxicity of the POEA surfactant in water rapidly declines in the presence of sediment due to a reduction in the surfactant concentration in the overlying water above the sediment.

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

    PubMed

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

    2013-03-01

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

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

    PubMed

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

    2014-08-01

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

  10. Estrogenic activity of alkylphenols, bisphenol S, and their chlorinated derivatives using a GFP expression system.

    PubMed

    Kuruto-Niwa, Ryoko; Nozawa, Ryushi; Miyakoshi, Takashi; Shiozawa, Tatsushi; Terao, Yoshiyasu

    2005-01-01

    Alkylphenol ethoxylates, widely used non-ionic surfactants, are biodegraded into alkylphenols such as nonylphenol (NP) and t-octylphenol (OP), short-chain ethoxylates such as NP-monoethoxylate (NP1EO) and NP-diethoxylate (NP2EO), and alkylphenoxy carboxylic acids such as 4-t-octylphenoxyacetic acid (OP1EC). Bisphenol S (BPS) is more heat-stable and photo-resistant than bisphenol A (BPA), and therefore replaces BPA. These chemicals could be chlorinated during wastewater treatment. We synthesized these compounds and their chlorinated derivatives to estimate their estrogenic activities using a GFP expression system. The EC(50) ranking of NP-related compounds was NP > ClNP > diClNP > NP1EO > ClNP1EO > NP2EO. The estrogenic activity of OP1EC was 10 times less potent than parent OP. Furthermore, BPS showed comparable estrogenic activity with BPA. The EC(50) ranking of BPS-related compounds was BPA ≥ BPS > triClBPS > diClBPS > ClBPS. Other tested BPS derivatives had no estrogenic activity. Chlorination of the tested chemicals did not enhance their estrogenic activity, in contrast to certain chlorinated BPAs. Thus, our results demonstrated that chlorinated derivatives of NP, OP, and BPS, even if artificially produced during wastewater processing, were less estrogenic than their parent chemicals, known as endocrine disruptors. PMID:21783468

  11. Alkylphenol ethoxylate degradation products in land-applied sewage sludge (biosolids).

    PubMed

    La Guardia, M J; Hale, R C; Harvey, E; Mainor, T M

    2001-12-15

    Alkylphenol ethoxylates, widely used in commercial and household detergents in the United States, can degrade during the wastewater treatment process to more toxic, estrogenic, and lipophilic compounds. These include octylphenol (OP), nonylphenols (NPs), nonylphenol monoethoxylates (NP1EOs), and nonylphenol diethoxylates (NP2EOs). These compounds have received considerable attention due to their acute toxicity and ability to disrupt the endocrine system. In Europe, regulations have been established to control their impact on the environment. In this study, biosolids derived from all 11 U.S. wastewater treatment plants examined contained detectable levels of OP, NPs, NP1EOs, and NP2EOs. Nine exceeded the current Danish land application limit (30 mg/kg; sum of NPs, NP1EOs, and NP2EOs) by 6-33x. NPs were the major component, and their concentrations therein ranged from 5.4 to 887 mg/kg (dry weight). OP, reportedly 10-20x more estrogenic than NP, was detected in these same nine biosolids at levels up to 12.6 mg/kg. Three biosolids were also subjected to the U.S. Environmental Protection Agency Toxicity Characteristic Leaching Procedure Method 1311. NPs and NP1EOs were both detected in the leachate; the former at concentrations from 9.4 to 309 microg/L. On the basis of effect levels published in the literature, alkylphenol ethoxylate degradates in U.S. biosolids may cause adverse environmental impacts. PMID:11775155

  12. 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.

  13. 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.

  14. AN LC/ESI-MS/MS METHOD FOR THE DETECTION OF ALKYLPHENOL ETHOXYLATES IN WATER AND SEDIMENT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Interest in substances suspected of causing endocrine disruption effects in biota has increased over the last few years. Nonyl- and octylphenol (NP and OP) and degradation products of their respective alkylphenol ethoxylates (APnEOs) are considered potential endocrine disrupters. These effects and...

  15. Influence of alkylphenols and trace elements in toxic, genotoxic, and endocrine disruption activity of wastewater treatment plants.

    PubMed

    Isidori, Marina; Lavorgna, Margherita; Palumbo, Maria; Piccioli, Veronica; Parrella, Alfredo

    2007-08-01

    Toxicity and endocrine interference of influent and effluent waters from domestic and industrial wastewater treatment plants were determined. In addition, chemical analyses were performed to detect the presence of 17beta-estradiol, 17alpha-ethinyl estradiol, nonylphenol, 4-octylphenol, and p-t-octylphenol as well as lead, copper, and cadmium in these matrices. The results showed that despite low acute toxic potential, most of the samples tested showed both genotoxicity and endocrine interference. Furthermore, to establish whether the observed effects were caused by the alkylphenols and the heavy metals detected, toxic, genotoxic, and endocrine interference tests also were performed on pure chemicals. The acute toxicity was measured on the crustacean Daphnia magna. The estrogenic activity was determined by using the yeast estrogen screen with Saccharomyces cerevisiae RMY326, whereas the SOS Chromotest and Ames test detected the genotoxicity on Escherichia coli PQ37 and Salmonella typhimurium TA98 and TA100, respectively. The results showed that the toxicity found in the matrices did not match the values found for pure chemicals, but a clear correlation was found between alkylphenols and genotoxicity. Both heavy metals and alkylphenols took part in the endocrine interference activity. PMID:17702343

  16. 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

  17. Characterization of alkylphenol degradation gene cluster in Pseudomonas putida MT4 and evidence of oxidation of alkylphenols and alkylcatechols with medium-length alkyl chain.

    PubMed

    Takeo, Masahiro; Prabu, Subbuswamy K; Kitamura, Chitoshi; Hirai, Makoto; Takahashi, Hana; Kato, Dai-Ichiro; Negoro, Seiji

    2006-10-01

    Alkylphenols (APs) are ubiquitous contaminants in aquatic environments and have endocrine disrupting and toxic effects on aquatic organisms. To investigate biodegradation mechanisms of APs, an AP degradation gene cluster was cloned from a butylphenol (BP)-degrading bacterium, Pseudomonas putida MT4. The gene cluster consisted of 13 genes named bupBA1A2A3A4A5A6CEHIFG. From the nucleotide sequences, bupA1A2A3A4A5A6 were predicted to encode a multicomponent phenol hydroxylase (PH), whereas bupBCEHIFG were expected to encode meta-cleavage pathway enzymes. A partial sequence of a putative NtrC-type regulatory gene, bupR, was also found upstream of the gene bupB. This result indicates that APs can be initially oxidized into alkylcatechols (ACs), followed by the meta-cleavage of the aromatic rings. To confirm this pathway, AP degradation tests were carried out using the recombinant P. putida KT2440 harboring the PH genes (bupA1A2A3A4A5A6). The recombinant strain oxidized 4-n-APs with an alkyl chain of up to C7 (< or = C7) efficiently and also several BPs including those with an alkyl chain with some degree of branching. Therefore, it was found that PH had a broad substrate specificity for APs with a medium-length alkyl chain (C3-C7). Moreover, the cell extract of a recombinant Escherichia coli harboring bupB (a catechol 2,3-dioxygenase gene) converted 4-n-ACs with an alkyl chain of < or = C9 into yellow meta-cleavage products with a maximum absorbance at 379 nm, indicating that the second step enzyme in this pathway is also responsible for the degradation of ACs with a medium-length alkyl chain. These results suggest that MT4 is a very useful strain in the biodegradation of a wide range of APs with a medium-length alkyl chain, which known nonylphenol-degrading Sphingomonas strains have never degraded. PMID:17116584

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

    PubMed

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

    2013-05-01

    This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP₁EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP1EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale. PMID:23054786

  19. Effects of diquat and fomesafen applied alone and in combination with a nonylphenol polyethoxylate adjuvant on Lemna minor in aquatic indoor microcosms.

    PubMed

    Gorzerino, Caroline; Quemeneur, Alphonse; Hillenweck, Anne; Baradat, Maryse; Delous, Georges; Ollitrault, Martine; Azam, Didier; Caquet, Thierry; Lagadic, Laurent

    2009-03-01

    The influence of tank-mix adjuvants on pesticide toxicity remains largely unknown. Agral 90, a nonylphenol polyethoxylated tank-mix adjuvant, has been used with diquat (bipyridylium herbicide) and fomesafen (diphenyl-ether herbicide) in aquatic indoor microcosms in order to compare the toxicity of the single compounds and of binary herbicide-adjuvant mixtures to Lemna minor. Twenty-four microcosms were used and treatments were performed with substances alone or with herbicide-adjuvant binary mixtures, at two concentrations levels (44.4 and 222.2 microg/L for the herbicides, and 100 and 500 microg/L for Agral 90). Toxicity was assessed weekly for 1 month through growth measurements, as inferred from the relative frond number (RFN) and relative frond area (RFA). Concentrations of diquat and fomesafen in water and sediments were measured weekly. The herbicides showed very different behaviour in microcosms, with a rapid disappearance of diquat from the aqueous phase whereas fomesafen levels remained almost constant over time. Diquat strongly inhibited the growth of L. minor whereas fomesafen had no effect on plant growth. Presence of the adjuvant only slightly reduced the effect of the lowest concentration of diquat, probably as a result of dispersion of the herbicide at the water surface. It is concluded that tank-mix adjuvant designed to improve herbicide efficiency in the terrestrial environment did not have any effect on aquatic plants when applied to the aquatic environment. PMID:18951630

  20. 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

  1. Is there a linkage between bioaccumulation and the effects of alkylphenols on male breams (Abramis brama)?

    PubMed

    Klein, Roland; Bartel, Martina; He, Xiaohua; Müller, Josef; Quack, Markus

    2005-05-01

    There was some evidence from a previous study that estrogenic disruptors, like alkylphenols, could effect fish in the small River Saar of Southwestern Germany. Concentrations of 4NP and 4NP1EO found in breams (Abramis brama) in the Saar River were much higher than those found in other sampling sites of the German Environmental Specimen Bank, including those from sampling sites in the Rivers Elbe, Rhine, Mulde, and Saale and in Lake Belau. We studied the relationship between accumulation and effect using vitellogenin (vtg) and a hepatosomatic index (HSI) of estrogenic effects and by measuring concentrations of AP and APE accumulated in breams caught at six sampling sites in the River Saar and one in the River Mosel. To link these results with those of the previous study we standardized our sampling efforts to obtain comparable data. Elevated vtg levels were found in the breams at all sampling sites near to or downstream of sewage plant discharges, whereas low vtg levels corresponded to sampling sites not influenced by municipal waste water. While HSI values did not correspond to the location of sampling sites, there was a weak but statistically significant correlation to vtg concentrations. Concentrations of four AP and APE were much more lower, as in the previous study, and were neither linked with sewage treatment plant discharges nor correlated with vtg levels. In conclusion, a linkage between accumulation and the effects of AP and APE could not be established, but the relationship between elevated vtg concentrations and municipal waste water, which contains other important endocrine disruptors, was clear. PMID:15721884

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

    PubMed

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

    2005-01-30

    Immunoenzyme assay (ELISA) is proposed and characterized for determination of alkylphenol ethoxylates, a primary class of manufactured non-ionic surfactants. The assay is based on the obtained polyclonal antibodies against nonylphenol (NP), the main stable intermediate of the decomposition of nonylphenol ethoxylates. A mixture of non-modified branched isomers of NP was applied as hapten coupled to protein carriers by Mannich reaction with the use of formaldehyde. The proposed ELISA format is based on immobilized NP-(soybean trypsin inhibitor) conjugate as a competitor of antigen molecules contained in the tested sample for binding with specific antibodies indirectly labeled via an anti-species immunoperoxidase conjugate. The developed ELISA allows to reveal NP with the limit of detection about 10ngml(-1) and NP-related compounds such as octylphenol, alkylphenoletoxylates, alkylphenolcarboxylates and their halogenated derivatives. The ELISA was applied for assaying polluted water samples, namely influents and effluents from different wastewater treatment plants (WWTP) and tap water. ELISA and chromatographic data demonstrate good correlation (r = 0.94), while ELISA gives higher values. Due to endocrine disrupting and other toxic activities of some metabolites of alkylphenolic non-ionic surfactants, the developed assay may be effectively used in ecological monitoring and sanitary control. PMID:18969808

  3. Determination of three alkylphenol isomers in various water samples using a new HPLC method based on a duet stationary phase.

    PubMed

    Cruceru, Ioana; Florescu, Andreea; Badea, Irinel Adriana; Vladescu, Luminita

    2012-10-01

    The level of three alkylphenols (APs) 4-nonylphenol, 4-octylphenol and 4-tert-octylphenol was monitored in various water samples using a new developed and validated HPLC method. The HPLC method employed a column with a mixed-mode stationary phase (C18/SCX) using a mobile phase of water to methanol = 15:85 (v/v) delivered at a flow rate of 1 mL/min at room temperature. Both diode array, DAD and fluorescence, FLD detectors were employed. The method is linear when APs concentration ranged from 0.025 to 0.5 μg/mL with a DAD detection at 279 nm and between 0.0008 and 0.1 μg/mL when the detection was made by FLD (excitation at 220 nm, emission at 315 nm). The limit of detection and limit of quantitation for alkylphenols were found to be 5 and 15 ng/mL, respectively (detection by DAD). The method was employed with good results for the determination of APs in the presence of polycyclic aromatic hydrocarbons in various water samples. PMID:22068312

  4. Occurrence and fate of emerging wastewater contaminants in Western Balkan Region.

    PubMed

    Terzić, Senka; Senta, Ivan; Ahel, Marijan; Gros, Meritxell; Petrović, Mira; Barcelo, Damia; Müller, Jutta; Knepper, Thomas; Martí, Isabel; Ventura, Francesc; Jovancić, Petar; Jabucar, Dalila

    2008-07-25

    This paper reports on a comprehensive reconnaissance of over seventy individual wastewater contaminants in the region of Western Balkan (WB; Bosnia and Herzegovina, Croatia and Serbia), including some prominent classes of emerging contaminants such as pharmaceuticals and personal care products, surfactants and their degradation products, plasticizers, pesticides, insect repellents, and flame retardants. All determinations were carried out using a multiresidue analytical approach, based on the application of gas chromatographic and liquid chromatographic techniques coupled to mass spectrometric detection. The results confirmed a widespread occurrence of the emerging contaminants in municipal wastewaters of the region. The most prominent contaminant classes, determined in municipal wastewaters, were those derived from aromatic surfactants, including linear alkylbenzene sulphonates (LAS) and alkylphenol polyethoxylates (APEO), with the concentrations in raw wastewater reaching into the mg/l range. All other contaminants were present in much lower concentrations, rarely exceeding few microg/l. The most abundant individual compounds belonged to several classes of pharmaceuticals (antimicrobials, analgesics and antiinflammatories, beta-blockers and lipid regulators) and personal care products (fragrances). Due to the rather poor wastewater management practices in WB countries, with less than 5% of all wastewaters being biologically treated, most of the contaminants present in wastewaters reach ambient waters and may represent a significant environmental concern. PMID:18420255

  5. 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. PMID:27318505

  6. 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

    2005-03-01

    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. PMID:15844521

  7. Diurnal variability of pharmaceutical, personal care product, estrogen and alkylphenol concentrations in effluent from a tertiary wastewater treatment facility.

    PubMed

    Nelson, Eric D; Do, Huy; Lewis, Roger S; Carr, Steve A

    2011-02-15

    Hourly samples of tertiary wastewater effluent were analyzed for 30 pharmaceuticals, personal care products, estrogenic steroids, and alkylphenols in order to better understand the rate at which these compounds enter the environment. Several distinct patterns of daily cycling were observed, and were characterized as three separate categories. The concentrations of compounds such as trimethoprim, sulfamethoxazole, naproxen, estrone, and triclosan varied greatly during a daily cycle, with relative standard deviations exceeding 100% of their daily mean. Less extreme daily cycles were seen for other compounds such as azithromycin, atenolol, tert-octylphenol, iopromide and gemfibrozil. Peak concentrations for most compounds occurred in the early evening (5-8 pm). However, some compounds including carbamazepine, primidone, fluoxetine, and triclocarban exhibited little or no variability. PMID:21189012

  8. Advanced oxidation of the commercial nonionic surfactant octylphenol polyethoxylate Triton™ X-45 by the persulfate/UV-C process: effect of operating parameters and kinetic evaluation

    PubMed Central

    Arslan-Alaton, Idil; Olmez-Hanci, Tugba; Genç, Bora; Dursun, Duygu

    2013-01-01

    This study explored the potential use of a sulfate radical (SO·−4)-based photochemical oxidation process to treat the commercial nonionic surfactant octylphenol polyethoxylate (OPPE) Triton™ X-45. For this purpose, the effect of initial S2O2−8 (0–5.0 mM) and OPPE (10–100 mg/L) concentrations on OPPE and its organic carbon content (TOC) removal were investigated at an initial reaction pH of 6.5. Results indicated that very fast OPPE degradation (100%) accompanied with high TOC abatement rates (90%) could be achieved for 10 and 20 mg/L aqueous OPPE at elevated S2O2−8 concentrations (≥2.5 mM). S2O2−8/UV-C treatment was still capable of complete OPPE removal up to an initial concentration of 40 mg/L in the presence of 2.5 mM S2O2−8. On the other hand, TOC removal efficiencies dropped down to only 40% under the same reaction conditions. S2O2−8/UV-C oxidation of OPPE was also compared with the relatively well-known and established H2O2/UV-C oxidation process. Treatment results showed that the performance of S2O2−8/UV-C was comparable to that of H2O2/UV-C oxidation for the degradation and mineralization of OPPE. In order to elucidate the relative reactivity and selectivity of SO·−4 and HO·, bimolecular reaction rate coefficients of OPPE with SO·−4 and HO· were determined by employing competition kinetics with aqueous phenol (47 μM) selected as the reference compound. The pseudo-first-order abatement rate coefficient obtained for OPPE during S2O2−8/UV-C oxidation (0.044 min−1) was found to be significantly lower than that calculated for phenol (0.397 min−1). In the case of H2O2/UV-C oxidation however, similar pseudo-first-order abatement rate coefficients were obtained for both OPPE (0.087 min−1) and phenol (0.140 min−1). From the kinetic study, second-order reaction rate coefficients for OPPE with SO·−4 and HO· were determined as 9.8 × 108 M−1 s−1 and 4.1 × 109 M−1 s−1, respectively. The kinetic study also revealed

  9. Advanced oxidation of the commercial nonionic surfactant octylphenol polyethoxylate TritonTM X-45 by the persulfate/UV-C process: effect of operating parameters and kinetic evaluation

    NASA Astrophysics Data System (ADS)

    Arslan-Alaton, Idil; Olmez-Hanci, Tugba; Genc, Bora; Dursun, Duygu

    2013-03-01

    This study explored the potential use of a sulfate radical (SO4●-)-based photochemical oxidation process to treat the commercial nonionic surfactant octylphenol polyethoxylate (OPPE) TritonTMX-45. For this purpose, the effect of initial S2O82- (0-5.0 mM) and OPPE (10-100 mg/L) concentrations on OPPE and its organic carbon content (TOC) removal were investigated at an initial reaction pH of 6.5. Results indicated that very fast OPPE degradation (100%) accompanied with high TOC abatement rates (90%) could be achieved for 10 and 20 mg/L aqueous OPPE at elevated S2O82- concentrations (>2.5 mM). S2O82-/UV-C treatment was still capable of complete OPPE removal up to an initial concentration of 40 mg/L in the presence of 2.5 mM S2O82-. On the other hand, TOC removal efficiencies dropped down to only 40% under the same reaction conditions. S2O82-/UV-C oxidation of OPPE was also compared with the relatively well-known and established H2O2/UV-C oxidation process. Treatment results showed that the performance of S2O82-/UV-C was comparable to that of H2O2/UV-C oxidation for the degradation and mineralization of OPPE. In order to elucidate the relative reactivity and selectivity of SO4●- and HO●, bimolecular reaction rate coefficients of OPPE with SO4●- and HO● were determined by employing competition kinetics with aqueous phenol (47 M) selected as the reference compound. The first-order abatement rate coefficient obtained for OPPE during S2O82-/UV-C oxidation (0.044 min-1) was found to be significantly lower than that calculated for phenol (0.397 min-1). In the case of H2O2/UV-C oxidation however, similar first-order abatement rate coefficients were obtained for both OPPE (0.087 min-1) and phenol (0.140 min-1). Second-order reaction rate coefficients for OPPE with SO4●- and HO● were determined as 9.8108 M-1s-1 and 4.1109 M-1s-1, respectively. The kinetic study also revealed that the selectivity of SO4●- was found to be significantly higher than that of

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

    PubMed Central

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

    2009-01-01

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

  11. 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). PMID:26931663

  12. 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. PMID:24420241

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

    PubMed

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

    2014-07-01

    Alkylphenols (APs) have been found as ubiquitous environmental pollutants with reproductive and developmental toxicity. In this study, APs in surface sediments of the Yellow Sea (YS) and East China Sea (ECS) inner shelf were analyzed to assess influences of riverine and atmospheric inputs of pollutants on the marine environment. NP concentrations ranged from 349.5 to 1642.8 ng/g (average 890.1 ng/g) in the YS sediments and from 31.3 to 1423.7 ng/g (average 750.1 ng/g) in the ECS inner shelf sediments. NP distribution pattern was mainly controlled by the sedimentary environment. OP concentration was 0.8-9.3 ng/g (average 4.7 ng/g) in the YS sediments and 0.7-11.1 ng/g (average 5.1 ng/g) in the ECS sediments. Assessment of the influence of distances from land on OP concentrations provided evidence for the predominance of coastal riverine and/or atmospheric inputs rather than long-range transport. And the biological pump may play an important role for sequestration of OP in the nearshore area. PMID:24411839

  14. Occurrence and Distribution Pattern of Alkylphenol Ethoxylates and Brominated Flame Retardants in Sediment Samples from Vaal River, South Africa.

    PubMed

    Chokwe, T B; Okonkwo, O J; Sibali, L L; Mporetji, S M

    2016-09-01

    High environmental concentrations for alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) have been observed near cities than in rural environment. This is due, in part, to sewage systems receiving effluents from many industrial processes along with domestic wastewater. While these classes of compounds are being phased out in most developed countries, there is still widespread use in low to middle income countries. To better understand the extent of APEs and BFRs contamination in the environment, this study reports on the concentration and distribution of APEs and BFRs in sediments samples collected from Vaal River, South Africa. Measurable concentrations of these contaminants were obtained using GC-MS after heptafluorobutyric derivatization. The concentrations range (ng g(-1)) for these pollutants were as follows: nd-46, 20-127, 24-38, 3-5, 14-28, 16-54 for octylphenol penta ethoxylates, nonylphenol ethoxylates (mono- di), nonylphenol penta ethoxylates, PBB101, PBDEs, and HBCD; respectively. The distribution observed in this study indicated higher levels of sediment contamination by APEs relative to BFRs. These results underline the need to further investigate the burden and risks associated with chemical contamination in developing countries. PMID:27443342

  15. National Inventory of Alkylphenol Ethoxylate Compounds in U.S. Sewage Sludges and Chemical Fate in Outdoor Soil Mesocosms

    PubMed Central

    Venkatesan, Arjun K.; Halden, Rolf U.

    2012-01-01

    We determined the first nationwide inventories of alkylphenol surfactants in U.S. sewage sludges (SS) using samples from the U.S. Environmental Protection Agency's 2001 national SS survey. Additionally, analysis of archived 3-year outdoor mesocosm samples served to determine chemical fates in SS-amended soil. Nonylphenol (NP) was the most abundant analyte (534±192 mg/kg) in SS composites, followed by its mono- and di-ethoxylates (62.1±28 and 59.5±52 mg/kg, respectively). The mean annual load of NP and its ethoxylates in SS was estimated at 2408–7149 metric tonnes, of which 1204–4289 is applied on U.S. land. NP compounds showed observable loss from SS/soil mixtures (1:2), with mean half-lives ranging from 301 to 495 days. Surfactant levels in U.S. SS ten-times in excess of European regulations, substantial releases to U.S. soils, and prolonged half-lives found under field conditions, all argue for the U.S. to follow Europe's move from 20 years ago to regulate these chemicals. PMID:23274446

  16. National inventory of alkylphenol ethoxylate compounds in U.S. sewage sludges and chemical fate in outdoor soil mesocosms.

    PubMed

    Venkatesan, Arjun K; Halden, Rolf U

    2013-03-01

    We determined the first nationwide inventories of alkylphenol surfactants in U.S. sewage sludges (SS) using samples from the U.S. Environmental Protection Agency's 2001 national SS survey. Additionally, analysis of archived 3-year outdoor mesocosm samples served to determine chemical fates in SS-amended soil. Nonylphenol (NP) was the most abundant analyte (534 ± 192 mg/kg) in SS composites, followed by its mono- and di-ethoxylates (62.1 ± 28 and 59.5 ± 52 mg/kg, respectively). The mean annual load of NP and its ethoxylates in SS was estimated at 2408-7149 metric tonnes, of which 1204-4289 is applied on U.S. land. NP compounds showed observable loss from SS/soil mixtures (1:2), with mean half-lives ranging from 301 to 495 days. Surfactant levels in U.S. SS ten-times in excess of European regulations, substantial releases to U.S. soils, and prolonged half-lives found under field conditions, all argue for the U.S. to follow Europe's move from 20 years ago to regulate these chemicals. PMID:23274446

  17. 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.) PMID:26381567

  18. 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

  19. 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

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

    PubMed

    Liao, Chunyang; Kannan, Kurunthachalam

    2014-07-01

    Exposure of humans to environmental phenolic compounds such as bisphenol A (BPA) and alkylphenols is a matter of concern, due to these compounds' ubiquitous occurrence and estrogenic potencies. Little is known about the levels of environmental phenolics in personal care products (PCPs). In this study, nonylphenol, two octylphenols, eight bisphenols (BPA and its analogs), and triclosan (TCS) were determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in PCP samples (n = 231) collected from China and the United States (U.S.). The concentrations of 4-n-nonylphenol (4-NP), 4-n-octylphenol (4-OP), 4-tert-octylphenol (4-t-OP), and TCS were in the ranges of <0.5-39,100 [geometric mean (GM): 21.5], <0.5-315 (0.680), <1.0-10,100 (2.69), and <0.5-53,900 (3.03) ng/g, respectively. The GM concentrations of individual bisphenols, including BPA, bisphenol S (BPS), and bisphenol F (BPF), were generally at sub-nanogram per gram levels. No significant differences in concentrations of the target compounds were found among various PCP categories or between China and the U.S. The estimated GM daily intakes of 4-NP, ∑OPs (sum of 4-OP and 4-t-OP), ∑BPs (sum of eight bisphenols), and TCS through dermal absorption from the use of PCPs were 0.932, 0.093, 0.072, and 0.016 μg/day, respectively, for adult Chinese women and 0.340, 0.054, 0.120, and 0.068 μg/day, respectively, for adult U.S. women. Body lotions, face creams, and liquid foundations accounted for the majority (>85 %) of the dermal exposure doses of the target phenolics. PMID:24639116

  1. 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...

  2. 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...

  3. Octyl- and Nonylphenol Ethoxylates and Carboxylates in Wastewater and Sediments by Isotope Dilution Liquid Chromatography/Tandem Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This work presents an LC-MS-MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using...

  4. 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. PMID:26765845

  5. A novel method for the rapid determination of polyethoxylated tallow amine surfactants in water and sediment using large volume injection with high performance liquid chromatography and tandem mass spectrometry.

    PubMed

    Ross, Andrew R S; Liao, Xiangjun

    2015-08-19

    Polyethoxylated tallow amine (POEA) surfactants have been used in many glyphosate-based herbicide formulations for agricultural, industrial and residential weed control. The potential for release of these compounds into the environment is of increasing concern due to their toxicity towards aquatic organisms. Current methods for analysis of POEA surfactants require significant time and effort to achieve limits of quantification that are often higher than the concentrations at which biological effects have been observed (as low as 2 ng mL(-1)). We have developed a rapid and robust method for quantifying the POEA surfactant mixture MON 0818 at biologically relevant concentrations in fresh water, sea water and lake sediment using reversed phase high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry. Water samples preserved by 1:1 v/v dilution with methanol are analyzed directly following centrifugation. Sediment samples undergo accelerated solvent extraction in aqueous methanol prior to analysis. Large volume (100 μL) sample injection and multiple reaction monitoring of a subset of the most abundant POEA homologs provide limits of quantification of 0.5 and 2.9 ng mL(-1) for MON 0818 in fresh water and sea water, respectively, and 2.5 ng g(-1) for total MON 0818 in lake sediment. Average recoveries of 93 and 75% were achieved for samples of water and sediment, respectively spiked with known amounts of MON 0818. Precision and accuracy for the analysis of water and sediment samples were within 10 and 16%, respectively based upon replicate analyses of calibration standards and representative samples. Results demonstrate the utility of the method for quantifying undegraded MON 0818 in water and sediment, although a more comprehensive method may be needed to identify and determine other POEA mixtures and degradation profiles that might occur in the environment. PMID:26343437

  6. The Vibronic Spectroscopy of Some P-Alkylphenols and Catechols as Examined by Means of Supersonic Jet Resonant Two-Photon Ionization

    NASA Astrophysics Data System (ADS)

    Grace, Louis Immanuel

    I present a set of ground-state assignments, based on infrared and Raman data, for p-ethylphenol, p-isopropylphenol, tyramine, tyrosine, 4-methylcatechol and 3-methoxytyramine. I present supersonic jet resonant two-photon ionization (R2PI) spectra and the corresponding vibronic assignments for all of these molecules and for catechol. Tyramine and tyrosine require a laser-desorption technique, which is described in detail. The ground-state spectra for the four p-alkylphenols studied are quite similar to each other. Thus, analogy to the p-cresol ground state is quite useful for making the assignments. The ground-state data for 4-methylcatechol and 3-methoxytyramine seem to be interpretable by analogy to the spectra of other tri-substituted benzenes. The R2PI spectra for the p-alkylphenols are also similar to each other, despite the fact that the nature of the substituent chain varies considerably among these molecules. The observed (lowest-energy) origins (v ^{''} = 0 to v^' = 0) are: For tyrosine, p-isopropylphenol, p-ethylphenol and tyramine, respectively, 35620, 35587, 35516 and 35492cm^{-1 }, and for 4-methylcatechol, 4-ethylcatechol, 3-methoxytyramine and catechol, respectively, 34781, 34877(?), 35325 and 35655cm^{-1}. Two bands previously assigned as origins in the fluorescence spectrum of tyramine are absent in the R2PI spectrum. Most of these molecules are stable in several geometries. To aid the ground-state assignments for the p-alkyl-phenols, and to examine the issue of multiple conformers, particularly of the catechols, I performed Hartree-Fock calculations at the 3-21G level via the GAUSSIAN program. Results of these are presented. I also attempted to obtain an R2PI spectrum for dopamine. Despite the fact that I tried many experiments with a variety of entrainment conditions, I was unable to do so. Some of the catechols exhibit unusual behavior in that they yield R2PI spectra only for a certain range of jet stagnation pressures. I present the results of

  7. 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. PMID:26101960

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

    PubMed

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

    2012-12-28

    A novel and green analytical methodology for the determination of alkylphenols (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol technical mixture) and bisphenol A in bivalve mollusc samples was developed and validated. The method was based on selective pressurized liquid extraction (SPLE) with a simultaneous in cell clean up combined with liquid chromatography–electrospray ionization tandem mass spectrometry in negative mode (LC–ESI-MS/MS). Quantitation was performed by standard addition curves in order to correct matrix effects. The analytical features of the method were satisfactory: relative recoveries varied between 80 and 107% and repeatability and intermediate precision were <20% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.34 (4-n-octylphenol) and 3.6 ng g(−1) dry weight (nonylphenol). The main advantages of the method are sensitivity, selectivity, automaticity, low volumes of solvents required and low sample analysis time (according with the principles of Green Chemistry). The method was applied to the analysis of mussel samples of Galicia coast (NW of Spain). Nonylphenol and 4-tert-octylphenol were measured in all samples at concentrations between 9.3 and 372 ng g(−1) dw. As an approach, the human daily intake of these compounds was estimated and no risk for human health was found. PMID:23218190

  9. 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. PMID:20961547

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

    PubMed

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

    2013-04-01

    Novel methods utilizing liquid chromatography-tandem mass spectrometry and gas chromatography-mass spectrometry were validated for low-level detection of 104 pharmaceuticals and personal care products ingredients (PPCPs) and four alkylphenols (APs) in environmental samples. The methods were applied to surface water, sediment, and mussel tissue samples collected from San Francisco Bay, CA, USA, an urban estuary that receives direct discharge from over forty municipal and industrial wastewater outfalls. Among the target PPCPs, 35% were detected in at least one sample, with 31, 10, and 17 compounds detected in water, sediment, and mussels, respectively. Maximum concentrations were 92 ng/L in water (valsartan), 33 ng/g dry weight (dw) in sediments (triclocarban), and 14 ng/g wet weight (ww) in mussels (N,N-diethyl-m-toluamide). Nonylphenol was detected in water (<2-73 ng/L), sediments (22-86 ng/g dw), and mussels (<0.04-95 ng/g ww), and nonylphenol mono- and diethoxylates were detected in sediments (<1-40 ng/g dw) and mussels (<5-192 ng/g ww). The concentrations of PPCPs and APs detected in the San Francisco Bay samples were generally at least an order of magnitude below concentrations expected to elicit toxic effects in aquatic organisms. This study represents the first reconnaissance of PPCPs in mussels living in an urban estuary and provides the first field-derived bioaccumulation factors (BAFs) for select compounds in aquatic organisms. PMID:23527629

  11. 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? PMID:24216260

  12. 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.

  13. Uptake and tissue distribution of C4-C7 alkylphenols in Atlantic cod (Gadus morhua): relevance for biomonitoring of produced water discharges from oil production.

    PubMed

    Sundt, Rolf C; Baussant, Thierry; Beyer, Jonny

    2009-01-01

    The sensitivity of different tissues for assessment of chronic low-dose environmental exposure of fish to alkylphenols (APs) was investigated. We exposed Atlantic cod (Gadus morhua) in the laboratory to tritium labelled 4-tert-butylphenol, 4n-pentylphenol, 4n-hexylphenol, and 4n-heptylphenol via seawater (8 ng/l) and via contaminated feed (5 microg/kg fish per day). Measurements of different fish tissues during eight days of exposure and eight subsequent days of recovery revealed that APs administered via spiked seawater were readily taken up whereas the uptake was far less efficient when APs were administered in spiked feed. AP residues were mainly located in the bile fluid whereas the concentrations in liver were very low, indicating a rapid excretion and the liver-bile axis to be the major route of elimination. The biological half-life of APs in the exposed cod was short, between 10 and 20 h. Our study shows that in connection with biomonitoring of AP exposure in fish, assessment of AP metabolites in bile fluid is a more sensitive tool than detection of parent AP levels in liver or other internal tissues. PMID:18945454

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

    PubMed

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

    2011-01-01

    In recent years there has been an increasing search for new antifungal compounds due to the side effects of conventional antifungal drugs and fungal resistance. The aims of this study were to test in vitro the activity of thymol, eugenol, estragole and anethole and some O-methyl-derivatives (methylthymol and methyleugenol) against Candida spp. and Microsporum canis. The broth microdilution method was used to determine the minimum inhibitory concentration (MIC). The minimum fungicidal concentrations (MFC) for both Candida spp. and M. canis were found by subculturing each fungal suspension on potato dextrose agar. Thymol, methylthymol, eugenol, methyl-eugenol, anethole, estragole and griseofulvin respectively, presented the following MIC values against M. canis: 4.8-9.7; 78-150; 39; 78-150; 78-150; 19-39 µg/mL and 0.006-2.5 mg/mL. The MFC values for all compounds ranged from 9.7 to 31 µg/mL. Concerning Candida spp, thymol, methylthymol, eugenol, methyleugenol, anethole, estragole and amphotericin, respectively, showed the following MIC values: 39; 620-1250; 150-620; 310-620; 620; 620-1250 and 0.25-2.0 mg/mL. The MFC values varied from 78 to 2500 µg/mL. All tested compounds thus showed in vitro antifungal activity against Candida spp. and M. canis. Therefore, further studies should be carried out to confirm the usefulness of these alkylphenols in vivo. PMID:25134762

  15. Characteristics of the alkylphenol and bisphenol A distributions in marine organisms and implications for human health: A case study of the East China Sea.

    PubMed

    Gu, Yunyun; Yu, Jie; Hu, Xialin; Yin, Daqiang

    2016-01-01

    The distributions of alkylphenol (AP) and bisphenol A (BPA) in marine organisms, including fish, prawns and molluscs, could reflect the exposure of AP and BPA directly and effectively. This paper provides the first report on the species-dependent distribution and the human health risks of four APs (4-t-octylphenol, 4-t-OP; 4-octylphenol, 4-OP;4-nonylphenol, 4-NP; 4-n-nonylphenol, 4-n-NP) and BPA in 95 wild and 88 processed marine biota samples from the East China Sea of the Yangtze River Delta area. 4-NP was the predominant compound with the highest detected concentration of 19,890.50ng/g ww. Significant pollution was observed in Taizhou, Shanghai and Ningbo. The species-dependent distribution was related to food habits, living patterns and trophic transfer. Higher residual concentrations of 4-t-OP, 4-OP, 4-n-NP and BPA were observed in fish species that consumed benthic organisms or demersal fish species, whereas 4-NP showed different results due to trophic dilution. The trophic magnification factors (TMFs) of the linear APs (4-OP and 4-n-NP) (1.22-2.93) were higher than those of the branched ones (4-t-OP and 4-NP) (0.72-0.90), indicating the relative metabolism stability of linear APs. 4-NP has the lowest TMF value of 0.72, and its trophic dilution might be observed because the branched carbon chain exhibits the lowest dispersion force compared to that of the other APs. As for the health risk, 7-year old children may be exposed to the highest health risk of 4-NP with 95th percentile values of the hazard quotient of 0.22 to 0.23; however, the risks of the other chemicals were relatively low. PMID:26379260

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

    PubMed

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

    2012-06-01

    This paper describes a method for the determination of three alkylphenols (APs), 4-tert-octylphenol (tOP), 4-n-octylphenol (OP) and 4-nonylphenol (NP), and six phthalate esters (PEs), dimethylphthalate (DMP), diethylphthalate (DEP), di-n-butylphthalate (DBP), n-butylbenzylphthalate (BBP), di-2-ethylhexylphthalate (DEHP) and di-n-octylphthalate (DOP), in vegetables using stir bar sorptive extraction (SBSE) in combination with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Ultrasonic radiation was used to extract the analytes from the solid food matrix, and the extract obtained was preconcentrated by SBSE. The different parameters affecting both stages were carefully optimized. The method was applied to analyze commercial vegetables, in the form of plastic packed salads and canned greens, as well as the corresponding filling liquids of the canned food. Quantification of the samples was carried out against aqueous standards using an internal standard (anthracene). The analysis of a 2 g vegetable sample provided detection limits between 12.7 and 105.8 pg g⁻¹ for OP and DEHP, respectively. Migration studies from the plastic packages of the vegetables samples analyzed were carried out. DEP, DBP and DEHP were found to have migrated from the bags to the simulant and the same compounds were quantified in lettuce, corn salad, arugula, parsley and chard, at concentration levels in the 8-51 ng g⁻¹ range. However, OP and NP were found in only two vegetable samples and one filling liquid, but neither was detected in any package. The proposed method provided recoveries of 83-118%. PMID:22533911

  17. 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. PMID:18706331

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

    PubMed

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

    2012-03-01

    Two rapid methods were evaluated for the simultaneous extraction of seven parabens and two alkylphenols from soil based on matrix solid-phase dispersion (MSPD) and microwave-assisted extraction (MAE). Soil extracts were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide and analyzed by gas chromatography with mass spectrometry. Extraction and clean-up of samples were carried out by both methods in a single step. A glass sample holder, inside the microwave cell, was used in MAE to allow the simultaneous extraction and clean-up of samples and shorten the MAE procedure. The detection limits achieved by MSPD were lower than those obtained by MAE because the presence of matrix interferences increased with this extraction method. The extraction yields obtained by MSPD and MAE for three different types of soils were compared. Both procedures showed good recoveries and sensitivity for the determination of parabens and alkylphenols in two of the soils assayed, however, only MSPD yielded good recoveries with the other soil. Finally, MSPD was applied to the analysis of soils collected in different sites of Spain. In most of the samples analyzed, methylparaben and butylparaben were detected at levels ranging from 1.21 to 8.04 ng g(-1) dry weight and 0.48 to 1.02 ng g(-1) dry weight, respectively. PMID:21792551

  19. 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

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

    PubMed Central

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

    2011-01-01

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

  1. 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

    2016-02-01

    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. PMID:26637951

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

    PubMed

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

    2012-02-01

    A fast, simple, sensitive and green analytical chemistry method for the simultaneous determination of alkylphenols (4-tert-octylphenol, 4-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A in seawater was developed and validated. The procedure was based on a dispersive liquid-liquid microextraction (DLLME) of a small volume of seawater sample (30 mL) using only 100 μL of 1-octanol, combined with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). The matrix effect was studied and compensated using deuterated labelled standards as surrogate standards for the quantitation of target compounds. The analytical features of the proposed method were satisfactory: repeatability and intermediate precision were <10% and recoveries were around 84-104% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.005 and 0.03 μg L⁻¹, therefore the levels established in the Directive 2008/105/EC were achieved. The applicability of the proposed method was demonstrated analyzing seawater samples from different sites of A Coruña (Northwest of Spain). The analyses showed the presence of all compounds at levels between 0.035 (bisphenol A) and 0.14 μg L⁻¹ (nonylphenol). PMID:22227360

  3. Radiolytic decomposition of multi-class surfactants and their biotransformation products in sewage treatment plant effluents.

    PubMed

    Petrovic, M; Gehringer, P; Eschweiler, H; Barceló, D

    2007-01-01

    Electron beam irradiation (EBI), as one of the most efficient advanced oxidation processes, was applied to the treatment of sewage treatment plant (STP) effluent, with the objective of evaluating the effectiveness of radiolytic decomposition of multi-class surfactants. Target compounds, included several high-volume surfactant groups, such as alkylphenol ethoxylates (APEOs) and their biotransformation products, linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylether sulfates (AES), coconut diethanol amides (CDEA), alcohol ethoxylates (AEO) and polyethylene glycols (PEGs). EBI treatment of STP effluent (total concentration of APEO-derived compounds 265mugl(-1), being APE(2)C the most abundant by-degradation products) resulted in efficient decomposition of all alkylphenolic compounds; elimination of 94% longer ethoxy chain nonylphenol ethoxylates (NPEO, n(EO)=3-15) was obtained when 3kGy were applied. Slightly less efficient decomposition of short ethoxy chain oligomers (NPEO(1) and NPEO(2)) was observed, resulting in disappearance of about 80% of the initially present compounds. LC-MS analysis of treated wastewater suggested that the mechanism of EBI degradation of APEOs is a combination of two parallel pathways: a progressive shortening and oxidation of the ethoxy chain, which resulted in a formation of short ethoxy chain oligomers and APECs and central fission that resulted in formation of PEGs. Decomposition of APECs at 1kGy initially yielded APs, which were subsequently eliminated applying higher radiation doses. With a radiation dose of 2kGy about 95% of NPE(1)C and 97% of NPE(2)C were decomposed. Similar elimination rates were obtained for octylphenolic compounds. Radiolytic treatment applied was also very effective in removing PEGs formed as by-products from APEO degradation, as well as in decomposing other surfactants, such as linear LAS, AS and AES. PMID:16808959

  4. 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.

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

    PubMed

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

    2006-05-15

    Snowbank samples were collected from snowbanks within a medium-sized airport for four years to characterize aircraft deicer and anti-icer (ADAF) components and toxicity. Concentrations of ADAF components varied with median glycol concentrations from individual sampling periods ranging from 65 to 5940 mg/L. Glycol content in snowbanks ranged from 0.17 to 11.4% of that applied to aircraft. Glycol, a freezing point depressant, was selectively removed during melt periods before snow and ice resulting in lower glycol concentrations after melt periods. Concentrations of ADAF components in airport runoff were similar during periods of snowmelt as compared to active ADAF application periods; however, due to the long duration of snowmelt events, greater masses of glycol were transported during snowmelt events. Alkylphenol ethoxylates (APEO), selected APEO degradation products, and 4- and 5-methyl-1H-benzotriazole were detected in snowbank samples and airport snowmelt. Concentrations of APEO parent products were greater in snowbank samples than in runoff samples. Relative abundance of APEO degradation products increased in the downstream direction from the snowbank to the outfalls and the receiving stream with respect to APEO parent compounds and glycol. Toxicity in Microtox assays remained in snowbanks after most glycol had been removed during melt periods. Increased toxicity in airport snowbanks as compared to other urban snowbanks was not explained by additional combustion or fuel contribution in airport snow. Organic markers suggest ADAF additives as a possible explanation for this increased toxicity. Results indicate that glycol cannot be used as a surrogate for fate and transport of other ADAF components. PMID:16749681

  6. 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.

  7. Reduction of endocrine disruptor emissions in the environment: the benefit of wastewater treatment.

    PubMed

    Janex-Habibi, Marie-Laure; Huyard, Alain; Esperanza, Mar; Bruchet, Auguste

    2009-04-01

    The occurrence and fate of four estrogens and five alkylphenolic compounds were studied in thirteen plants with various treatment processes, sizes and countries. Complete load mass balance, including water and sludge phases, has shown a high reduction of the total load of hormones, around 90%. The removal of alkylphenols was more variable, due to the degradation of nonylphenol (NP) precursors - alkylphenol polyethoxylates (APnEO) - during the treatment, resulting in significant production of shorter and toxic alkylphenols (NP and short polyethoxylates) that concentrate in the sludges. Under anaerobic conditions, such as anaerobic digestion process, the load of NP was in most cases observed to increase. When considering the environmental impact, the high reduction of endocrine disrupting compounds (EDC) concentrations between raw wastewater and effluent enables to satisfy the requirements of the Water Framework Directive for NP except in very critical situations where the dilution factor of the effluent in the river would be lower than 7. For sludges, the pending European Directive on spreading of sludge on land would be complied with in all cases. PMID:19203777

  8. Alkylphenols and phthalates in bottled waters.

    PubMed

    Amiridou, Diana; Voutsa, Dimitra

    2011-01-15

    The aim of this study was to investigate the occurrence of endocrine disrupting compounds (EDCs) in bottled waters. The examined compounds were bisphenol A (BPA), nonylphenol (NP), tert-octylphenol (tOP), dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), di(2-ethylhexyl)phthalate (DEHP) and di(n-octyl)phthalate (DNOP). The presence of EDCs in bottled waters under poor storage conditions was also investigated after exposure outdoors under realistic conditions for 15 and 30 days. EDCs were recovered after liquid-liquid extraction and determined by employing Gas Chromatography-Mass Spectrometry. Most of these compounds were detected in bottled water from different brands purchased from local market. Storage at outdoor conditions had no significant effect on the concentrations of the examined compounds. Only BPA occurred at higher concentrations in polycarbonate containers exhibited an increasing trend during exposure. The estimated exposure to EDCs via consumption of drinking water was very low. PMID:20933324

  9. REGIONAL METHODS INITIATIVE FOR ALKYLPHENOL ENDOCRINE DISRUPTERS

    EPA Science Inventory

    Nonylphenol and the ethoxylates are amenable to GC/MS analysis but the carboxylates are better analyzed using LC/MS. The Central Regional Laboratory (CRL) intends to do this with standards of known purity using a triple quadruple instrument. The purified standards will be used to...

  10. Octyl and nonylphenol ethoxylates and carboxylates in wastewater and sediments by liquid chromatography/tandem mass spectrometry.

    PubMed

    Loyo-Rosales, Jorge E; Rice, Clifford P; Torrents, Alba

    2007-08-01

    This work presents an LC-MS-MS-based method for the quantitation of nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs) in water, sediment, and suspended particulate matter, and three of their carboxylated derivatives in water. The alkylphenol ethoxylates (APEOs) were analyzed using isotope dilution mass spectrometry with [(13)C(6)]-labeled analogues, whereas the carboxylated derivatives were determined by external standard quantitation followed by confirmation using standard additions. The method was used to study APEO's behavior in a wastewater treatment plant (WWTP), where total dissolved NP0-16EO concentration was reduced by approximately 99% from influent (390 microg l(-1)) to final effluent (4 microg l(-1)), and total OP0-5EO concentration decreased by 94% from 3.1 to 0.2 microg l(-1). In contrast, the carboxylated derivatives were formed during the process with NP0-1EC concentrations increasing from 1.4 to 24 microg l(-1). Short-chain APEOs were present in higher proportions in particulate matter, presumably due to greater affinity for solids compared to the long-chain homologues. NP (0.49 microg l(-1)) and NP0-1EC (4.8 microg l(-1)) were the only APEO-related compounds detected in a surface water sample from a WWTP-impacted estuary; implying that 90% of the mass was in the form of carboxylated derivatives. Sediment analysis showed nonylphenol to be the single most abundant compound in sediments from the Baltimore Harbor area, where differences in homologue distribution suggested the presence of treated effluent in some of the sites and non-treated sources in the rest. PMID:17395243

  11. Concentrations and mass loadings of hormones, alkylphenols, and alkylphenol ethoxylates in healthcare facility wastewaters.

    PubMed

    Nagarnaik, P M; Mills, M A; Boulanger, B

    2010-02-01

    Healthcare facility wastewaters are an anticipated source of known endocrine disrupting chemicals to the environment. In this study, the composition and magnitude of eight steroid hormones, octylphenol (OP), nonylphenol (NP), 16 nonylphenol ethoxylates (NPEOs), and 10 octylphenol ethoxylates (OPEOs) in wastewater from a(n) hospital, nursing facility, assisted living facility, and independent living facility are presented. Steroid hormone concentrations were variable for each sampling location, ranging from a non-detectable concentration of 17beta-ethynylestradiol in all samples to 127ngL(-1) androstenedione in the hospital's wastewater composite. OP and NP were not detected in any site's samples. However, NPEOs were found at each sampling location with a maximum combined concentration of 260microgL(-1) for NPEOs with a chain length between 3 and 18 units in the assisted living facility composite sample. OPEOs were only found in the hospital and nursing facilities samples with a maximum combined OPEO concentration of 13microgL(-1) for OPEOs with a chain length between 2 and 12 units in hospital wastewater. The total mass loading of hormones to the municipal sewer system from each facility ranged from 2.5mgd(-1) at the assisted living facility to 138mgd(-1) at the hospital. The total mass loading of the alklyphenol ethoxylates (NPEO+OPEO) is considerably higher than the estimated hormone mass loadings, ranging from 1.8gd(-1) at the independent living facility to 54gd(-1) at the hospital facility. PMID:20079514

  12. Attenuation of Selected Emerging Contaminants During River Transport

    NASA Astrophysics Data System (ADS)

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

    2002-12-01

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

  13. Extraction of humic acid by coacervate: investigation of direct and back processes.

    PubMed

    Ghouas, H; Haddou, B; Kameche, M; Derriche, Z; Gourdon, C

    2012-02-29

    The two aqueous phases extraction process is widely used in environmental clean up of industrial effluents and fine chemical products for their reuse. This process can be made by cloud point of polyethoxylated alcohols and micellar solubilization phenomenon. It is commonly called "coacervate extraction" and is used, in our case, for humic acid extraction from aqueous solution at 100mg/L. The surfactants used are alcohol polyethoxylate and alkylphenol polyethoxylate. Phase diagrams of binary water/surfactant and pseudo-binary are plotted. The extraction results are expressed by the following responses: percentage of solute extracted, E (%), residual concentrations of solute and surfactant in dilute phase (X(s,w), and X(t,w) respectively) and volume fraction of coacervate at equilibrium (ϕ). For each parameter, the experimental results are fitted to empirical equations in three dimensions. The aim of this study is to find out the best compromise between E and ϕC. The comparison between experimental and calculated values allows models validation. Sodium sulfate, cetyltrimethylammonium bromide (CTAB) addition and pH effect are also studied. Finally, the possibility of recycling the surfactant has been proved. PMID:22260753

  14. Nonylphenol polyethoxylate coated body-center-cubic iron nanocrystals for ferrofluids with technical applications

    NASA Astrophysics Data System (ADS)

    Ortega, D.; Pérez, N.; Vilas, J. L.; Garitaonandia, J. S.; Suzuki, K.; Marín, J. R.; Rodríguez, M.

    2013-05-01

    An approach to the design of a suitable system for technological applications, such as magneto-rheological fluids with controllable performance, showing high saturation magnetization and low coercivity and remanence, is presented. This approach is based on the synthesis of stable iron nanoparticles with a relatively thick polymeric coating—the non-ionic surfactant nonylphenol polyethoxylate—by a microemulsion method with NaBH4 as a reducing agent. X-ray diffractometry, Mössbauer spectroscopy, and high resolution electron microscopy reveal a body-center-cubic structure in the iron cores. The resulting nanoparticles are predominantly spherical, having an average core size of 7 nm and a constant shell thickness of 3 nm. Magnetic measurements reveal a higher saturation magnetization (127.4 Am2 kg-1 at 300 K and 153.2 Am2 kg-1 at 5 K) than in other approaches and a small coercive field of 12 mT. X-ray diffractometry results account for the presence of iron borate traces as a secondary phase, formed at the initial stages of the synthesis during the reduction process of precursors. Preliminary studies under oxidant conditions show a reduction in saturation magnetization lower than 9% over a six months period.

  15. Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge.

    PubMed

    Hung, Nguyen Viet; Tateda, Masafumi; Ike, Michihiko; Fujita, Masanori; Tsunoi, Shinji; Tanaka, Minoru

    2004-01-01

    Nonylphenol(NP), nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) are biodegradation end products (BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28 degrees C fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient (K(F)) and linear sorption coefficient (K(D)) showed that sorption capacity of the investigated compounds were in order NP > NP2EO > NP1EO > NP1EC approximately NP2EC. For NP, NP1EO and NP2EO, high values of calculated K(F) and K(D) indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K(F) and K(D) absorbed weakly to activated sludge and tended to preferably remain in aqueous phase. PMID:15495957

  16. 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. PMID:27176941

  17. 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. PMID:16949635

  18. Automated chemiluminescence immunoassay for a nonionic surfactant using a recycled spinning-pausing controlled washing procedure on a compact disc-type microfluidic platform.

    PubMed

    Guo, Shuai; Ishimatsu, Ryoichi; Nakano, Koji; Imato, Toshihiko

    2015-02-01

    A fully automated and integrated chemiluminescence immunoassay, carried out on a compact disc (CD)-type microfluidic platform, for the detection of alkylphenol polyethoxylates (APnEOs) is described. The pattern of the CD-type microchip was designed so as to permit the sequential solution delivery of the sample solution, the washing solution and the luminol solution, which are required in the chemiluminescence immunoassay process, along with a designed rotation program for spinning the CD-type microchip. The procedure for flowing the washing solution, the volume of which was limited on the CD-type microchip, was optimized by using a recycled spinning-pausing rotation program to overcome the non-specific adsorption of the horseradish peroxidase labeled APnEOs at the detection area. The detection limit of the immunoassay is about 10 ppb. PMID:25435234

  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. PMID:17123581

  20. Interlaboratory trial on the analysis of alkylphenols, alkylphenol ethoxylates, and bisphenol A in water samples according to ISO/CD 18857-2.

    PubMed

    Stottmeister, E; Heemken, O P; Hendel, P; Donnevert, G; Frey, S; Allmendinger, H; Sawal, G; Jandel, B; Geiss, S; Donau, R; Koch, A; Heinz, I; Ottaviani, M; Veschetti, E; Hartl, W; Kubwabo, C; Benthe, C; Tobinski, V; Woldmann, H; Spilker, R

    2009-08-15

    ISO/CD 18857-2 (International Organization for Standardization, Geneva) describes a new international standard method for the determination of octylphenol, nonylphenol, their mono- and diethyoxylates, and bisphenol A in nonfiltered samples of drinking, ground, surface, and wastewater. The method is based on the extraction of the analytes from an acidified water sample by solid phase extraction, solvent elution, derivatization, and determination by gas chromatography with mass spectrometric detection. For validation of this method, 14 laboratories from 4 different countries in Europe and Canada participated in an interlaboratory trial to determine the performance characteristics of the method, which are intended for publication in the corresponding standard. The interlaboratory trial was evaluated according to ISO 5725-2 and included two duplicate nonfiltered water samples: surface water containing the target compounds in an analyte concentration range from 0.05 to 0.4 microg/L and wastewater containing the target compounds in a concentration ranged from 0.1 to 5 microg/L. The repeatability variation coefficients (within-laboratory precision) varied for all samples and compounds between 1.9 and 7.8%, showing a sufficiently high repeatability of the method. The reproducibility variation coefficients (between-laboratory precision) were found to vary within a satisfactory range of 10.0-29.5% for surface water and 10.8-22.5% for wastewater. The recoveries as a measure of accuracy varied from 98.0 to 144.1% for surface water and from 95.4 to 108.6% for wastewater. The determined concentrations of the samples compared well to the "true" values, thus showing very satisfactory accuracy of the method. In the chromatogram of the surface water sample, a high unresolved background made up of coextractable matrix compounds was apparent. It is conceivable that compounds from this background may be responsible for enhanced recoveries of 144.1% for 4-nonylphenol (mixture of isomers) and of 123.4% for 4-nonylphenol monoethoxylate (mixture of isomers) in the surface water samples. The isotope-marked standard compounds developed in this context proved to be reliable internal standards that allow a precise and accurate quantitation of all compounds specified in ISO/CD 18857-2. The results of the interlaboratory trial confirmed that the analytical method is robust and reliable and can be used as a standard method to analyze the target compounds in water samples. PMID:19627127

  1. 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...

  2. 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. PMID:26590059

  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. PMID:21520955

  4. 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.

  5. 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...

  6. 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).

  7. 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...

  8. Toxicity of nonylphenol on the cnidarian Hydra attenuata and environmental risk assessment.

    PubMed

    Pachura-Bouchet, S; Blaise, C; Vasseur, P

    2006-08-01

    Alkylphenols and their derivatives, alkylphenol polyethoxylates (APEs), are synthetic chemicals of concern owing to their endocrine properties. Nonylphenol (NP) is a critical APE metabolite because of its recalcitrance to biodegradation, toxicity, and ability to bio-accumulate in aquatic organisms. Studies of NP effects in vertebrates demonstrated estrogenic disrupting properties in fish, birds, reptiles, and mammal cells in which NP displaces the natural estrogen from its receptor. Less is known on its toxicity toward invertebrates. Effects on reproduction have been reported, but toxicity on development has been poorly documented thus far. We investigated NP toxicity on survival and regeneration of the freshwater coelenterate Hydra attenuata. Hydra is known for its regenerative capacity and its sensitivity to chemical pollution. It has been used for over 20 years to screen for teratogenicity of chemicals (Johnson et al. (1982) Teratog Carcinog Mutagen 2:263-276). Our results showed that hydra appeared as one of the most sensitive species to acute and chronic toxicity of NP compared to several freshwater invertebrates. Regeneration was disrupted at NP concentrations lower than those affecting survival. Toxicity thresholds of NP for aquatic vertebrates and invertebrates are also reported and discussed in the context of environmental risk assessment and of water quality objectives recommended for surface waters in industrialized countries. NP levels have decreased during the last decade because of a voluntary agreement of surfactant producers and users. At present, concentrations of NP found in surface waters are far below 1 microg/L in Europe, but can reach several microg/L when wastewater treatment plant inefficiency occurs. PMID:16841324

  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. PMID:25017637

  10. Organic Contaminants in Chinese Sewage Sludge: A Meta-Analysis of the Literature of the Past 30 Years.

    PubMed

    Meng, Xiang-Zhou; Venkatesan, Arjun K; Ni, Yi-Lin; Steele, Joshua C; Wu, Ling-Ling; Bignert, Anders; Bergman, Åke; Halden, Rolf U

    2016-06-01

    The production of sewage sludge is increasing in China but with unsafe disposal practices, causing potential risk to human health and the environment. Using literature from the past 30 years (N = 159), we conducted a meta-analysis of organic contaminants (OCs) in Chinese sludge. Most data were available from developed and populated regions, and no data were found for Tibet. Since 1987, 35 classes of chemicals consisting of 749 individual compounds and 1 mixture have been analyzed, in which antibiotics and polycyclic aromatic hydrocarbons (PAHs) were the most targeted analytes. For 13 classes of principal OCs (defined as chemicals detected in over five studies) in sludge, the median (expressed in nanograms per gram dry weight) was the highest for phthalate esters (27 900), followed by alkylphenol polyethoxylates (12 000), synthetic musks (5800), antibiotics (4240), PAHs (3490), ultraviolet stabilizers (670), bisphenol analogs (160), organochlorine pesticides (110), polybrominated diphenyl ethers (100), pharmaceuticals (84), hormones (69), perfluorinated compounds (21), and polychlorinated biphenyls (15). Concentrations of PAHs in sludges collected between 1998 and 2012 showed a decreasing trend. Study findings suggest the need for a Chinese national sewage sludge survey to identify and regulate toxic OCs, ideally employing both targeted as well as nontargeted screening approaches. PMID:27144960

  11. 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., II; 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.

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

    PubMed

    Céspedes, Raquel; Lacorte, Sílvia; Ginebreda, Antonio; Barceló, Damià

    2006-07-01

    This study presents a quantitative estimation of the analysis and fate of several emerging pollutants, some of them endocrine-disrupting compounds, in surface water samples collected at several locations along the Ter River and two of its tributaries. Influent and effluent waters and particulate matter from five sewage treatment plants (STP) that discharge into these rivers were also studied. The target compounds analyzed were: nonylphenol ethoxylates (NPEO), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), phthalates, alcohol ethoxylates (AEO) and benzothiazoles. Chemical analysis by liquid chromatography-mass spectrometry using an electrospray interface (LC-ESI-MS) revealed the presence of low amounts (between 0.06 and 17.5 microg L(-1)) of the target compounds NPE(1+2)O and NP, which were detected in 100% and 84% of the samples respectively. Maximum concentrations occurred in the STPs associated with the municipalities of Vic and Girona. From the fate and behavior data obtained for the various compounds analyzed in the STP influent and effluent, we can conclude that the STPs are effective at removing large amounts (more than 70%) of the compounds studied from the water. PMID:16794817

  13. 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

  14. 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 ??g/g wet mass in the fish samples. ?? Elsevier B.V. All rights reserved.

  15. 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.

  16. GC-MS determination of bisphenol A and alkylphenol ethoxylates in river water from India and their ecotoxicological risk assessment.

    PubMed

    Selvaraj, Krishna Kumar; Shanmugam, Govindaraj; Sampath, Srimurali; Larsson, D G Joakim; Ramaswamy, Babu Rajendran

    2014-01-01

    Water samples from three rivers in southern India were analyzed for octylphenol (OP), nonylphenol (NP), and bisphenol A (BPA) residues by gas chromatography and mass spectrometry. The concentrations of OP, NP and BPA ranged from ND (not detected) to 16.3 ng/L, ND to 2200 ng/L, and 2.8 to 136 ng/L with detection frequencies of 96%, 66% and 100%, respectively. All three rivers showed a similar distribution pattern of NP>BPA>OP, however, the Kaveri river had elevated levels. The phenolic compounds in rivers are expected to cause potential toxicity to aquatic organism including crustaceans, molluscs, insects and fish. In respect to aquatic risk assessment, NP showed a greater hazard quotient (HQ) than did OP and BPA, and the highest HQ (62) was observed for fish in the Kaveri river. The backwater and estuarine NP levels may pose a risk to larvae of oysters and barnacles. Based on tolerable daily intake and reference dose, BPA and NP levels are considered safe for humans. However, NP levels in some water samples were greater than the drinking water safety limit (0.5 µg/L). This is the first report on phenolic compounds and their associated aquatic risks in Indian rivers. PMID:24183982

  17. Development of molecularly imprinted polymer in porous film format for binding of phenol and alkylphenols from water.

    PubMed

    Gryshchenko, Andriy O; Bottaro, Christina S

    2014-01-01

    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

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

    PubMed

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

    2011-12-01

    A simple method based on solid phase extraction (SPE) coupled with high performance liquid chromatography-mass spectrometry (HPLC-MS) was developed for the determination of octylphenol (OP), nonylphenol (NP), octylphenol ethoxylates (OPEOs) and nonylphenol ethoxylates (NPEOs) in brine. The extraction and cleanup of brine samples were performed on C18 solid-phase extraction cartridges. The complete separation among OP, NP, OPEOs and NPEOs was achieved on a Hypersil GOLD analytical column with methanol-water as the mobile phase. The determination was achieved using HPLC-MS with electrospray ionization (ESI) in selected ion monitoring mode. The results showed that the average recoveries of target compounds were 59.6% - 104.4% and the corresponding relative standard deviations (RSDs, n = 3) were 1.0% - 13.5%. The instrumental limits of detection for the compounds were 0.08 - 3 microg/L. This method was applied to the analysis of the samples of seawater near Dalian coast. The results showed that both NP and NPEOs were detected in all samples and their concentrations in seaport and oil port were much higher than those in other sampling sites. PMID:22500440

  19. Occurrence and distribution of bisphenol A and alkylphenols in the water of the Gulf of Gdansk (Southern Baltic).

    PubMed

    Staniszewska, Marta; Koniecko, Iga; Falkowska, Lucyna; Krzymyk, Ewelina

    2015-02-15

    In 2011-2012, the concentrations of bisphenol A (BPA), 4-tert-octylophenol (OP) and 4-nonylphenol (NP) in surface and near-bottom water of the Gulf of Gdansk, as well as inflowing rivers, were similar to those in other regions of Europe; BPA from <5.0 to 277.9 ng dm(-3), OP from <1.0 to 834.5 ng dm(-3), and NP from <4.0 to 228.6 ng dm(-3). The atmospheric transportation of phenol derivatives and their deposition into the water of the gulf was indicated by high enrichment factor values (EF) in the sea surface microlayer in relation to the sub-surface layer. The main route of BPA, OP and NP transportation into the waters of the Gulf of Gdansk is the River Vistula. In spring, significant amounts of bisphenol A and 4-nonylphenol were introduced to the coastal zone with meltwater. The main factors affecting the variability of BPA, OP and NP concentrations in surface and near-bottom water, particularly in summer, were increased tourism in the coastal region, water temperature and dissolved oxygen concentration. PMID:25491361

  20. 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.

  1. The effects of 4-nonylphenol contamination on livers of Tilapia fish (Oreochromus spilurs) in Jeddah.

    PubMed

    Abdulla Bin-Dohaish, El-jawaher

    2012-01-01

    Alkylphenol polyethoxylates is a group of estrogenic compounds. Natural or synthetic types of these compounds react with the endocrine system by binding hormone receptors, resulting in interference with their action, which is why they are called endocrine disrupting chemicals. Among their hydrolytic products are nonylphenols (NP), which are considered pollutants of aquatic environments. The objective of this study was to evaluate the pathological alterations on liver tissue of fish exposed to these compounds for long durations, starting from beginning of life and during the period of sexual maturity. Tilapia fish were obtained from Abhur fish farms, reared in the laboratory in special basins, and divided into two groups. The first maternal group was untreated and their larvae were divided into three sub-groups: control; exposed to 15μg/L; and exposed to 30 μg/L. The second maternal group was divided into 2 sub-groups: with larvae exposed to 15μg/L; and with their larvae exposed to 30 μg/L. Larvae and mother exposed to different concentrations of NP (15 and 30 μg/L) showed an increased accumulation of NP in both livers and muscles compared to the control group due to bioaccumulation. Tissue section examinations of the treated group (15 μg NP /L) showed disruption of liver architecture, with lyses, loss of nuclei, necrosis, and fatty infiltration. The changes were more marked in tissues exposed to (30 μg NP /L). Although this pollution was not lethal, its effect may be reflected in vital activities and in the economy. PMID:22688979

  2. Fate of endocrine disrupting compounds in membrane bioreactor systems.

    PubMed

    Hu, J Y; Chen, X; Tao, G; Kekred, K

    2007-06-01

    Yeast estrogen screen (YES) bioassay and liquid chromatography-mass spectrum-mass spectrum (LC-MS-MS) analysis were performed to investigate the fate of active and potential endocrine disrupting compounds in 3 pilot-scale and 2 lab-scale membrane bioreactor (MBR) systems. Compared with the overall estrogenicities of sewage treatment plant (STP) effluents from references, the MBR systems studied have relatively good performance in the removal of estrogenicity. Estrone (E1) was removed with relatively high efficiency (80.2-91.4%), but 17beta-estradiol (E2) was removed with moderate efficiency (49.3-66.5%) by the MBRs. However, the experimental results indicated that after the treatment by MBR, substantial amounts of E1, estrone-3-sulfate (E1-3S), estrone-3-glucuronide (E1-3G), and 17beta-estradiol-glucuronides (E2-G) passed through treatment systems and entered into the aquatic environment. The reduction in the levels of overall equivalent E1 (68.4%) and that of overall equivalent E2 (80.8%) was demonstrated for the pilot-scale MBR-B. For alkylphenol compounds, bisphenol A (BPA) was removed well with a removal efficiency of 68.9 -90.1%, but 4-nonylphenol (4-NP) concentration was amplified (removal efficiency of -439.5 to -161.1%) after MBR treatment which could be caused by the transformation of its parent compounds, nonylphenol polyethoxylates (NPnEOs). The amounts of adsorbed estrogens per kg dry mass was relatively low, due to short hydraulic retention time and high mixed liquor suspended solids in MBRs, compared to that in STPs. PMID:17612196

  3. Isomer-specific determination of 4-nonylphenols using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry.

    PubMed

    Eganhouse, Robert P; Pontolillo, James; Gaines, Richard B; Frysinger, Glenn S; Gabriel, Frédéric L P; Kohler, Hans-Peter E; Giger, Walter; Barber, Larry B

    2009-12-15

    Technical nonylphenol (tNP), used for industrial production of nonylphenol polyethoxylate surfactants, is a complex mixture of C(3-10)-phenols. The major components, 4-nonylphenols, are weak endocrine disruptors whose estrogenicities vary according to the structure of the branched nonyl group. Thus, accurate risk assessment requires isomer-specific determination of 4-NPs. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/ToFMS) was used to characterize tNP samples obtained from seven commercial suppliers. Under optimal chromatographic conditions, 153-204 alkylphenol peaks, 59-66 of which were identified as 4-NPs, were detected. The 4-NPs comprised approximately 86-94% of tNP, with 2-NPs and decylphenols making up approximately 2-9% and approximately 2-5%, respectively. The tNP products were analyzed for eight synthetic 4-NP isomers, and results were compared with published data based on GC/MS analysis. Significant differences were found among the products and between two samples from a single supplier. The enhanced resolution of GC x GC coupled with fast mass spectral data acquisition by ToFMS facilitated identification of all major 4-NP isomers and a number of previously unrecognized components. Analysis of tNP altered by the bacterium, Sphingobium xenophagum Bayram, revealed several persistent 4-NPs whose structures and estrogenicities are presently unknown. The potential of this technology for isomer-specific determination of 4-NP isomers in environmental matrices is demonstrated using samples of wastewater-contaminated groundwater and municipal wastewater. PMID:19924899

  4. Effects of sewage effluent and ethynyl oestradiol upon molecular markers of oestrogenic exposure, maturation and reproductive success in the sand goby (Pomatoschistus minutus, Pallas).

    PubMed

    Robinson, Craig D; Brown, Elaine; Craft, John A; Davies, Ian M; Moffat, Colin F; Pirie, David; Robertson, Fiona; Stagg, Ronald M; Struthers, Susan

    2003-01-24

    Male fish in several UK estuaries are known to be exposed to oestrogenic contamination, and whilst a limited number of studies have shown that exposure to oestrogens can reduce the reproductive success of fish, the impact of environmentally relevant exposures is less clear. The aim of this study was, therefore, to investigate the effects of exposure to environmentally realistic concentrations of a sewage effluent and the synthetic oestrogen 17alpha-ethynyl oestradiol (EE(2)) upon the reproductive success of a marine fish. Sand goby (Pomatoschistus minutus) were exposed for 7 months to EE(2) or a sewage effluent containing known xeno-oestrogens (alkylphenol polyethoxylates) and bred using within treatment crosses. Nominal exposure concentrations were 6 ng l(-1) EE(2), 0.3 or 0.03% v/v sewage effluent. At the end of the breeding trials, expression of hepatic zona radiata protein (Zrp) and vitellogenin (Vtg) mRNA were determined using two recently developed cDNA probes. Exposure to 6 ng l(-1) EE(2) induced Zrp and Vtg mRNA expression in male and female sand goby, impaired male maturation and reproductive behaviour, reduced female fecundity and reduced egg fertility. As a consequence, fertile egg production of the EE(2)-exposed population was reduced by 90%. Exposure to sewage effluent (0.3% v/v) increased adult mortality and female Zrp and Vtg mRNA expression, but did not induce male vitellogenesis. Exposure to EE(2) and 0.3% v/v sewage effluent impaired development of the male urogenital papilla. Fish exposed to 0.03% v/v sewage effluent produced more fertile eggs than those exposed to 0.3% effluent, or those receiving no effluent. It is concluded that male vitellogenesis in an oestrogenically exposed population may be accompanied by reduced reproductive success, but that it may not be indicative of altered reproductive output in a population exposed to an industrial sewage effluent. PMID:12505380

  5. Reproductive health in humans and wildlife: are adverse trends associated with environmental chemical exposure?

    PubMed

    Harrison, P T; Holmes, P; Humfrey, C D

    1997-10-20

    In recent years, evidence from disparate observations has indicated adverse changes in the reproductive health and fecundity of animals and humans. In humans, there is strong evidence for such trends in the incidences of testicular and female breast cancer, and concern has also been expressed regarding semen quality, cryptorchidism, hypospadias and polycystic ovaries. Laboratory studies have indicated that some chemicals in the environment, both natural and synthetic, have the potential to disrupt the endocrine system and that these could, at least theoretically, be partly responsible for the observed changes. Chemicals thus identified include the naturally occurring steroid hormones, phyto- and myco-estrogens, and anthropogenic chemicals such as synthetic hormones, organotins, organochlorine pesticides, polychlorinated biphenyls, dioxins, alkylphenol polyethoxylates, phthalates and bisphenol-A. While there is no direct evidence from human studies to confirm a causal link between exposure and effect, concern exists and is strengthened by reports of adverse reproductive and developmental effects in wildlife, possibly mediated via endocrine disruptive pathways. The development of imposex in neogastropod molluscs exposed to tributyltin has been attributed to such a mechanism and in wild populations of fish, alligators and birds, instances of masculinisation or feminisation in polluted areas have been noted. Among mammals, disturbed fertility of Florida panthers and some marine species has also been reported. A concentrated research and monitoring programme is required to clarify the nature and extent of effects on reproductive health in humans and wildlife, and to assess human and wildlife exposure to relevant naturally occurring or anthropogenic endocrine disrupting substances. This will enable a more robust evaluation of the contribution that environmental chemical exposure may have on adverse trends in the reproductive health of humans and wildlife. PMID:9372623

  6. Isomer-specific determination of 4-nonylphenols using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry

    USGS Publications Warehouse

    Eganhouse, R.P.; Pontolillo, J.; Gaines, R.B.; Frysinger, G.S.; Gabriel, F.L.P.; Kohler, H.-P.E.; Giger, W.; Barber, L.B.

    2009-01-01

    Technical nonylphenol (tNP), used for industrial production of nonylphenol polyethoxylate surfactants, is a complex mixture of C3-10-phenols. The major components, 4-nonylphenols, are weak endocrine disruptors whose estrogenicities vary according to the structure of the branched nonyl group. Thus, accurate risk assessment requires isomer-specific determination of 4-NPs. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/ ToFMS) was used to characterize tNP samples obtained from seven commercial suppliers. Under optimal chromatographic conditions, 153-204 alkylphenol peaks, 59-66 of which were identified as 4-NPs, were detected. The 4-NPs comprised ???86-94% of tNP, with 2-NPs and decylphenols making up???2-9%and???2-5%, respectively. The tNP products were analyzed for eight synthetic 4-NP isomers, and results were compared with published data based on GC/ MS analysis. Significant differences were found among the products and between two samples from a single supplier. The enhanced resolution of GC x GC coupled with fast mass spectral data acquisition by ToFMS facilitated identification of all major 4-NP isomers and a number of previously unrecognized components. Analysis of tNP altered by the bacterium, Sphingobium xenophagum Bayram, revealed several persistent 4-NPs whose structures and estrogenicities are presently unknown. The potential of this technology for isomer-specific determination of 4-NP isomers in environmental matrices is demonstrated using samples of wastewatercontaminated groundwater and municipal wastewater. ?? 2009 American Chemical Society.

  7. 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...

  8. 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.

  9. Development and validation of a liquid chromatography isotope dilution mass spectrometry method for the reliable quantification of alkylphenols in environmental water samples by isotope pattern deconvolution.

    PubMed

    Fabregat-Cabello, Neus; Sancho, Juan V; Vidal, Andreu; González, Florenci V; Roig-Navarro, Antoni Francesc

    2014-02-01

    We present here a new measurement method for the rapid extraction and accurate quantification of technical nonylphenol (NP) and 4-t-octylphenol (OP) in complex matrix water samples by UHPLC-ESI-MS/MS. The extraction of both compounds is achieved in 30min by means of hollow fiber liquid phase microextraction (HF-LPME) using 1-octanol as acceptor phase, which provides an enrichment (preconcentration) factor of 800. On the other hand we have developed a quantification method based on isotope dilution mass spectrometry (IDMS) and singly (13)C1-labeled compounds. To this end the minimal labeled (13)C1-4-(3,6-dimethyl-3-heptyl)-phenol and (13)C1-t-octylphenol isomers were synthesized, which coelute with the natural compounds and allows the compensation of the matrix effect. The quantification was carried out by using isotope pattern deconvolution (IPD), which permits to obtain the concentration of both compounds without the need to build any calibration graph, reducing the total analysis time. The combination of both extraction and determination techniques have allowed to validate for the first time a HF-LPME methodology at the required levels by legislation achieving limits of quantification of 0.1ngmL(-1) and recoveries within 97-109%. Due to the low cost of HF-LPME and total time consumption, this methodology is ready for implementation in routine analytical laboratories. PMID:24423386

  10. 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.

    PubMed

    Barber, Larry B; Lee, Kathy E; Swackhamer, Deborah L; Schoenfuss, Heiko L

    2007-04-20

    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, 17beta-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. PMID:17331597

  11. Rapid determination of alkylphenols in aqueous samples by in situ acetylation and microwave-assisted headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry.

    PubMed

    Wu, Yu-Pei; Wang, Yu-Chen; Ding, Wang-Hsien

    2012-08-01

    A rapid and solvent-free procedure for the determination of 4-tert-octylphenol and 4-nonylphenol isomers in aqueous samples is described. The method involves in-situ acetylation and microwave-assisted headspace solid-phase microextraction prior to their determination using gas chromatography-ion trap mass spectrometry operated in the selected ion storage mode. The dual experimental protocols to evaluate the effects of various derivatization and extraction parameters were investigated and the conditions optimized. Under optimized conditions, 300 μL of acetic anhydride mixed with 1 g of potassium hydrogencarbonate and 2 g of sodium chloride in a 20 mL aqueous sample were efficiently extracted by a 65 μm polydimethylsiloxane-divinylbenzene fiber that was located in the headspace when the system was microwave irradiated at 80 W for 5 min. The limits of quantitation were 5 and 50 ng/L for 4-tert-octylphenol and 4-nonylphenol isomers, respectively. The precision for these analytes, as indicated by relative standard deviations, were less than 8% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 74 to 88%. A standard addition method was used to quantitate 4-tert-octylphenol and 4-nonylphenol isomers, and the concentrations ranged from 120 to 930 ng/L in various environmental water samples. PMID:22899640

  12. 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...

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

    PubMed Central

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

    2015-01-01

    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. PMID:26074662

  14. 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. PMID:26970874

  15. 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...

  16. Selective adsorption of nonionic surfactant on hexagonal mesoporous silicates (HMSs) in the presence of ionic dyes.

    PubMed

    Punyapalakul, Patiparn; Takizawa, Satoshi

    2006-10-01

    Selective adsorption of alkylphenol polyethoxylates (APnEOs) from synthetic textile wastewater was investigated using hexagonal mesoporous silicates (HMSs). HMSs are synthetic silicate that have uniform mesopores, large surface areas and uniform surface functional groups. Five different types of HMSs were synthesized by surfactant-templating methods, and three of them were grafted with organic surface functional groups, i.e., n-octyldimethyl-, 3-aminopropyltriethoxy-, and 3-mercaptopropyl-groups. Titanium-substituted HMS was also made in the same way as HMS. Adsorption capacities and selectivities of these HMSs for APnEOs were investigated in batch adsorption experiments either in single-solute APnEO solutions or in mixed solutions with ionic dyes. Triton X-100 was used as a model APnEO and either Basic Yellow 1 or Acid Blue 45 was used as cationic or anionic dyes, respectively. All the HMSs except 3-aminopropyltriethoxy-grafted HMS had higher adsorption capacities of Triton X-100 than powdered activated carbon. HMS and Ti-HMS had the highest BET surface areas and mesopore volumes measured by the nitrogen adsorption method, and thereby the highest adsorption capacities for Triton X-100. Surface charge was the most important attractive force between HMSs and dyes. FT-IR spectra proved that hydrophilic HMSs adsorbed both Basic Yellow 1 and Acid Blue 45 by hydrogen bonding. Acid-base titration experiments revealed that all the HMSs except 3-aminopropyltriethoxy-grafted HMS were negatively charged at neutral pH, whereas PAC and 3-aminopropyltriethoxy-grafted HMS were positively charged. Due to negative surface charge, the anionic dye (Acid Blue 45) was not adsorbed on the four HMSs, which proves high selectivities of these HMSs for Triton X-100 over Acid Blue 45. On the contrary, a small amount of cationic dye (Basic Yellow 1) was adsorbed on all HMSs, but 3-aminopropyltriethoxy-grafted HMS showed the lowest adsorption capacity for Basic Yellow 1 due to positive

  17. PROPERTIES OF FOOD GRADE (EDIBLE) SURFACTANTS AFFECTING SUBSURFACE REMEDIATION OF CHLORINATED SOLVENTS

    EPA Science Inventory

    In this research, several food grade (edible) surfactants are systematically evaluated for various loss mechanisms: precipitation, adsorption, and coacervation (for nonionic surfactants). Cloud points for the polyethoxylate sorbitan (T-MAZ) surfactants are much higher than aquife...

  18. 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. PMID:25618664

  19. 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...

  20. 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...

  1. 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 ...

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

    PubMed Central

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

    2010-01-01

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

  3. 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. PMID:25683631

  4. 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. PMID:23849955

  5. Precipitation of mixtures of anionic and cationic surfactants; 3: Effect of added nonionic surfactant

    SciTech Connect

    Shiau, B.J.; Harwell, J.H.; Scamehorn, J.F. . Inst. for Applied Surfactant Research)

    1994-10-15

    The precipitation of an anionic surfactant by a cationic surfactant in the presence of a nonionic surfactant is examined. The precipitation domains for sodium dodecyl sulfate/dodecyl-pyridinium chloride were measured over a wide range of surfactant concentrations as a function of nonylphenol polyethoxylate concentration. Increasing the nonylphenol polyethoxylate concentration decreases the tendency for precipitation to occur. A model for predicting precipitation domains in ternary surfactant mixtures has been developed and verified experimentally. The model allows the nonionic surfactant to affect the precipitation behavior only by lowering the critical micelle concentration of the mixture. Small deviations between theory and experiments along part of the anionic-rich micelle boundary result from adsorption of SDS on the precipitate which gives the microcrystals a negative charge and prevents their growth to a visible size.

  6. ACUTE TOXICITY OF PARA-NONYLPHENOL TO SALTWATER ANIMALS

    EPA Science Inventory

    ?para-Nonylphenol (PNP), a mixture of alkylphenols used in producing nonionic surfactants, is distributed widely in surface waters and aquatic sediments, where it can affect saltwater species. This article describes a database for acute toxicity of PNP derived for calculating a n...

  7. 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. PMID:25460685

  8. ON-SITE GC/MS ANALYSIS OF CHAPMAN GASIFICATION SEPARATOR LIQUOR

    EPA Science Inventory

    The report gives results of a characterization of a wastewater stream from a coal gasification plant, using on-site extraction and GC/MS analysis. Extractable material in the wastewater was primarily phenols and alkylphenols, accounting for about 99% of the total mass identified....

  9. 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

    ... Register issue of January 28, 2008 (73 FR 4861) (FRL-8344-5) available on-line at http://www.epa.gov... 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...

  10. 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...

  11. 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...

  12. Contaminants Of Emerging Concern Within The Ohio River And Its Tributaries

    EPA Science Inventory

    Contaminants of emerging concern such as PPCPs, alkylphenols, EDCs, and PFCs in waterways have been increasing public concern. The extent and persistence of their occurrence in surface waters remains unclear. Though ther are many sources of these contaminants, research has focu...

  13. Contaminants Of Emerging Concern Within The Mainstem Of The Ohio River And its Tributaries

    EPA Science Inventory

    Contaminants of emerging concern such as PPCPs, alkylphenols, EDCs, and PFCs in waterways have been of increasing public concern. The extent and persistence of their occurrence in surface waters remains unclear. Though there are many sources of these contaminants, research has ...

  14. DEVELOPING RAPID ASSESSMENT TOOLS TO EVALUATE THE BIOLOGICAL EFFECTS OF COMPLEX AND BIOLOGICALLY ACTIVE CHEMICAL MIXTURES

    EPA Science Inventory

    Phase 1 of the project, the analysis of two wastewater effluents, and Phase 2A, controlled laboratory exposure experiments have been completed for all compounds and mixtures (estrogens, alkylphenols, pharmaceuticals).  The linkage of observed behavioral, anatomical and...

  15. Effects of immunotoxic activity of the major essential oil of Angelica purpuraefolia Chung against Aedes aegypti L.

    PubMed

    Park, Yool-Jin; Chung, Ill-Min; Moon, Hyung-In

    2010-12-01

    The rhizomes parts of Angelica purpuraefolia were extracted and the major essential oils composition and immunotoxic effects were studied. The analyses were conducted by gas chromatography and mass spectroscopy (GC-MS) revealed that the essential oils of A. purpuraefolia. The A. purpuraefolia essential oil (APEO) yield was 0.37%, and GC/MS analysis revealed that its major constituents were β-Phellandrene (32.11%), Nerolidol (10.11%), Pyrimidine derivative (27.33%), Heptadecane (4.33%), and Celorbicol (6.33%). The essential oil had a significant toxic effect against early fourth-stage larvae of Aedes aegypti L with an LC(50) value of 31.21 ppm and an LC(90) value of 87.22 ppm. The results could be useful in search for newer, safer, and more effective natural immunotoxic agents against A. aegypti. PMID:20163192

  16. A study of the thermodynamic properties of surfactant mixtures: Mixed micelle formation and mixed surfactant adsorption

    SciTech Connect

    Lopata, J.J.

    1992-12-31

    The volumetric mixing in anionic/nonionic, cationic/nonionic, and anionic/cationic mixed micelles was determined by examining the total surfactant apparent molar volumes at total surfactant concentrations much greater than the mixture critical micelle concentration. The mixed surfactant systems investigated were: sodium dodecyl sulfate and a polyethoxylated nonylphenol, at 0.15 M NaCl and with no added NaCl; cetyl pyridinium chloride and polyethoxylated nonylphenol, at 0.03 M NaCl; and sodium dodecyl sulfate and dodecyl pyridinium chloride, at 0.15 M NaCl. The results of this study suggest that the electrostatic interactions in the mixed micelles do no significantly effect the molar volume of the mixed micelle. Therefore, the micelle hydrophobic core dominates the volumetric mixing in mixed micelles. The adsorption of sodium dodecyl sulfate and a polyethoxylated nonylphenol and well defined mixtures thereof was measured on gamma alumina. A pseudo-phase separation model to describe mixed anionic/nonionic admicelle (adsorbed surfactant aggregate) formation was developed. In this model, regular solution theory was used to describe the anionic/nonionic surfactant interactions in the mixed admicelle and a patch-wise adsorption model was used to describe surfactant adsorption on a heterogeneous surface. Regular solution theory was tested on specific homogeneous surface patches by examining constant total surfactant adsorption levels. For the adsorption of binary surfactant mixtures adsorbing at total equilibrium concentrations above the mixture critical micelle concentration, simultaneous solution of the pseudo-phase separation models for mixed admicelle and mixed micelle formation predicts that the surfactant compositions in the monomer, micelle, and admicelle pseudo-phases are constant at a constant total adsorption level.

  17. Influence of resinous compounds in petroleum oils on formation of protective films by additives with labeled atoms

    SciTech Connect

    Faradzhev, K.F.

    1988-09-01

    The role of resinous compounds present in oil media in terms of their effects of protective film formation and corrosive wear of metal is investigated. Radioactive additives consisting of barium salts of an alkylphenol sulfide and an alkylphenol disulfide, containing a functional group of sulfur 35, were synthesized. These additives were added to the test oil in an amount of 3%. In most cases, the additives tend to form more stable films on the metal surface when they are used in oils containing resinous compounds than when they are used in individual groups of hydrocarbons. The quantity and efficiency of the protective film formed by the additive depends not only on the hydrocarbon structure of the oil hydrocarbons, but also on the quality of the additive, the nature of the metal, and the content of resinous compounds in the oil and the structure of these compounds.

  18. 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. PMID:16232469

  19. Degradation of 4-amylphenol and 4-hexylphenol by a new activated sludge isolate of Pseudomonas veronii and proposal for a new subspecies status.

    PubMed

    Ajithkumar, Bindu; Ajithkumar, Vasudevan P; Iriye, Ryozo

    2003-01-01

    Novel Pseudomonas strains INA04, INA05, and INA06, were isolated from activated sludge. Strain INA06 was found to degrade long chain alkylphenols such as 4-n-amylphenol and 4-n-hexylphenol as the sole source of carbon, apart from co-metabolic degradation of 4-n-nonylphenol in the presence of phenol, while INA04 and INA05 could grow on phenol, but could not grow well on alkylphenols. Induction studies on strain INA06 revealed a broad substrate-specific phenol hydroxylase, for the metabolism of phenol and alkylphenols, inducible with phenol or para-substituted alkylphenol. They bore close resemblance to members of Pseudomonas sensu stricto. 16S rDNA sequence homology of INA06 was closest to P. veronii (99.7%). DNA-DNA hybridization pointed out higher linkage (64% similarity) to the type strain of P. veronii than to other species of Pseudomonas sensu stricto (>60%). The BOX-PCR profile of all INA strains was similar, but different from that of P. veronii. Since biochemical characteristics were similar to those of P. veronii, and genetic relatedness was at the margin of species differentiation level (70%), we propose these strains to be treated as a new subspecies of P. veronii. The type strain of this new subspecies, named P. veronii subsp. inensis subsp. nov., is strain INA06. The accession number of strain INA05 is CIP 107595=JCM11829, and that of INA06 is CIP107594(T)=JCM11828(T). The 16S rDNA sequence accession number (DDBJ/EMBL/GenBank) of strain INA06 is AB056120. PMID:12576154

  20. 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

  1. A new analytical protocol for the determination of 62 endocrine-disrupting compounds in indoor air.

    PubMed

    Laborie, Stéphanie; Moreau-Guigon, Elodie; Alliot, Fabrice; Desportes, Annie; Oziol, Lucie; Chevreuil, Marc

    2016-01-15

    The objective of this study was to develop and validate a new analytical protocol for simultaneous determination of 62 semi-volatile organic compounds in both phases of indoor air. Studied compounds belong to several families: polybrominated diphenyl ethers, polychlorinated biphenyls, hexachlorobenzene, pentachlorobenzene, phthalates, polyaromatic hydrocarbons, parabens, tetrabromobisphenol A, bisphenol A, hexabromocyclododecane, triclosan, alkylphenols, alkylphenol ethoxylates, synthetic musks (galaxolide and tonalide) and pesticides (lindane and cypermethrin). A medium volume sampling system was used to collect simultaneously these endocrine-disrupting compounds (EDCs) from the gaseous and particulate phases. An accelerated solvent extraction method was optimized to obtain all EDCs in a single extract by atmospheric phase. Their extraction from the sorbents and their analysis by liquid and gas chromatography-mass spectrometry (LC/MS/MS, GC/MS and GC/MS/MS) was validated using spiked sorbents (recovery study and analytical uncertainty analysis by fully nested design). The developed protocol achieved low limits of quantification (<0.5ng m(-3)) and low uncertainty values (<5ng m(-3)) for all compounds. Once validated, the method was applied to indoor air samples from four locations (a house, an apartment, a day nursery and an office) and compared to literature to confirm its efficiency. All target EDCs were quantified in the samples and were primarily present in the gaseous phase. The major contaminants found in indoor air were, in descending order, phthalates, synthetic musks, alkylphenols and parabens. PMID:26592587

  2. Stormwater retention basin efficiency regarding micropollutant loads and ecotoxicity.

    PubMed

    Sébastian, Christel; Barraud, Sylvie; Gonzalez-Merchan, Carolina; Perrodin, Yves; Visiedo, Régis

    2014-01-01

    Retention basin efficiency in micropollutant removal has not been very well studied, in particular for pollutants highlighted by the European Water Framework Directive of 2000 such as pesticides, polybrominated diphenyl ethers (PBDEs) and alkylphenols. This study is based on in situ experiments carried out on a stormwater retention basin with the aim of estimating the basin efficiency in trapping and removing micropollutants from stormwater run-off from an industrial catchment drained by a separate sewer system. Along with stormwater, the basin receives some dry weather effluent flows, which are supposedly non-polluted. Ninety-four substances from five families (metals, polycyclic aromatic hydrocarbons (PAHs), PBDEs, alkylphenols and pesticides) were analyzed during 10 event campaigns in urban wet weather discharges at the inlet and outlet of the basin. The ecotoxicity of the samples was also tested. The results show high inter-event variability in both chemical and ecotoxic characteristics. They indicate good event efficiency concerning heavy metals and most PAHs. The studied pesticides, mainly found in the dissolved fraction, were not trapped. Particulate fraction study highlighted that settling is not the main process explaining micropollutant removal in a retention basin, as was noted for alkylphenols and PBDEs. PMID:24622545

  3. Removal of endocrine-disrupting chemicals in activated sludge treatment works.

    PubMed

    Johnson, A C; Sumpter, J P

    2001-12-15

    The release of endocrine-disrupting chemicals into the aquatic environment has raised the awareness of the central role played by sewage treatment in lowland water quality. This review focuses on the activated sludge process, which is commonly used to treat sewage in large towns and cities and which successfully removes the bulk of the organic compounds that enter the works. However, not all compounds are completely broken down or converted to biomass. For example, the estrogenic alkylphenols and steroid estrogens found in effluent are the breakdown products of incomplete breakdown of their respective parent compounds. Batch microcosm studies have indicated that estrone, ethinylestradiol, and alkylphenols will not be completely eliminated in activated sludge over typical treatment times. Field data suggest that the activated sludge treatment process can consistently remove over 85% of estradiol, estriol, and ethinylestradiol. The removal performance for estrone appears to be less and is more variable. Because of its relatively high hydrophobicity, the accumulation of alkylphenol in sludge has been observed. Although it has not been examined, accumulation of ethinylestradiol in sludge is a possibility due to its recalcitrance and hydrophobicity. A comparison between the concentrations of some of the major endocrine-active chemicals in effluents and their biological potencies has been made, to direct attention to the chemicals of most concern. While water purification techniques such as UV or activated charcoal could significantly remove these microorganic contaminants, the high costs involved suggest that research into the potential for treatment optimization should receive more attention. PMID:11775141

  4. Occurrence and spatial distribution of emerging contaminants in the unsaturated zone. case study: Guadalete River basin (Cadiz, Spain).

    PubMed

    Corada-Fernández, Carmen; Jiménez-Martínez, Joaquín; Candela, Lucila; González-Mazo, Eduardo; Lara-Martín, Pablo A

    2015-01-01

    Irrigation with reclaimed water is becoming a common practice in arid- and semi-arid regions as a consequence of structural water resource scarcity. This practice can lead to contamination of the vadose zone if sewage-derived contaminants are not removed properly. In the current work, we have characterized soils from the Guadalete River basin (SW Spain), which are often irrigated with reclaimed water from a nearby wastewater treatment plant and amended using sludge. Physico-chemical, mineralogical and hydraulic properties were measured in soil samples from this area (from surface up to 2 m depth). Emerging contaminants (synthetic surfactants and pharmaceutically active compounds, or PhACs) were also determined. Synthetic surfactants, widely used in personal care products (PCPs), were found in a wide range of concentrations: 73-1300 μg kg(-1) for linear alkylbenzene sulfonates (LAS), 120-496 μg kg(-1) for alkyl ethoxysulfates (AES), 19-1090 μg kg(-1) for alcohol polyethoxylates (AEOs), and 155-280 μg kg(-1) for nonylphenol polyethoxylates (NPEOs). The presence of surfactant homologues with longer alkyl chains was predominant due to their sorption capacity. A positive correlation was found between LAS and AEOs and soil organic carbon and clay content, respectively. Out of 64 PhACs analyzed, only 7 were detected occasionally (diclofenac, metoprolol, fenofibrate, carbamazepine, clarithromycin, famotidine and hydrochlorothiazide), always at very low concentrations (from 0.1 to 1.3 μg kg(-1)). PMID:24890839

  5. NMR method for accurate quantification of polysorbate 80 copolymer composition.

    PubMed

    Zhang, Qi; Wang, Aifa; Meng, Yang; Ning, Tingting; Yang, Huaxin; Ding, Lixia; Xiao, Xinyue; Li, Xiaodong

    2015-10-01

    (13)C NMR spectroscopic integration employing short relaxation delays and a 30° pulse width was evaluated as a quantitative tool for analyzing the components of polysorbate 80. (13)C NMR analysis revealed that commercial polysorbate 80 formulations are a complex oligomeric mixture of sorbitan polyethoxylate esters and other intermediates, such as isosorbide polyethoxylate esters and poly(ethylene glycol) (PEG) esters. This novel approach facilitates the quantification of the component ratios. In this study, the ratios of the three major oligomers in polysorbate 80 were measured and the PEG series was found to be the major component of commercial polysorbate 80. The degree of polymerization of -CH2CH2O- groups and the ratio of free to bonded -CH2CH2O- end groups, which correlate with the hydrophilic/hydrophobic nature of the polymer, were analyzed, and were suggested to be key factors for assessing the likelihood of adverse biological reactions to polysorbate 80. The (13)C NMR data suggest that the feed ratio of raw materials and reaction conditions in the production of polysorbate 80 are not well controlled. Our results demonstrate that (13)C NMR is a universal, powerful tool for polysorbate analysis. Such analysis is crucial for the synthesis of a high-quality product, and is difficult to obtain by other methods. PMID:26356097

  6. Surfactant loss control in chemical flooding: Spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Quarterly technical progress report, January 1, 1993--March 31, 1993

    SciTech Connect

    Somasundaran, P.

    1993-05-01

    The aim of this project is to elucidate the mechanisms of adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effect of surfactant structure, surfactant combinations and other inorganic and polymeric species will be determined using solids of relevant mineralogy. A multi-pronged approach consisting of micro & nano spectroscopy, microcalorimetry, electrokinetics, surface tension and wettability win be used to achieve the goals. The results of this study should help in controlling surfactant loss in chemical flooding and also in developing optimum structures and conditions for efficient chemical flooding processes. Adsorption of selected individual surfactants on oxide minerals was studied. The aim was to determine the effect of structure on surfactant adsorption at the solid-liquid as well as at the liquid-air interface. Nonionic polyethoxylated alkyl phenols and anionic meta xylene sulfonates (MXS) were the surfactants studied. Electrokinetic behavior was also determined along with adsorption in order to determine the role of electrostatic forces in determining the adsorption. In addition, the effect of varying the number of ethylene oxide groups on the adsorption of polyethoxylated alkyl phenols on silica was determined since the ethoxyl groups offer unique opportunities to control adsorption as well as wettability. Effect of pH was studied both because it is a parameter with first order effect and also because pH effects can help in developing mechanisms.

  7. Revised culture-based system for identification of Malassezia species.

    PubMed

    Kaneko, Takamasa; Makimura, Koichi; Abe, Michiko; Shiota, Ryoko; Nakamura, Yuka; Kano, Rui; Hasegawa, Atsuhiko; Sugita, Takashi; Shibuya, Shuichi; Watanabe, Shinichi; Yamaguchi, Hideyo; Abe, Shigeru; Okamura, Noboru

    2007-11-01

    Forty-six strains of Malassezia spp. with atypical biochemical features were isolated from 366 fresh clinical isolates from human subjects and dogs. Isolates obtained in this study included 2 (4.7%) lipid-dependent M. pachydermatis isolates; 1 (2.4%) precipitate-producing and 6 (14.6%) non-polyethoxylated castor oil (Cremophor EL)-assimilating M. furfur isolates; and 37 (34.3%) M. slooffiae isolates that were esculin hydrolyzing, 17 (15.7%) that were non-tolerant of growth at 40 degrees C, and 2 (1.9%) that assimilated polyethoxylated castor oil. Although their colony morphologies and sizes were characteristic on CHROMagar Malassezia medium (CHROM), all strains of M. furfur developed large pale pink and wrinkled colonies, and all strains of M. slooffiae developed small (<1 mm) pale pink colonies on CHROM. These atypical strains were distinguishable by the appearance of their colonies grown on CHROM. Three clinically important Malassezia species, M. globosa, M. restricta, and M. furfur, were correctly identified by their biochemical characteristics and colony morphologies. The results presented here indicate that our proposed identification system will be useful as a routine tool for the identification of clinically important Malassezia species in clinical laboratories. PMID:17881545

  8. Two-stage phyto-microremediation of tannery effluent by Spirodela polyrrhiza (L.) Schleid. and chromium resistant bacteria.

    PubMed

    Singh, Asha; Vyas, Dhiraj; Malaviya, Piyush

    2016-09-01

    Two-stage sequential treatment of tannery effluent was conducted employing a wetland plant, Spirodela polyrrhiza (L.) Schleid., and chromium (Cr) resistant bacterial strains. The bacterial strains were isolated from Cr-enriched environmental matrices and rhizosphere of Spirodela polyrrhiza. The phyto-rhizoremediation of tannery effluent by Spirodela and its rhizospheric bacteria (Cellulomonas biazotea APBR1-6, Bacillus safensis APBR2-12, Staphylococcus warneri APBR3-5, Microbacterium oleivorans APBR2-6), followed by microremediation by Cr resistant bacteria (Micrococcus luteus APBS5-1, Bacillus pumilus APBS5-2, Bacillus flexus APBE3-1, Virgibacillus sediminis APBS6-1) resulted in reduction of pollution parameters [COD (81.2%), total Cr (97.3%), Cr(VI) (99.3%), Pb(II) (97.0%), Ni (95.7%)]. The LC-MS analysis showed that many pollutants detected in untreated tannery effluent were diminished after bioremediation or long chains of alcohol polyethoxylates viz. C18EO6 in untreated effluent were broken down into smaller unit of alcohol polyethoxylate ((+)HHO[CH2CH2O]H), indicating that bacteria and Spirodela polyrrhiza, alongwith its rhizospheric associates utilized them as carbon and energy source. PMID:27318662

  9. 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.

  10. Combined effects of pharmaceuticals, personal care products, biocides and organic contaminants on the growth of Skeletonema pseudocostatum.

    PubMed

    Petersen, Karina; Heiaas, Harald Hasle; Tollefsen, Knut Erik

    2014-05-01

    Organisms in the environment are exposed to a number of pollutants from different compound groups. In addition to the classic pollutants like the polychlorinated biphenyls, polyaromatic hydrocarbons (PAHs), alkylphenols, biocides, etc. other compound groups of concern are constantly emerging. Pharmaceuticals and personal care products (PPCPs) can be expected to co-occur with other organic contaminants like biocides, PAHs and alkylphenols in areas affected by wastewater, industrial effluents and intensive recreational activity. In this study, representatives from these four different compound groups were tested individually and in mixtures in a growth inhibition assay with the marine algae Skeletonema pseudocostatum (formerly Skeletonema costatum) to determine whether the combined effects could be predicted by models for additive effects; the concentration addition (CA) and independent action (IA) prediction model. The eleven tested compounds reduced the growth of S. pseudocostatum in the microplate test in a concentration-dependent manner. The order of toxicity of these chemicals were irgarol>fluoxetine>diuron>benzo(a)pyrene>thioguanine>triclosan>propranolol>benzophenone 3>cetrimonium bromide>4-tert-octylphenol>endosulfan. Several binary mixtures and a mixture of eight compounds from the four different compound groups were tested. All tested mixtures were additive as model deviation ratios, the deviation between experimental and predicted effect concentrations, were within a factor of 2 from one or both prediction models (e.g. CA and IA). Interestingly, a concentration dependent shift from IA to CA, potentially due to activation of similar toxicity pathways at higher concentrations, was observed for the mixture of eight compounds. The combined effects of the multi-compound mixture were clearly additive and it should therefore be expected that PPCPs, biocides, PAHs and alkylphenols will collectively contribute to the risk in areas contaminated by such complex

  11. Endocrine disruptors in sewage treatment plants, receiving river waters, and sediments: integration of chemical analysis and biological effects on feral carp.

    PubMed

    Petrovic, Mira; Solé, Montserrat; López de Alda, María J; Barceló, Damià

    2002-10-01

    Occurrence of alkylphenol ethoxylates or their metabolites (alkylphenols and carboxylated derivatives), as well as natural and synthetic steroids in sewage treatment plant (STP) effluents and in their receiving waters, has been related to biological effects, measured as alterations of plasma vitellogenin (VTG) concentration in natural fish populations. Water composites of STP influents, effluents, sludge, river water, sediment, and feral carps (Cyprinus carpio) were analyzed over a seven-month period in two tributaries of the Llobregat River (NE Spain). Solid-phase extraction/liquid chromatography/mass spectrometry (SPE-LC-MS) analysis revealed concentrations of up to 31 microg/L for nonylphenol ethoxylates (NPEOs), 15 microg/L for nonylphenol (NP), and 35 microg/L for nonylphenoxy carboxylate (NPE1C) in river water downstream of STPs. These compounds were also found to accumulate in river sediment with concentrations ranging from 10 to 820 microg/kg of NPEOs and from 22 to 645 microg/kg for NP. Natural and synthetic estrogens and progestogens also occurred in the water and sediments analyzed but in the ng/L and microg/kg range, respectively. Vitellogenin fluctuated among sites and sampling periods, but it was found to be increased in male carp collected downstream of the main STP. A correlation between endocrine-disrupting compounds (EDCs) in water and sediment and plasma VTG concentration in male carp was observed, especially for alkylphenolic compounds in water and sediment samples (r = 0.83-0.84 for n = 24) and for estriol and estrone in water (r = 0.78 and 0.94 for n = 9 and 8, respectively). PMID:12371491

  12. Identification and steroid receptor activity of products formed from the bromination of technical nonylphenol.

    PubMed

    Hill, Elizabeth M; Smith, Michael D

    2006-09-01

    Alkylphenols are commonly present in wastewater effluents and may contribute to the total hormonal loading of receiving waters due to their weakly estrogenic properties. However the presence of reactive bromine species in some treated wastewaters can result in the formation of brominated alkylphenols which may also possess steroid receptor activity. In this study, the products of bromination of technical nonylphenol (NP) were identified, purified and tested in vitro in recombinant yeast steroid receptor transcription assays. Bromination of NP in the presence of acetic acid resulted in the formation of one major product which was identified as 2-bromo-4-nonylphenol (NPBr). In the presence of methanol/water, bromination of NP resulted in the formation 2,6-dibromo-4-nonylphenol (NPBr2) as well as a number of other minor polybrominated products. The EC50 of NPBr in the yeast estrogen receptor transcription (YES) assay was 6.7x10(-6) M, which was 48 fold less active than NP and 86,000 fold less active than the estrogen agonist 17beta-estradiol NPBr2 was not active in the YES assay. NP, NPBr and NPBr2 were all weakly androgenic in the yeast androgen receptor transcription assay but at concentrations which were 100,000 fold less active than the androgen receptor agonist dihydrotestosterone. Neither NP, NPBr or NPBr2 exhibited appreciable anti-estrogenic or anti-androgenic activity in the yeast receptor transcription assays. This study suggests that bromination of NP markedly reduces its estrogen receptor transcription activity but has no effect on the weak androgen receptor transcription activity of the alkylphenol. PMID:16473392

  13. 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

  14. Surfactant loss control in chemical flooding: Spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Quarterly technical progress report, April 1, 1993--June 30, 1993

    SciTech Connect

    Somasundaran, P.

    1993-08-31

    The aim of this contract is to elucidate the mechanisms underlying adsorption and surface precipitation of flooding surfactants on reservoir minerals. The results of this study should help in controlling surfactant loss in chemical flooding and also in developing optimum structures and conditions for efficient chemical flooding processes. Adsorption of single surfactants on silica and alumina as well as the solution behavior of surfactant mixtures was studied during this quarter. The adsorption of surfactants at the solid-liquid interface was correlated with changes in interfacial behavior such as wettability and zeta potential. Surface tension was used to study interactions between surfactant mixtures in solution. Mixed micellization of sodium dodecyl sulfate and dodecyl phenoxy polyethoxylated alcohol was found to be non-ideal. Regular solution theory adequately describes the interactions. The adsorption isotherm of a cationic surfactant, tetradecyl trimethyl ammonium chloride (TTAC), on alumina was determined at two values of pH. Changes in the settling rate of alumina suspensions after TTAC adsorption were also followed to describe the evolution of the adsorbed layer. At high surface coverage it was observed that the alumina surface became hydrophilic suggesting the formation of a TTAC bilayer at the surface. Wettability of silica after adsorption of nonyl phenyl polyethoxylated alcohols (with number of polyethylene oxide groups varying from 10-40) was measured using flotation to determine the orientation of the adsorbed layer. Effect of number of ethylene oxide groups was also determined. The amount of silica floated after the nonionic surfactant adsorption was same irrespective of the ethylene oxide chain length.

  15. 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. PMID:15856792

  16. Polar organic chemical integrative sampler (POCIS): application for monitoring organic micropollutants in wastewater effluent and surface water.

    PubMed

    Miège, Cécile; Budzinski, Hélène; Jacquet, Romain; Soulier, Coralie; Pelte, Thomas; Coquery, Marina

    2012-02-01

    In this paper, we discuss the advantages and drawbacks of POCIS (Polar Organic Chemical Integrative Sampler) for the evaluation of river water quality downstream of wastewater treatment plants. POCIS proved well adapted to sampling alkylphenols and several pharmaceuticals. Concentration factors and the decrease in limits of quantification, compared to grab water sample analyses, were significant except for hormones, β-blockers and bronchodilators. Promising preliminary results obtained in situ on deuterated atenolol used as a performance reference compound need to be confirmed in-lab. This work confirms that POCIS is a valuable tool for monitoring hydrophilic organic molecules in river and wastewaters. PMID:22193508

  17. Intersex condition and molecular markers of endocrine disruption in relation with burdens of emerging pollutants in thicklip grey mullets (Chelon labrosus) from Basque estuaries (South-East Bay of Biscay).

    PubMed

    Bizarro, C; Ros, O; Vallejo, A; Prieto, A; Etxebarria, N; Cajaraville, M P; Ortiz-Zarragoitia, M

    2014-05-01

    Endocrine disrupting chemicals (EDCs) interfere with the functioning of the endocrine system, causing reproductive and developmental disturbances in aquatic wildlife. Appearance of intersex gonads and elevated plasma levels of vitellogenin in male fish are well known biomarkers of exposure to xenoestrogenic EDCs. In the present study, intersex condition and transcription levels of vtg and cyp19a1b were assessed in five thicklip grey mullet populations from the Basque coast (Bay of Biscay). Levels of EDCs (estrogenic hormones, polycyclic musks, bisphenol-A, phthalates, alkylphenols and pesticides) were determined in water and fish bile. Intersex gonads were observed in three out of five mullet populations. Vtg and cyp19a1b were up-regulated in mullet populations with relatively higher EDCs load. Phthalates and pesticides were the most abundant EDCs in bile, followed by alkylphenols, musks, bisphenol-A and estrogenic hormones. Statistically significant correlations were found between concentrations of individual and total EDCs in bile and water samples and transcription levels of vtg and cyp19a1b. PMID:24262030

  18. 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.

  19. 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. PMID:22706016

  20. Priority and emerging pollutants in sewage sludge and fate during sludge treatment.

    PubMed

    Mailler, R; Gasperi, J; Chebbo, G; Rocher, V

    2014-07-01

    This paper aims at characterizing the quality of different treated sludges from Paris conurbation in terms of micropollutants and assessing their fate during different sludge treatment processes (STP). To achieve this, a large panel of priority and emerging pollutants (n=117) have been monitored in different STPs from Parisian wastewater treatment plants including anaerobic digestion, thermal drying, centrifugation and a sludge cake production unit. Considering the quality of treated sludges, comparable micropollutant patterns are found for the different sludges investigated (in mg/kg DM - dry matter). 35 compounds were detected in treated sludges. Some compounds (metals, organotins, alkylphenols, DEHP) are found in every kinds of sludge while pesticides or VOCs are never detected. Sludge cake is the most contaminated sludge, resulting from concentration phenomenon during different treatments. As regards treatments, both centrifugation and thermal drying have broadly no important impact on sludge contamination for metals and organic compounds, even if a slight removal seems to be possible with thermal drying for several compounds by abiotic transfers. Three different behaviors can be highlighted in anaerobic digestion: (i) no removal (metals), (ii) removal following dry matter (DM) elimination (organotins and NP) and iii) removal higher than DM (alkylphenols - except NP - BDE 209 and DEHP). Thus, this process allows a clear removal of biodegradable micropollutants which could be potentially significantly improved by increasing DM removal through operational parameters modifications (retention time, temperature, pre-treatment, etc.). PMID:24797622

  1. 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. PMID:24496035

  2. Effects of prolonged exposure to 4-tert-octylphenol on toxicity and indices of oestrogenic exposure in the sand goby (Pomatoschistus minutus, Pallas).

    PubMed

    Robinson, Craig D; Brown, Elaine; Craft, John A; Davies, Ian M; Moffat, Colin F

    2004-07-01

    Alkylphenolic compounds are present in estuarine and marine environments. They are moderately bioaccumulative, and oestrogenic to fish following three week, in vivo, exposures. The effects of prolonged exposure are, as yet, unclear. Sand goby (Pomatoschistus minutus) were exposed to measured concentrations of 4-tert-octylphenol (OP) in a 28-day, dose-ranging study, and a six month temporal response study. Following 28-days exposure to measured 31+/-6 or 101+/-47 microg l(-1) OP (mean+/-SD), immature male sand goby showed elevated vitellogenin (VTG) mRNA expression. Plasma alkali-labile phosphate concentrations were elevated in both sexes and were higher in females than males. Although measured OP concentrations were variable, they were significantly different for each treatment and a range of concentration-dependent effects were observed. The LC(50) for chronic OP exposure (8 weeks) was 29+/-6 microg l(-1), and both sexes demonstrated concentration and duration dependent increases in VTG mRNA expression. Exposure to 28+/-20 microg l(-1) OP (median+/-95% CI) for 6 months inhibited development of male nuptial colouration and sperm duct glands. These findings are discussed in relation to environmental concentrations of alkylphenols and ecological concerns. PMID:15046944

  3. Which coastal and marine environmental contaminants are truly emerging?

    PubMed

    Maruya, Keith A; Dodder, Nathan G; Tang, Chi-Li; Lao, Wenjian; Tsukada, David

    2015-02-01

    To better understand the past and present impact of contaminants of emerging concern (CECs) in coastal and marine ecosystems, archived samples were analyzed for a broad suite of analytes, including pharmaceuticals and personal care products (PPCPs), flame retardants (including PBDEs), perfluorinated compounds (PFCs), and current-use pesticides. Surface sediment, mussels (Mytilus spp.) and sediment core samples collected from the California (USA) coast were obtained from environmental specimen banks. Selected CECs were detected in recent surface sediments, with nonylphenol (4-NP), its mono- and di-ethoxylates (NP1EO and NP2EO), triclocarban, and pyrethroid insecticides in the greatest abundance. Alkylphenols, triclocarban, and triclosan were present in sediment core segments from the 1970s, as well as in Mytilus tissue collected during the 1990s. Increasing concentrations of some CECs (e.g., miconazole, triclosan) were observed in the surface layers (ca. 2007) of a sediment core, in contrast to peak concentrations of 4-NP and triclocarban corresponding to input during the 1970s, and an apparent peak input for PBDEs during the 1990s. These results suggest that chemicals sometimes referred to as "emerging" (e.g., alkylphenols, triclocarban) have been present in the aquatic environment for several decades and are decreasing in concentration, whereas others (e.g., miconazole, triclosan) are increasing. PMID:24743956

  4. Activated sludge acclimatisation kinetics to non-ionic surfactants.

    PubMed

    Carvalho, G; Novais, J M; Pinheiro, H M

    2003-01-01

    The biodegradation of surfactants is a frequent and complex problem in domestic and industrial wastewater treatment processes. In addition to the resulting metabolites being sometimes refractory, the complete biodegradation of many of the most employed non-ionic surfactants requires long hydraulic retention times and the presence of specialised bacterial consortia. Preliminary acclimatisation tests highlighted the importance of the sludge acclimatisation state to a specific surfactant substrate for biotreatment efficiency. This paper reports on studies aimed at quantifying activated sludge acclimatisation and memory retention levels when subjected to changes in the type of surfactant included in the feed. Several transitions were tested, namely from an alkylphenol ethoxylate to a linear alkyl ethoxylate and the reverse, and between alkyl ethoxylates with different hydrophobic and hydrophilic molecular chain lengths. The kinetic results showed that sludge activation and memory loss were more dynamic for primary biodegradation It was found that the sludge was harder to adapt to alkylphenol ethoxylate than to alkyl ethoxylate. The former also apparently introduced an inhibitory effect, resulting in very slow degradation kinetics when imposed to alkyl ethoxylate acclimatised sludge. When replacing an alkyl ethoxylate with another surfactant of the same family, a longer ethoxylate chain reduced the degradation rates. This effect was further enhanced by simultaneously increasing the hydrophobic chain length of the substrate. The acclimatisation kinetic after the replacement of an alkyl ethoxylate by a longer counterpart was slower than the reverse case, and memory was also more easily lost. PMID:12641258

  5. The use of enzyme-linked immunosorbent assays (ELISA) for the determination of pollutants in environmental and industrial wastes.

    PubMed

    Hirobe, M; Goda, Y; Okayasu, Y; Tomita, J; Takigami, H; Ike, M; Tanaka, H

    2006-01-01

    Twelve enzyme-linked immunosorbent assays (ELISA), for the determination of surfactants [linear alkylbenzene sulfonates (LAS), alkyl ethoxylates (AE), and alkylphenol ethoxylates (APE)], endocrine disruptors [alkylphenol (AP), AP + APE, and bisphenol A (BPA)], estrogens [17beta-estradiol (E2), estrone (El), estrogen (ES: El + E2 + estriol (E3)), 1 7alfa-ethynylestradiol (EE2)], dioxins and polychlorinated biphenyls (PCBs), were validated on environmental water and industrial wastes. The lowest quantification limits of these ELISAs were 0.05 microg/L (BPA, E2, El, ES and EE2), 2 microg/L (AE), 3 microg/L (dioxins and PCBs), 5 microg/L (AP, AP + APE) and 20 microg/L (LAS and APE). To apply these ELISAs to environmental or industrial waste samples, simple and appropriate pre-treatment methods were also developed for each ELISA. With optimized pre-treatments, the values of ELISAs were well co-related, in all cases, to those of instrumental analytical methods such as liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry (LC-MS/MS), and high-resolution gas chromatography mass spectrometry (HR-GC-MS), etc. PMID:17302299

  6. Degradation of octylphenol and nonylphenol by ozone - part I: direct reaction.

    PubMed

    Ning, Bo; Graham, Nigel J D; Zhang, Yanping

    2007-06-01

    This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol. PMID:17349676

  7. Biotransformation of halogenated nonylphenols with sphingobium xenophagum bayram and a nonylphenol-degrading soil-enrichment culture.

    PubMed

    Li, Yongmei; Montgomery-Brown, John; Reinhard, Martin

    2011-02-01

    When discharged in chlorinated wastewater, alkylphenol ethoxylate metabolites (APEMs) are often discharged in halogenated form (XAPEMs, X = Cl, or Br). The potential environmental impact of XAPEM release was assessed by studying the biotransformation of halogenated nonylphenol by Sphingobium xenophagum Bayram and a soil-enrichment culture. S. xenophagum Bayram transformed chlorinated nonylphenol (ClNP) slowly and nearly completely to form nonyl alcohol; the monobrominated nonylphenol (BrNP) and dibrominated nonylphenol were transformed cometabolically with nonylphenol (NP) as the primary substrate. The presence of either ClNP or BrNP in the S. xenophagum Bayram cultures retarded the transformation of nonhalogenated NP. NP-degrading soil cultures transformed nonhalogenated NP to a mixture of nonyl alcohols but were not capable of transforming either ClNP or BrNP. The presence of either ClNP or BrNP retarded the transformation of nonhalogenated NP in the soil cultures, as was observed in S. xenophagum Bayram cultures. Predicting the environmental fate of alkylphenol ethoxylate residues requires considering APEM halogenation during effluent chlorination and inhibitory effects as well as the refractory nature of halogenated metabolites. PMID:20677004

  8. 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

  9. 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.

  10. 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. PMID:21115189

  11. Novel double bond-transferring hydroxylation reaction involved in microbial metabolism of eugenol.

    PubMed

    Furukawa, H; Nagasawa, T

    1998-12-13

    We isolated a eugenol-degrading bacterium, Pseudomonas fluorescens E118. This strain produced a novel enzyme, eugenol dehydrogenase, which catalyzes the conversion of eugenol into coniferyl alcohol. The enzyme was purified from the eugenol-induced cells of P. fluorescens E118. The purified enzyme appeared to be homogeneous, judging from the analysis of polyacrylamide gel electrophoresis. The enzyme was a 68-kDa protein composed of two different subunits (alpha subunit, 10 kDa; and beta subunit, 58 kDa). The enzyme exhibited a cytochrome c-like absorption spectrum. The alpha subunit corresponded to cytochrome c. The enzyme catalyzed the dehydrogenation of 4-alkylphenol into the corresponding alkyl 1-(4-hydroxyphenyl)-alcohol derivatives. The reaction products were isolated and identified physicochemically. The enzyme catalyzed the enantioselective hydroxylation of p-alkylphenols. p-Ethylphenol and p-propylphenol were converted to S-(-)-p-(1-hydroxyphenyl)ethanol and S-(-)-p(1-hydroxyphenyl)propanol, respectively. PMID:10075640

  12. 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.

  13. 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.

  14. 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.

  15. Increased Risk for Congenital Heart Defects in Children Carrying the ABCB1 Gene C3435T Polymorphism and Maternal Periconceptional Toxicants Exposure

    PubMed Central

    Zhou, Kaiyu; Zhan, Yalan; Li, Yifei; Li, Huaying; Qiao, Lina; Wang, Fang; Hua, Yimin

    2013-01-01

    Backgrounds The etiology of congenital heart defect (CHD) is commonly believed to involve the interaction of multiple environmental and genetic factors. This study aimed to explore the joint effects of the ABCB1 gene C3435T polymorphism and maternal periconceptional toxicants exposure on the CHD risk in a Han Chinese population. Methods An age and gender matched case-control study with standardized data collection involving 201 pairs was conducted. Periconceptional toxicants exposure was obtained through a structured questionnaire. A job exposure matrix (JEM) was used for toxicants exposure assessment. Genotyping of the ABCB1 C3435T polymorphism was performed by sequencing. Logistic regression analysis was performed to assess the joint effects of the ABCB1 gene C3435T polymorphism and toxicants exposure on the risk of CHD. Placenta tissues and umbilical cords were collected to investigate the impact of C3435T polymorphism on the transcription and translation activities of ABCB1 gene. Results Maternal periconceptional exposures to phthalates (adjusted OR: 1.6; 95%CI: 1.0–2.6) and alkylphenolic compounds (adjusted OR:1.8; 95%CI:1.1–3.0) were associated with a higher incidence of CHDs in general. More cases were carriers of the ABCB1 CC/CT genotypes (OR: 2.0, 95%CI: 1.1–3.5, P-value: 0.021). Children carrying the CC/CT genotype and periconceptionally exposed to phthalates and alkylphenolic compounds suffered almost 3.5-fold increased risk of having CHD than non-exposed children with TT genotype (adjusted OR: 3.5, 95%CI: 1.5–7.9, P-value: 0.003), and the OR changed to 4.4 for septal defects (adjusted OR: 4.4,95%CI:1.8–10.9,P-value:0.001). The ABCB1 mRNA expression of the TT genotype was significantly higher than that of the CC genotype (P = 0.03). Compared with TT genotype, lower P-glycoprotein expression was observed for the CC/CT genotypes. Conclusion The C3435T polymorphism in the ABCB1 gene of fetus increases the risks of CHD in a Han Chinese

  16. 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.

  17. Monitoring North Sea oil production discharges using passive sampling devices coupled with in vitro bioassay techniques.

    PubMed

    Harman, Christopher; Farmen, Eivind; Tollefsen, Knut Erik

    2010-09-01

    Semipermeable membrane devices (SPMDs) and polar organic integrative chemical samplers (POCIS) were deployed in vicinity of an offshore oil production platform discharging production water (produced water) to the North Sea. Extracts from SPMDs and POCIS were subjected to chemical analysis for polycyclic aromatic hydrocarbons (PAHs) and alkylphenols (APs) respectively, and also assessed for acute toxicity (cytotoxicity), estrogen receptor (ER)-mediated production of vitellogenin (Vtg) and induction of 7-ethoxyresorufin-O-deethylase (EROD) activity in primary hepatocytes from rainbow trout (Oncorhynchus mykiss). Chemical analysis of the extracts revealed a gradient of exposure away from the platform for low molecular weight PAH and AP, whereas no exposure gradient was apparent for high molecular weight PAH, as expected. These data coupled with earlier work allowed a tentative general exposure scenario to be determined. The passive sampler extracts also caused modulation of the bioassay toxicity endpoints, although a clear gradient of response relative to the discharge point could not be identified. PMID:20683536

  18. Analytical study of endocrine-disrupting chemicals in leachate treatment process of municipal solid waste (MSW) landfill sites.

    PubMed

    Asakura, Hiroshi; Matsuto, Toshihiko; Tanaka, Nobutoshi

    2007-01-01

    Influent and processed water were sampled at different points in the leachate treatment facilities of five municipal solid waste (MSW) landfill sites. Then, the concentrations of endocrine-disrupting chemicals (EDCs), namely, alkylphenols (APs), bisphenol A (BPA), phthalic acid esters (PAEs) and organotin compounds (OTs), in the treated leachate samples were determined and the behavior of the EDCs in the treatment processes was discussed. The concentrations of APs were as low as those in surface waters, and no OTs were detected (detection limit: 0.01 microg/L). Meanwhile, diethylhexyl phthalate (DEHP), which was the most abundant of the four substances measured as PAEs, and BPA were found in all of the influent samples. BPA was considerably degraded by aeration, except when the water temperature was low and the total organic carbon (TOC) was high. By contrast, aeration, biological treatment, and coagulation/sedimentation removed only a small amount of DEHP. PMID:17585294

  19. Temperature dependence of the vapour tension of methyl-substituted phenol derivatives

    SciTech Connect

    S.G. Gagarin

    2007-05-15

    Notable among the coking products of coal are phenol and its derivatives, derived for the coal tar and water layer above ht tar. Given that phenol an its derivatives are mainly extracted from coal tar fractions by rectification, information on how the vapor tension of the individual components depends on the temperature is of great importance. For phenol and various substituted alkylphenols there are tabular data. In the pre-computer era these data were sufficient for the separation of phenol mixtures. However, the development and introduction of information technology in the coal industry and in the design process demands the mathematical description of the physicochemical processes of coking products. The temperature dependence of the saturated vapor pressure for organic compounds is commonly described by the Antoine equation.

  20. 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. PMID:10720741

  1. Sources, fluxes and risk of organic micropollutants to the Cantabrian Sea (Spain).

    PubMed

    Sánchez-Avila, Juan; Vicente, Joana; Echavarri-Erasun, Beatriz; Porte, Cinta; Tauler, Romà; Lacorte, Silvia

    2013-07-15

    The sources, distribution and risk of 51 organic micropollutants (OMPs) in the Cantabrian coastal environment (NW Spain) were evaluated. Gas chromatography coupled to tandem mass spectrometry was used to determine polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, polybrominated diphenyl ethers, phthalates esters, bisphenol A and alkylphenols. 45 OMPs were detected in coastal/estuarine waters. Wastewater treatment plant effluents and emissary discharges were identified as the main sources of contamination. The accumulation of OMPs in sediments and the bioaccumulation in 21 days caged mussels were also assessed. Chemical results were combined with the "Combined Monitoring-based and Modeling-based Priority Setting Scheme" COMMPS procedure for risk assessment analysis. Finally, the chemical status of the different sampling locations was estimated using site risk indexes. Those indexes can be conveniently displayed in quality geographical maps and are considered a valuable tool for the environmental management and risk assessment of the region under study. PMID:23673206

  2. 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. PMID:26552534

  3. [Analysis of estrogens, nonylphenol, 4-tert-octylphenol and bisphenol A in the sediments].

    PubMed

    Wu, Wei; Shi, Jiang-Hong; Chen, Qing-Cai; Zhang, Hui; Liu, Xiao-Wei

    2013-02-01

    Estrogens and alkylphenols have received much attention because of its endocrine disrupting effects to aquatic ecosystem in recent years. The fate of these compounds in sediments which is a repository of many organic pollutants has an important significance on the study of behaviors of target compounds in the environment. It is difficult to separate trace estrogens from sediments with complex matrices. Alkali extraction, liquid-liquid extraction and LC-MS/MS were used to analyze estrogens, nonylphenol, 4-tert-octylphenol and bisphenol A in sediments based on their physicochemical properties. The results showed that recoveries of the seven target compounds were 61.3%-93.7%. The established pretreatment method can effectively remove pollutants that cannot dissolve in alkali solution or that cannot dissolve in both acid and alkali solution. It can widely be used to analyze sediments and soil samples because of its low cost and simple operation but with high recoveries and low detection limit. PMID:23668147

  4. Syntheses, spectroscopic and structural properties of phenoxysilyl compounds: X-ray structures, FT-IR and DFT calculations

    NASA Astrophysics Data System (ADS)

    Jabłońska, Agnieszka; Ponikiewski, Łukasz; Ejsmont, Krzysztof; Herman, Aleksander; Dołęga, Anna

    2013-12-01

    The reaction of silicon disulfide with alkylphenols yields tetraphenoxysilane, cyclodisilthiane and silanethiol. The outcome of the reaction depends on the presence of the steric hindrance in the ortho position on the reacting phenol. New products of the reaction of silicon disulfide with phenols are characterized by FT-IR, NMR, X-ray diffraction and DFT calculations. The intramolecular interactions in the compounds are mainly XH---π (X = C, S) whereas the intermolecular interactions are either very weak CH---π/CH---O contacts found in aryloxysilane or electrostatic dipole-dipole attraction in cyclodisilthiane and silanethiol. The S-H---π interactions in the obtained silanethiol are analyzed with the use of DFT/GGA BLYP-D XC potentials. The energy of intramolecular S-H---π interaction is estimated.

  5. 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.

  6. Ardisia: health-promoting properties and toxicity of phytochemicals and extracts.

    PubMed

    de Mejía, Elvira González; Ramírez-Mares, Marco Vinicio

    2011-11-01

    Ardisia species (Myrsinaceae) are found throughout tropical and subtropical regions of the world. Traditional medicinal uses attributed to Ardisia include alleviation of liver cancer, swelling, rheumatism, earache, cough, fever, diarrhea, broken bones, dysmenorrhea, respiratory tract infections, traumatic injuries, inflammation, pain, snake and insect bites, birth complications and to improve general blood circulation, among others. Ardisia species are rich in polyphenols, triterpenoid saponins, isocoumarins, quinones and alkylphenols. A summary of the uses, potential health benefits, adverse reactions and important bioactive phytochemicals isolated from the Ardisia species is presented. Future research needs to include more toxicological studies, more comprehensive chemical characterization of extracts, bioavailability, extract standardization, investigation of possible herb-drug interactions, plant improvement with regards to bioactivity and composition, and additional human and animal studies to confirm the health-promoting properties claimed for Ardisia species. The information presented here exemplifies the potential of Ardisia species as a source of chemotherapeutic, chemo-modulating and/or chemopreventive agents. PMID:22003924

  7. The separation and synthesis of lipidic 1,2- and 1,3-diols from natural phenolic lipids for the complexation and recovery of boron.

    PubMed

    Tyman, John H P; Mehet, Satinderjit K

    2003-12-01

    A study has been made of the semi-synthesis of 1,3-diols (anacardic alcohols) from natural phenolic lipid resources from Anacardium occidentale and Anacardium giganteum which have given C15 and C11 derivatives, respectively. An isomeric 1,3-diol (isoanacardic alcohol) has been obtained from cardanol separated from technical cashew nut-shell liquid. Homologous 1,3-diols have been synthesised from a range of synthetic 2-alkyl-, 3-alkyl- and 4-alkylphenols and from 6-alkylsalicylic acids. The natural 1,2-diol, urushiol, from Rhus vernicifera has been purified. All these lipidic compounds have been studied for their complexation and the potential recovery of boron as boric acid. PMID:14623453

  8. In vitro evaluation of the disinfection efficacy on Eimeria tenella unsporulated oocysts isolated from broilers.

    PubMed

    Guimarães, José S; Bogado, Alexey L Gomel; da Cunha, Thiago Cezar B; Garcia, João Luis

    2007-01-01

    The objective of this study was to evaluate in vitro the action of eight chemical principles by disinfection efficacy (DE) of Eimeria tenella oocysts. Disinfection efficacy was evaluated by either destruction or sporulation inhibition of the oocysts. Eight treatments were performed: T1 (Glutaraldehyde 42.5 g + Benzalkonium Chloride 7.5 g); T2 (Benzalkonium chloride + quaternary ammonium salt); T3 (formol 37% + Sodium Dodecylbenzene Sulfonate 12%); T4 (sodium hypochlorite 2%); T5 (Orthodichlorobenzene 60% + Xylene 30%); T6 (Polyoctyl polyamino ethyl glycine + Polyoxyethylene alkylphenol ether + Sodium Chloride); T7 (Chloramine T) and finally T8 (free iodine 2.25% + Phosphoric acid 15 g). The control test was carried out with distilled water (T9). The best DE were observed, respectively, in T3 (79.49%), T5 (75.60%) and T4 (65.56%) treatments. PMID:17706006

  9. The purification and characterization of 4-ethylphenol methylenehydroxylase, a flavocytochrome from Pseudomonas putida JD1.

    PubMed

    Reeve, C D; Carver, M A; Hopper, D J

    1989-10-15

    The enzyme 4-ethylphenol methylenehydroxylase was purified from Pseudomonas putida JD1 grown on 4-ethylphenol. It is a flavocytochrome c for which the Mr was found to be 120,000 by ultracentrifuging and 126,000 by gel filtration. The enzyme consists of two flavoprotein subunits each of Mr 50,000 and two cytochrome c subunits each of Mr 10,000. The redox potential of the cytochrome is 240 mV. Hydroxylation proceeds by dehydrogenation and hydration to give 1-(4'-hydroxyphenyl)ethanol, which is also dehydrogenated by the same enzyme to 4-hydroxyacetophenone. The enzyme will hydroxylate p-cresol but is more active with alkylphenols with longer-chain alkyl groups. It is located in the periplasm of the bacterium. PMID:2556994

  10. 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. PMID:21719036

  11. Utilization of coal as a source of chemicals

    SciTech Connect

    Demirbas, A.

    2007-07-01

    Coal consists carbon-based substances can be used as a source of specialty aromatic chemicals and aliphatic chemicals. Four widespread processes allow for making chemicals from coals: gasification, liquefaction, direct conversion, and co-production of chemicals and fuels along with electricity. Coal is gasified to produce synthesis gas (syngas) with a gasifier which is then converted to paraffinic liquid fuels and chemicals by Fischer-Tropsch synthesis. Liquid product from coal gasification mainly contains benzene, toluene, xylene (BTX), phenols, alkylphenols, and cresol. Methanol is made using coal or syngas with hydrogen and carbon monoxide in a 2 to 1 ratio. Coal-derived methanol has many preferable properties as it is free of sulfur and other impurities. Syngas from coal can be reformed to hydrogen. Ammonium sulfate from coal tar by pyrolysis can be converted to ammonia. The humus substances can be recovered from brown coal by alkali extraction.

  12. 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. PMID:21392814

  13. 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%. PMID:26902668

  14. 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. PMID:23618141

  15. 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. PMID:26736051

  16. Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

    PubMed

    Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

    2016-09-01

    Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings. PMID:27343586

  17. Technical, occupational health and environmental aspects of metal degreasing with aqueous cleaners.

    PubMed

    Lavoué, Jérôme; Bégin, Denis; Géerin, Michel

    2003-08-01

    Aqueous cleaners used for metal degreasing are detergent formulations containing surfactants (such as linear alkylbenzene sulphonates, alkylphenol ethoxylates or alcohol ethoxylates), builders (such as hydroxides, phosphates or silicates), sequestrants (such as EDTA or NTA), anti-corrosive agents (such as ethanolamines), solvents (such as glycol ethers or d-limonene) and other specialty additives. Generally sold as concentrates, they are typically diluted between 3 and 20 times in water, leading to solutions containing only a few per cent active products. The cleaning efficiency depends on physicochemical phenomena such as wetting, solubilization, emulsification, dispersion, sequestration and saponification, and is enhanced by thermal and mechanical energy. Cleaning equipment is based on spraying or immersion of the parts and may include drying and rinsing steps. Because of the complexity and variability of the mixtures, the occupational health and environmental evaluation of aqueous cleaners is based on the study of their components. Aqueous cleaners are generally believed to present a low risk to workers' health and to the environment. However, some anionic surfactants and strong alkalis are skin and eye irritants, ethanolamines are allergenic and several glycol ethers of the ethylene glycol family are proven systemic toxicants that are easily absorbed through the skin. Although most components of aqueous cleaners are biodegradable and of low ecotoxicity, alkylphenol ethoxylates degrade into persistent and toxic compounds. Phosphates, if released directly into the environment, may cause eutrophication of rivers and lakes. Waste recycling or treatment by specialized facilities is usually required for spent solutions containing contaminants such as oils and heavy metals. From a technical, toxicological and environmental standpoint, aqueous cleaners can be used successfully to replace traditional organic solvents used in metal degreasing. PMID:12890654

  18. Multi-component analysis of polar water pollutants using sequential solid-phase extraction followed by LC-ESI-MS.

    PubMed

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

    2003-06-01

    A multi-component screening analysis method for polar to medium-polar water pollutants was developed. Sample clean-up and group separation are performed by sequential solid-phase extraction (SSPE) using automated SPE with C18 and polymeric sorbent materials. Analyses are performed by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) using a single-quadrupole instrument. More than 90 priority compounds of environmental interest--comprising the most important chemical and substance classes: phenols, carboxylic acids, aromatic sulfonates, aromatic amines, pharmaceuticals, surfactants, dyes, and pesticides--have been chosen for the experiments. The compounds are divided by the SSPE procedure into 3 different polarity classes. The extraction recoveries were determined in the 3 fractions for every single substance, and were for most of the analytes in the range of 50-100%. A mixture of hexane-dichloromethane was used for the elution of nonpolar compounds like alkylphenols from C18. Methanol and acetone are well suited for the elution of more polar substances. The limits of detection (LODs) were determined for all compounds. Effluents from municipal and industrial wastewater treatment plants (WWTPs) treating waste water from textile industries; and the corresponding receiving waters (rivers and lakes) have been analysed with the developed method. Urban and industrial pollution was observed in rivers and streams in the area north of Milan, Italy. In the water samples different phenols (nitrophenols, bisphenol A, nonylphenol), alkylphenol ethoxylate surfactants, their metabolites with endocrine disrupting potential, aromatic sulfonates, linear alkylbenzenesulfonate surfactants, dyes, pesticides, pharmaceuticals, and a dichlorobenzidine compound were identified. PMID:12833980

  19. Analysis of endocrine disrupters and related compounds in sediments and sewage sludge using on-line turbulent flow chromatography-liquid chromatography-tandem mass spectrometry.

    PubMed

    Gorga, Marina; Insa, Sara; Petrovic, Mira; Barceló, Damià

    2014-07-25

    A novel fully automated method based on dual column switching using turbulent flow chromatography followed by liquid chromatography coupled to tandem mass spectrometry (TFC-LC-MS/MS) was applied for the determination of endocrine disruptors (EDCs) and related compounds in sediment and sewage sludge samples. This method allows the unequivocal identification and quantification of the most relevant environmental EDCs such as natural and synthetic estrogens and their conjugates, antimicrobials, parabens, bisphenol A (BPA), alkylphenolic compounds, benzotriazoles, and organophosphorus flame retardants, minimizing time of analysis and alleviating matrix effects. Applying this technique, after the extraction of the target compounds by pressurized liquid extraction (PLE), sediment and sewage sludge extracts were directly injected to the chromatographic system and the analytes were concentrated into the clean-up loading column. Using six-port switching system, the analytes were transferred to the analytical column for subsequent detection by MS-MS (QqQ). In order to optimize this multiplexing system, a comparative study employing six types of TurboFlow™ columns, with different chemical modifications, was performed to achieve the maximum retention of analytes and best elimination of matrix components. Using the optimized protocol low limits of quantification (LOQs) were obtained ranging from 0.0083 to 1.6 ng/g for sediment samples and from 0.10 to 125 ng/g for sewage sludge samples (except for alkylphenol monoethoxylate). The method was used to evaluate the presence and fate of target EDCs in the Ebro River which is the most important river in Spain with intensive agricultural and industrial activities in the basin that contribute to deteriorating soil and water quality. PMID:24909438

  20. Comparative toxicity and bioconcentration of nonylphenol in freshwater organisms.

    PubMed

    Spehar, Robert L; Brooke, Larry T; Markee, Thomas P; Kahl, Michael D

    2010-09-01

    Degradation of alkylphenol ethoxylates to more persistent alkylphenols such as nonylphenol occurs in wastewater treatment plants where nonylphenol is released to aquatic systems. In this study, acute and chronic tests were conducted to determine the toxicity and bioconcentration of nonylphenol to freshwater organisms for use in deriving national water quality criteria. Acute median effect concentrations (EC50s) based on loss of equilibrium, immobility, and lethality for species representing several taxonomic groups ranged from 21 to 596 microg/L. The EC50s were up to a factor of 2 less than median lethal concentrations (LC50s) and decreased with time over the test periods of 24 to 96 h. In chronic tests, early life stages of rainbow trout were 14 times more sensitive to nonylphenol than in acute tests and approximately 20 times more sensitive than Daphnia magna exposed over their complete life cycle. Comparisons of chronic test endpoints showed that 20% effect concentrations (EC20s), determined by regression testing, and chronic values, determined by hypothesis testing, were similar for both the rainbow trout and Daphnia magna. The lowest mean tissue-effect concentrations of nonylphenol appeared to be greater for the fathead minnow than bluegill, and ranged from approximately 130 to 160 microg/g after 96-h exposure and from approximately 20 to 90 microg/g after 28-d exposure. Mean lipid normalized bioconcentration factors (BCFs) associated with no-effect concentrations were approximately 180 and 50 for the fathead minnow and bluegill, respectively. The present test results suggest that long-term exposures to nonylphenol at concentrations found in some surface waters could adversely impact sensitive components of freshwater communities. PMID:20821669

  1. Detection and evaluation of endocrine-disruption activity in water samples from Portuguese rivers.

    PubMed

    Quirós, Laia; Céspedes, Raquel; Lacorte, Sílvia; Viana, Paula; Raldúa, Demetrio; Barceló, Damià; Piña, Benjamin

    2005-02-01

    Water samples (n = 183) from Portuguese rivers were tested for the presence of endocrine disruptors using the recombinant yeast assay (RYA) combined with chemical identification of compounds having endocrine-disruption properties by liquid chromatography coupled to mass spectrometry. Ten selected locations were sampled monthly for a period of 20 months, from April 2001 to December 2002. More than 90% of samples showed either no detectable or low levels of estrogenicity (<0.1 ng/L of estradiol equivalents). The remaining samples (17 in total, 9.3%) showed estrogenicity values ranging from 0.1 to 1.7 ng/L of estradiol equivalents; only two samples showed values greater than 1 ng/L of estradiol equivalents. Most highly estrogenic samples (13 of 17 samples) originated in five sampling sites clustered in two zones near Porto and Lisbon. Chemical analysis detected alkylphenolic compounds (octyl- and nonylphenol plus nonylphenol ethoxylates) in all samples, albeit at concentrations less than 1 microg/L for each compound in 80% of samples. Total analyte concentration exceeded 10 microg/L in only 10 samples, with all but one of those originating from only two sampling sites. In these two locations, a good correlation was observed between the concentrations of octylphenol, nonylphenol, and to a lesser extent, bisphenol A in the samples and their estrogenicity values as calculated by RYA. We conclude that estrogenic activity can be explained by alkylphenol contamination in only these sites; for the remainder, we propose that pesticides and urban waste may be the main factors responsible for estrogenic contamination. PMID:15719999

  2. 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. PMID:22341470

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

    PubMed

    Schlenk, Daniel; Sapozhnikova, Yelena; Irwin, Mary Ann; Xie, Lingtian; Hwang, Wendy; Reddy, Sharanya; Brownawell, Bruce J; Armstrong, Jeff; Kelly, Mike; Montagne, David E; Kolodziej, Edward P; Sedlak, David; Snyder, Shane

    2005-11-01

    The exposure and uptake of environmental estrogenic compounds have been reported in previous studies of demersal flatfish species in the central Southern California Bight (SCB), USA. The objective of this study was to evaluate the estrogenic or feminizing activity of marine sediments from the SCB by using in vivo vitellogenin (VTG) assays in male or juvenile fish. In 2003, sediments were collected near wastewater outfalls serving the counties of Los Angeles (LACSD) and Orange (OCSD), and the city of San Diego (SD), California, USA. Cultured male California halibut (CH; Paralichthys californicus) were either directly exposed to sediments for 7 d or treated with two intraperitoneal injections of sediment extract over 7 d. The 17beta-estradiol (E2) equivalent values ranged from 1 to 90 microg/kg with LACSD > SD > OCSD. Measurable concentrations of E2 were observed in all sediment extracts and ranged from 0.16 to 0.45 ng/g. Estrone (El) was only observed in sediments near the LACSD outfall (0.6 ng/g). Alkylphenols and alkylphenol ethoxylates were observed in all sediment samples, but were highest near the OCSD outfall, where concentrations of nonylphenol were 3,200 ng/g. Fractionation studies of the LACSD sediment extract collected in 2004 failed to demonstrate relationships between VTG expression and 62 analytes, including E2, which was observed in the whole extract (2.9 ng/g). Oxybenzone (1.6 ng/g) was identified in bioactive fractions as well as unknown compounds of relatively high polarity. These results indicate that estrogen receptor-based assays may underestimate environmental estrogenic activity and estrogenic compounds other than classic natural and xenoestrogens may contribute to estrogenic activity of sediments from the SCB. PMID:16398118

  4. 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. PMID:23683400

  5. 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. PMID:26063514

  6. Enhancement of Oral Bioavailability of Curcumin by a Novel Solid Dispersion System.

    PubMed

    Hu, Liandong; Shi, Yanjing; Li, Jian Heng; Gao, Na; Ji, Jing; Niu, Feng; Chen, Queting; Yang, Xiaoning; Wang, Shaocheng

    2015-12-01

    The objective of this study was to improve the solubility and bioavailability of curcumin by a new curcumin dripping pills (Cur-DPs) formulation using melt mixing methods. The optimal formulation consisted of Polyethoxylated 40 hydrogenated castor oil (Cremophor RH40), Poloxamer 188, and Polyethylene glycol 4000 (PEG 4000). Differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier-transform infrared spectroscopy (FT-IR) were used to verify the forming of Cur-DPs. All the physical characterization information proved the formation of Cur-DPs, and the results demonstrated the superiority of the dripping pills in dissolution rates. The pharmacokinetic study of Cur-DPs was performed in rats compared to the pure curcumin suspension. The oral bioavailability of poorly water-soluble curcumin was successfully improved by CUR-DPs. And the stability of prepared Cur-DP was also in a good state in 3 months. These results identified the Cur-DPs was an effective new approach for pharmaceutical application. PMID:25804949

  7. Effectiveness of liposomal paclitaxel against MCF-7 breast cancer cells.

    PubMed

    Heney, Melanie; Alipour, Misagh; Vergidis, Dimitrios; Omri, Abdelwahab; Mugabe, Clement; Th'ng, John; Suntres, Zacharias

    2010-12-01

    Paclitaxel is an effective chemotherapeutic agent that is widely used for the treatment of several cancers, including breast, ovarian, and non-small-cell lung cancer. Due to its high lipophilicity, paclitaxel is difficult to administer and requires solubilization with Cremophor EL (polyethoxylated castor oil) and ethanol, which often lead to adverse side effects, including life-threatening anaphylaxis. Incorporation of paclitaxel in dimyristoylphosphatidylcholine:dimyristoylphosphatidylglycerol (DPPC:DMPG) liposomes can facilitate its delivery to cancer cells and eliminate the adverse reactions associated with the Cremophor EL vehicle. Accordingly, the effectiveness of liposomal paclitaxel on MCF-7 breast cancer cells was examined. The results from this study showed that (i) the lipid components of the liposomal formulation were nontoxic, (ii) the cytotoxic effects of liposomal paclitaxel were improved when compared with those seen with conventional paclitaxel, and (iii) the intracellular paclitaxel levels were higher in MCF-7 cells treated with the liposomal paclitaxel formulation. The results of these studies showed that delivery of paclitaxel as a liposomal formulation could be a promising strategy for enhancing its chemotherapeutic effects. PMID:21164564

  8. Anaerobic degradation of alcohol ethoxylates and polyethylene glycols in marine sediments.

    PubMed

    Traverso-Soto, Juan M; Rojas-Ojeda, Patricia; Sanz, José Luis; González-Mazo, Eduardo; Lara-Martín, Pablo A

    2016-02-15

    This research is focused on alcohol polyethoxylates (AEOs), nonionic surfactants used in a wide variety of products such as household cleaners and detergents. Our main objective in this work was to study the anaerobic degradation of these compounds and their main aerobic degradation products and precursors (polyethylene glycols, PEGs, which are also used for many other applications) in marine sediments, providing the first data available on this topic. First, we observed that average AEO sediment-water partition coefficients (Kd) increased towards those homologs having longer alkyl chains (from 257 L/kg for C12 to 5772 L/kg for C18),which were less susceptible to undergo biodegradation. Overall, AEO and PEG removal percentages reached up to 99.7 and 93%, respectively, after 169 days of incubation using anaerobic conditions in sediments ([O2] = 0 ppm, Eh = -170 to -380 mV and T = 30 °C). Average half-life was estimated to be in a range from 10 to 15 days for AEO homologs (C12AEO8-C18AEO8), and 18 days for PEGEO8.Methanogenic activity proved to be intense during the experiment, confirming the occurrence of anaerobic conditions. This is the first study showing that AEOs and PEGs can be degraded in absence of oxygen in marine sediments, so this new information should be taken into account for future environmental risk assessments on these chemicals. PMID:26657255

  9. Co-Formulants in Glyphosate-Based Herbicides Disrupt Aromatase Activity in Human Cells below Toxic Levels

    PubMed Central

    Defarge, Nicolas; Takács, Eszter; Lozano, Verónica Laura; Mesnage, Robin; Spiroux de Vendômois, Joël; Séralini, Gilles-Eric; Székács, András

    2016-01-01

    Pesticide formulations contain declared active ingredients and co-formulants presented as inert and confidential compounds. We tested the endocrine disruption of co-formulants in six glyphosate-based herbicides (GBH), the most used pesticides worldwide. All co-formulants and formulations were comparably cytotoxic well below the agricultural dilution of 1% (18–2000 times for co-formulants, 8–141 times for formulations), and not the declared active ingredient glyphosate (G) alone. The endocrine-disrupting effects of all these compounds were measured on aromatase activity, a key enzyme in the balance of sex hormones, below the toxicity threshold. Aromatase activity was decreased both by the co-formulants alone (polyethoxylated tallow amine—POEA and alkyl polyglucoside—APG) and by the formulations, from concentrations 800 times lower than the agricultural dilutions; while G exerted an effect only at 1/3 of the agricultural dilution. It was demonstrated for the first time that endocrine disruption by GBH could not only be due to the declared active ingredient but also to co-formulants. These results could explain numerous in vivo results with GBHs not seen with G alone; moreover, they challenge the relevance of the acceptable daily intake (ADI) value for GBHs exposures, currently calculated from toxicity tests of the declared active ingredient alone. PMID:26927151

  10. 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. PMID:27162129

  11. Paclitaxel loading in PLGA nanospheres affected the in vitro drug cell accumulation and antiproliferative activity

    PubMed Central

    Vicari, Luisa; Musumeci, Teresa; Giannone, Ignazio; Adamo, Luana; Conticello, Concetta; De Maria, Ruggero; Pignatello, Rosario; Puglisi, Giovanni; Gulisano, Massimo

    2008-01-01

    Background PTX is one of the most widely used drug in oncology due to its high efficacy against solid tumors and several hematological cancers. PTX is administered in a formulation containing 1:1 Cremophor® EL (polyethoxylated castor oil) and ethanol, often responsible for toxic effects. Its encapsulation in colloidal delivery systems would gain an improved targeting to cancer cells, reducing the dose and frequency of administration. Methods In this paper PTX was loaded in PLGA NS. The activity of PTX-NS was assessed in vitro against thyroid, breast and bladder cancer cell lines in cultures. Cell growth was evaluated by MTS assay, intracellular NS uptake was performed using coumarin-6 labelled NS and the amount of intracellular PTX was measured by HPLC. Results NS loaded with 3% PTX (w/w) had a mean size < 250 nm and a polydispersity index of 0.4 after freeze-drying with 0.5% HP-Cyd as cryoprotector. PTX encapsulation efficiency was 30% and NS showed a prolonged drug release in vitro. An increase of the cytotoxic effect of PTX-NS was observed with respect to free PTX in all cell lines tested. Conclusion These findings suggest that the greater biological effect of PTX-NS could be due to higher uptake of the drug inside the cells as shown by intracellular NS uptake and cell accumulation studies. PMID:18657273

  12. New mechanism of γ-H2AX generation: Surfactant-induced actin disruption causes deoxyribonuclease I translocation to the nucleus and forms DNA double-strand breaks.

    PubMed

    Zhao, Xiaoxu; Yang, Gang; Toyooka, Tatsushi; Ibuki, Yuko

    2015-12-01

    We previously showed that nonionic surfactants, nonylphenol polyethoxylates (NPEOs), induced phosphorylation of histone H2AX, forming γ-H2AX. In this study, we analyzed the mechanism of γ-H2AX generation by an NPEO with 15 ethylene oxide units (NPEO(15)). In MCF-7 breast carcinoma cells, NPEO(15) treatment induced γ-H2AX in a dose-dependent manner. EDTA and ZnCl2, two inhibitors of deoxyribonuclease I (DNase I), inhibited both the γ-H2AX and DNA double-strand breaks induced by NPEO(15). NPEO(15) disrupted filamentous actin and released free DNase I as detected by cell fractionation analysis. Based on immunofluorescence staining of DNase I and monitoring DNase I-GFP localization, DNase I was translocated from the cytosol to the nucleus of cells after treatment with NPEO(15). This translocation did not occur with the common DNA damage inducers ultraviolet B irradiation and hydrogen peroxide. Other surfactants, Tween 20, Triton X-100 and Nonidet P-40, also generated γ-H2AX. These results show that γ-H2AX induction by surfactants including NPEOs, occurs via a new mechanism involving release of free DNase I with actin disruption. This mechanism is distinct from the process of γ-H2AX generation caused by direct chemically induced DNA damage. PMID:26653977

  13. Acidic pretreatment of wheat straw in decanol for the production of surfactant, lignin and glucose.

    PubMed

    Marinkovic, Sinisa; Le Bras, Jean; Nardello-Rataj, Véronique; Agach, Mickaël; Estrine, Boris

    2012-01-01

    Wheat straw is an abundant residue of agriculture which is increasingly being considered as feedstock for the production of fuels, energy and chemicals. The acidic decanol-based pre-treatment of wheat straw has been investigated in this work. Wheat straw hemicellulose has been efficiently converted during a single step operation into decyl pentoside surfactants and the remaining material has been preserved keeping all its promises as potential feedstock for fuels or value added platform chemicals such as hydroxymethylfurfural (HMF). The enzymatic digestibility of the cellulose contained in the straw residue has been evaluated and the lignin prepared from the material characterized. Wheat-based surfactants thus obtained have exhibited superior surface properties compared to fossil-based polyethoxylates decyl alcohol or alkyl oligoglucosides, some of which are largely used surfactants. In view of the growing importance of renewable resource-based molecules in the chemical industry, this approach may open a new avenue for the conversion of wheat straw into various chemicals. PMID:22312256

  14. Acidic Pretreatment of Wheat Straw in Decanol for the Production of Surfactant, Lignin and Glucose

    PubMed Central

    Marinkovic, Sinisa; Le Bras, Jean; Nardello-Rataj, Véronique; Agach, Mickaël; Estrine, Boris

    2012-01-01

    Wheat straw is an abundant residue of agriculture which is increasingly being considered as feedstock for the production of fuels, energy and chemicals. The acidic decanol-based pre-treatment of wheat straw has been investigated in this work. Wheat straw hemicellulose has been efficiently converted during a single step operation into decyl pentoside surfactants and the remaining material has been preserved keeping all its promises as potential feedstock for fuels or value added platform chemicals such as hydroxymethylfurfural (HMF). The enzymatic digestibility of the cellulose contained in the straw residue has been evaluated and the lignin prepared from the material characterized. Wheat-based surfactants thus obtained have exhibited superior surface properties compared to fossil-based polyethoxylates decyl alcohol or alkyl oligoglucosides, some of which are largely used surfactants. In view of the growing importance of renewable resource-based molecules in the chemical industry, this approach may open a new avenue for the conversion of wheat straw into various chemicals. PMID:22312256

  15. Natural Gas Residual Fluids: Sources, Endpoints, and Organic Chemical Composition after Centralized Waste Treatment in Pennsylvania.

    PubMed

    Getzinger, Gordon J; O'Connor, Megan P; Hoelzer, Kathrin; Drollette, Brian D; Karatum, Osman; Deshusses, Marc A; Ferguson, P Lee; Elsner, Martin; Plata, Desiree L

    2015-07-21

    Volumes of natural gas extraction-derived wastewaters have increased sharply over the past decade, but the ultimate fate of those waste streams is poorly characterized. Here, we sought to (a) quantify natural gas residual fluid sources and endpoints to bound the scope of potential waste stream impacts and (b) describe the organic pollutants discharged to surface waters following treatment, a route of likely ecological exposure. Our findings indicate that centralized waste treatment facilities (CWTF) received 9.5% (8.5 × 10(8) L) of natural gas residual fluids in 2013, with some facilities discharging all effluent to surface waters. In dry months, discharged water volumes were on the order of the receiving body flows for some plants, indicating that surface waters can become waste-dominated in summer. As disclosed organic compounds used in high volume hydraulic fracturing (HVHF) vary greatly in physicochemical properties, we deployed a suite of analytical techniques to characterize CWTF effluents, covering 90.5% of disclosed compounds. Results revealed that, of nearly 1000 disclosed organic compounds used in HVHF, only petroleum distillates and alcohol polyethoxylates were present. Few analytes targeted by regulatory agencies (e.g., benzene or toluene) were observed, highlighting the need for expanded and improved monitoring efforts at CWTFs. PMID:26147419

  16. Co-Formulants in Glyphosate-Based Herbicides Disrupt Aromatase Activity in Human Cells below Toxic Levels.

    PubMed

    Defarge, Nicolas; Takács, Eszter; Lozano, Verónica Laura; Mesnage, Robin; Spiroux de Vendômois, Joël; Séralini, Gilles-Eric; Székács, András

    2016-03-01

    Pesticide formulations contain declared active ingredients and co-formulants presented as inert and confidential compounds. We tested the endocrine disruption of co-formulants in six glyphosate-based herbicides (GBH), the most used pesticides worldwide. All co-formulants and formulations were comparably cytotoxic well below the agricultural dilution of 1% (18-2000 times for co-formulants, 8-141 times for formulations), and not the declared active ingredient glyphosate (G) alone. The endocrine-disrupting effects of all these compounds were measured on aromatase activity, a key enzyme in the balance of sex hormones, below the toxicity threshold. Aromatase activity was decreased both by the co-formulants alone (polyethoxylated tallow amine-POEA and alkyl polyglucoside-APG) and by the formulations, from concentrations 800 times lower than the agricultural dilutions; while G exerted an effect only at 1/3 of the agricultural dilution. It was demonstrated for the first time that endocrine disruption by GBH could not only be due to the declared active ingredient but also to co-formulants. These results could explain numerous in vivo results with GBHs not seen with G alone; moreover, they challenge the relevance of the acceptable daily intake (ADI) value for GBHs exposures, currently calculated from toxicity tests of the declared active ingredient alone. PMID:26927151

  17. HPLC/ESI-quadrupole ion trap mass spectrometry for characterization and direct quantification of amphoteric and nonionic surfactants in aqueous samples

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

    An amphoteric (cocamidopropylbetaine, CAPB) and a nonionic (alcohol polyethoxylate, AE) surfactant were characterized by electrospray ionization quadrupole ion trap mass spectrometry (ESI-MS) as to their homologue distribution and ionization/fragmentation chemistry. Quantitative methods involving reversed-phase gradient HPLC and (+)ESI-MSn were developed to directly determine these surfactants in hydroponic plant growth medium that received simulated graywater. The predominant homologues, 12 C alkyl CAPB and 9 EO AE, were monitored to represent the total amount of the respective surfactants. The methods demonstrated dynamic linear ranges of 0.5-250 ng (r2 > 0.996) for CAPB and 8-560 ng (r2 > 0.998) for AE homologue mixture, corresponding to minimum quantification limits of 25 ppb CAPB and 0.4 ppm AE with 20-microL injections. This translated into an even lower limit for individual components due to the polydispersive nature of the surfactants. The procedure was successfully employed for the assessment of CAPB and AE biodegradation in a hydroponic plant growth system used as a graywater bioreactor.

  18. Nonylphenol ethoxylates and their metabolites in sewage treatment plants and rivers of Tianjin, China.

    PubMed

    Yu, Yong; Zhai, Hongyan; Hou, Shaogang; Sun, Hongwen

    2009-09-01

    Nonylphenol polyethoxylates (NPnEO) and nonylphenol (NP) have provoked much environmental concern because of their weak estrogenic activities. We monitored NPnEO and their metabolites in rivers in Tianjin and in a sewage treatment plant of Tianjin monthly for 1 year. The total concentrations of NPnEO and NP in influent, up to 47.2 microgL(-1) in August, were higher in summer than in other seasons. During the 12 months survey, NP was accumulated in most effluent samples with a mean value of 2.92 microgL(-1). The average concentrations of nonylphenol monoethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO) and nonylphenol triethoxylate (NP3EO) in effluents were 1.26, 1.53 and 1.06 microgL(-1), which corresponds to percent removals of 75%, 60% and 62%, respectively. In rivers of Tianjin, NP2EO and nonylphenoxyethoxy acetic acid (NP2EC) exhibited the highest concentrations in the surface water, up to 1.38 and 9.59 microgL(-1), respectively. The pollution of nonylphenolic substances in sediments of Haihe River belongs to moderate or severe level in the world, with the total concentration between 4.1 and 9.9 microgg(-1), dry weight. PMID:19596133

  19. Surfactant loss control in chemical flooding: Spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1992--September 30, 1993

    SciTech Connect

    Somasundaran, P.

    1994-07-01

    The aim of this research project is to investigate mechanisms underlying adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effects of surfactant structure, surfactant combinations, various inorganic and polymeric species, and solids mineralogy will be determined. A multi-pronged approach consisting of micro & nano spectroscopy, microcalorimetry, electrokinetics, surface tension and wettability; is used in this study. The results obtained should help in controlling surfactant loss in chemical flooding and in developing optimum structures and conditions for efficient chemical flooding processes. During the first year of this three year contract, adsorption of single surfactants and select surfactant mixtures was studied at the solid-liquid and gas-liquid interfaces. Surfactants studied include alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride. Adsorption of surfactant mixtures of varying composition was also investigated. The microstructure of the adsorbed layer was characterized using fluorescence spectroscopy. Changes interfacial properties such as wettability, electrokinetics and stability of reservoir minerals were correlated with the amount of reagent adsorbed. Strong effects of the structure of the surfactant and position of functional groups were revealed.

  20. Occurrence and Biodegradation of Nonylphenol in the Environment

    PubMed Central

    Mao, Zhen; Zheng, Xiao-Fei; Zhang, Yan-Qiu; Tao, Xiu-Xiang; Li, Yan; Wang, Wei

    2012-01-01

    Nonylphenol (NP) is an ultimate degradation product of nonylphenol polyethoxylates (NPE) that is primarily used in cleaning and industrial processes. Its widespread use has led to the wide existence of NP in various environmental matrices, such as water, sediment, air and soil. NP can be decreased by biodegradation through the action of microorganisms under aerobic or anaerobic conditions. Half-lives of biodegradation ranged from a few days to almost one hundred days. The degradation rate for NP was influenced by temperature, pH and additions of yeast extracts, surfactants, aluminum sulfate, acetate, pyruvate, lactate, manganese dioxide, ferric chloride, sodium chloride, hydrogen peroxide, heavy metals, and phthalic acid esters. Although NP is present at low concentrations in the environment, as an endocrine disruptor the risks of long-term exposure to low concentrations remain largely unknown. This paper reviews the occurrence of NP in the environment and its aerobic and anaerobic biodegradation in natural environments and sewage treatment plants, which is essential for assessing the potential risk associated with low level exposure to NP and other endocrine disruptors. PMID:22312266

  1. Fate and degradation of nonylphenolic compounds during wastewater treatment process.

    PubMed

    Lian, Jing; Liu, Junxin

    2013-08-01

    In order to explore the biodegradation behavior of nonylphenolic compounds during wastewater treatment processing, two full-scale wastewater treatment plants were investigated and batch biodegradation experiments were conducted. The biodegradation pathways under the various operational conditions were identified from batch experiments: shortening of ethoxy-chains dominated under the anaerobic condition, whereas oxidizing of the terminal alcoholic group prevailed over the other routes under the aerobic condition. Results showed that the anoxic condition could accelerate the biodegradation rates of nonylphenolic compounds, but had no influence on the biodegradation pathway. The biodegradation rates of nonylphenol (NP) and short-chain nonylphenol polyethoxylates (NPnEOs, n: number of ethoxy units) increased from the anaerobic condition, then the anoxic, finally to the aerobic condition, while those of long-chain NPnEOs and nonylphenoxy carboxylates (NPECs) seemed similar under the various conditions. Under every operational condition, long-chain NPnEOs showed the highest biodegradation activity, followed by NPECs and short-chain NPnEOs, whereas NP showed relatively recalcitrant characteristics especially under the anaerobic condition. In addition, introducing sulfate and nitrate to the anaerobic condition could enhance the biodegradation of NP and short-chain NPnEOs by supplying more positive redox potentials. PMID:24520688

  2. Preparation, characterization, cytotoxicity and pharmacokinetics of liposomes containing water-soluble prodrugs of paclitaxel.

    PubMed

    Ceruti, M; Crosasso, P; Brusa, P; Arpicco, S; Dosio, F; Cattel, L

    2000-01-01

    Paclitaxel (Taxol) is a diterpenoid isolated from Taxus brevifolia, used clinically for the treatment of ovarian and breast cancer. Due to its aqueous insolubility it is administered dissolved in ethanol and Cremophor EL (polyethoxylated castor oil), which has serious side effects. In order to eliminate this vehicle, in previous work we entrapped paclitaxel in conventional and in polyethylene glycol coated liposomes. However, in neither formulation did we obtain satisfactory entrapment efficiency. In this study we increased the paclitaxel concentration entrapped in liposomes by incorporating different water-soluble prodrugs, such as the 2'-succinyl, 2'-methylpyridinium acetate and 2'-mPEG ester paclitaxel derivatives, in the lipid vesicles. Liposomes containing 2'-mPEG (5000)-paclitaxel showed the best performance in terms of stability, entrapment efficiency and drug concentration (6.5 mgml(-1)). The in vitro cytotoxic activity of this liposomal prodrug was similar to that of the parent drug. The pharmacokinetic parameters for the free and for the liposomal prodrugs fitted a bi-exponential plasma disposition. The most important change in pharmacokinetic values of the prodrug vs. the free drug liposomal formulations was t(1/2)beta, plasma lifetime, which was longer in liposomes containing 2'-mPEG (5000)-paclitaxel. PMID:10640588

  3. Surfactant loss control in chemical flooding spectroscopic and calorimetric study of adsorption and precipitation on reservoir minerals. Annual report, September 30, 1992--September 30 1995

    SciTech Connect

    Casteel, J.

    1996-07-01

    The aim of this research project was to investigate mechanisms governing adsorption and surface precipitation of flooding surfactants on reservoir minerals. Effects of surfactant structure, surfactant combinations, various inorganic and polymeric species, and solids mineralogy have been determined. A multi-pronged approach consisting of micro & nano spectroscopy, electrokinetics, surface tension and wettability is used in this study. The results obtained should help in controlling surfactant loss in chemical flooding and in developing optimum structures and conditions for efficient chemical flooding processes. During the three years contract period, adsorption of single surfactants and select surfactant mixtures was studied at the solid-liquid and gas-liquid interfaces. Alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride were the surfactants studied. Adsorption of surfactant mixtures of varying composition was also investigated. The microstructure of the adsorbed layer was characterized using fluorescence spectroscopy. Changes in interfacial properties such as wettability, electrokinetics and stability of reservoir minerals were correlated with the amounts of reagent adsorbed. Strong effects of the structure of the surfactant and position of functional groups were revealed. Changes of microstructure upon dilution (desorption) were also studied. Presence of the nonionic surfactants in mixed aggregate leads to shielding of the charge of ionic surfactants which in turn promotes aggregation but reduced electrostatic attraction between the charged surfactant and the mineral surface. Strong consequences of surfactant interactions in solution on adsorption as well as correlations between monomer concentration in mixtures and adsorption were revealed.

  4. Laboratory column studies of chlorinated solvent remediation in subsurface media using food grade surfactants

    SciTech Connect

    Shiau, B.J.; Sabatini, D.A.; Harwell, J.H.

    1995-12-01

    Laboratory column studies were conducted to evaluate enhanced removal of chlorinated solvents using food grade surfactants via solubilization and microemulsification (mobilization) mechanisms. Nonionic T-MAZ-60 (sorbitan polyethoxylate monostearate) was used for solubilization studies, and mixtures of anionic bis-2-ethylhexyl sodium sulfosuccinate (AOT) and sodium mono and dimethyl naphthalene sulfonate (SMDNS) were used for microemulsification (Winsor Type III) studies. Solubility enhancements of PCE demonstrated that microemulsification is an order of magnitude more efficient than solubilization in the two media utilized (glass beads and alluvial sand). The kinetics of PCE elution during steady-state conditions were discussed via mass transfer rate coefficients (K{sub 1}); K{sub 1} values for surfactant systems are one to two orders of magnitude greater than those for water only (based on extra-micellar concentrations). Two distinct regions were observed for the transient portion of PCE elution; log-linear plots indicate a transition in mass transfer processes for surfactant-enhanced PCE dissolution.

  5. Analysis of nonylphenol and nonylphenol ethoxylates in sewage sludge by high performance liquid chromatography following microwave-assisted extraction.

    PubMed

    Fountoulakis, Michalis; Drillia, Panagiota; Pakou, Constantina; Kampioti, Adamantia; Stamatelatou, Katerina; Lyberatos, Gerasimos

    2005-09-30

    Nonylphenol polyethoxylates (NPnEOs) constitute a significant portion of the non-ionic surfactant market. The presence of nonylphenol (NP) in the aquatic environment is often a product of the microbial breakdown of NPEOs through discharge of industrial effluents and sewage treatment plants. The aim of this work is to develop the microwave-assisted extraction for the determination of the NP and NPEO in sewage sludge and compare this method with more traditional methods such as Soxhlet extraction and sonication. The method efficiency was evaluated as to the linearity, repeatability, accuracy, and sensitivity. Recoveries were 61.4% for NPEO and 91.4% for NP with repeatability less than 5%. The detection limit was 1.82 microg/g for NPEO and 2.86 microg/g for NP. The developed method was applied on sewage sludge samples from the sewage treatment plants of three Greek cities: Athens, Patras and Heraklion and were ranged 12.8-233.5 mg/kg for NPEO and 3.6-93 mg/kg for NP. PMID:16130770

  6. Grafted ionomer complexes and their effect on protein adsorption on silica and polysulfone surfaces

    PubMed Central

    de Keizer, Arie; Detrembleur, Christophe; Cohen Stuart, Martien A.; Norde, Willem

    2010-01-01

    We have studied the formation and the stability of ionomer complexes from grafted copolymers (GICs) in solution and the influence of GIC coatings on the adsorption of the proteins β-lactoglobulin (β-lac), bovine serum albumin (BSA), and lysozyme (Lsz) on silica and polysulfone. The GICs consist of the grafted copolymer PAA28-co-PAPEO22 {poly(acrylic acid)-co-poly[acrylate methoxy poly(ethylene oxide)]} with negatively charged AA and neutral APEO groups, and the positively charged homopolymers: P2MVPI43 [poly(N-methyl 2-vinyl pyridinium iodide)] and PAH∙HCl160 [poly(allylamine hydrochloride)]. In solution, these aggregates are characterized by means of dynamic and static light scattering. They appear to be assemblies with hydrodynamic radii of 8 nm (GIC-PAPEO22/P2MVPI43) and 22 nm (GIC-PAPEO22/PAH∙HCl160), respectively. The GICs partly disintegrate in solution at salt concentrations above 10 mM NaCl. Adsorption of GICs and proteins has been studied with fixed angle optical reflectometry at salt concentrations ranging from 1 to 50 mM NaCl. Adsorption of GICs results in high density PEO side chains on the surface. Higher densities were obtained for GICs consisting of PAH∙HCl160 (1.6 ÷ 1.9 chains/nm2) than of P2MVPI43 (0.6 ÷ 1.5 chains/nm2). Both GIC coatings strongly suppress adsorption of all proteins on silica (>90%); however, reduction of protein adsorption on polysulfone depends on the composition of the coating and the type of protein. We observed a moderate reduction of β-lac and Lsz adsorption (>60%). Adsorption of BSA on the GIC-PAPEO22/P2MVPI43 coating is moderately reduced, but on the GIC-PAPEO22/PAH∙HCl160 coating it is enhanced. PMID:21125002

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

    PubMed Central

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

    2009-01-01

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

  8. WETTABILITY AND PREDICTION OF OIL RECOVERY FROM RESERVOIRS DEVELOPED WITH MODERN DRILLING AND COMPLETION FLUIDS

    SciTech Connect

    Jill S. Buckley; Norman R. Morrow

    2004-05-01

    We report on progress in three areas. In part one, the wetting effects of synthetic base oils are reported. Part two reports progress in understanding the effects of surfactants of known chemical structures, and part three integrates the results from surface and core tests that show the wetting effects of commercial surfactant products used in synthetic and traditional oil-based drilling fluids. An important difference between synthetic and traditional oil-based muds (SBM and OBM, respectively) is the elimination of aromatics from the base oil to meet environmental regulations. The base oils used include dearomatized mineral oils, linear alpha-olefins, internal olefins, and esters. We show in part one that all of these materials except the esters can, at sufficiently high concentrations, destabilize asphaltenes. The effects of asphaltenes on wetting are in part related to their stability. Although asphaltenes have some tendency to adsorb on solid surfaces from a good solvent, that tendency can be much increased near the onset of asphaltene instability. Tests in Berea sandstone cores demonstrate wetting alteration toward less water-wet conditions that occurs when a crude oil is displaced by paraffinic and olefinic SBM base oils, whereas exposure to the ester products has little effect on wetting properties of the cores. Microscopic observations with atomic forces microscopy (AFM) and macroscopic contact angle measurements have been used in part 2 to explore the effects on wetting of mica surfaces using oil-soluble polyethoxylated amine surfactants with varying hydrocarbon chain lengths and extent of ethoxylation. In the absence of water, only weak adsorption occurs. Much stronger, pH-dependent adsorption was observed when water was present. Varying hydrocarbon chain length had little or no effect on adsorption, whereas varying extent of ethoxylation had a much more significant impact, reducing contact angles at nearly all conditions tested. Preequilibration of

  9. Synthesis of nonionic-anionic colloidal systems based on alkaline and ammonium β-nonylphenol polyethyleneoxy (n = 3-20) propionates/dodecylbenzenesulfonates with prospects for food hygiene

    PubMed Central

    2012-01-01

    Background The main objective of this work was to obtain a binary system of surface-active components (nonionic soap – alkaline and/or ammonium dodecylbenzenesulfonate) with potential competences in food hygiene, by accessing a scheme of classical reactions (cyanoethylation, total acid hydrolysis and stoichiometric neutralization with inorganic alkaline and/or organic ammonium bases) adapted to heterogeneously polyethoxylated nonylphenols (n = 3-20). In the processing system mentioned, dodecylbenzenesulfonic acid, initially the acid catalyst for the exhaustive hydrolysis of β-nonylphenolpolyethyleneoxy (n = 3-20) propionitriles, becomes together with the nonionic soap formed the second surface-active component of the binary system. Results In the reaction scheme adopted the influence of the main operating (duration, temperature, molar ratio of reagents) and structural parameters (degree of oligomerization of the polyoxyethylene chain) on the processing yields for the synthetic steps was followed. The favorable role of the polyoxyethylene chain size is remarked, through its specific conformation and its alkaline cations sequestration competences on the yields of cyanoethylation, but also the beneficial influence of phase-transfer catalysts in the total acid hydrolysis step. The chemical stability of dodecylbenzenesulfonic acid (DBSH) at the temperature and strongly acidic pH of the reaction environment is confirmed. The controlled change of the amount of DBSH in the final binary system will later confer it potential colloidal competences in food hygiene receipts. Conclusions The preliminary synthetic tests performed confirmed the prospect of obtaining a broad range of useful colloidal competences in various food hygiene scenarios. PMID:22958389

  10. In vitro effect of various xenobiotics on trout gill cell volume regulation after hypotonic shock.

    PubMed

    Leguen, I; Prunet, P

    2001-08-01

    Their functions and localisation can expose gill cells to volume changes. To maintain their vital functions, these gill cells must regulate their own volume after cellular swelling or shrinkage. Recently, we showed that rainbow trout pavement gill cells in primary culture have the capacity to regulate their own volume after cellular swelling induced by hypotonic shock. This so-called regulatory volume decrease (RVD) is associated with intracellular calcium increase, which occurs as a transient peak followed by a plateau when maintained a hypotonic condition. Return to an isotonic medium restores baseline [Ca2+]i level. In this study, the effect of different xenobiotics on cellular swelling induced RVD and its calcium signal was investigated in trout pavement gill cells in primary culture. These cells were exposed to different pollutants after confluent epithelium was obtained. After 36 h in xenobiotics exposure in vitro, cellular volume and intracellular calcium concentration were measured. Nonylphenol poly- and di-ethoxylate were lethal at concentrations of 10 and 100 microM, respectively. With 10 microM of the diethoxylate form, cells did not die but, unlike non-treated cells, burst during hypotonic shock (2/3rd strength Ringer solution). With 1 microM nonylphenol polyethoxylate (NPnEO), RVD and [Ca2+]i were reduced. Copper (10 and 100 microM) had no significant effect on gill cell volume regulation. However, the heavy metal modified calcium response to hypotonic shock by inhibiting return to baseline level under isotonic conditions. 10 microM prochloraz and 2,4-dichloroaniline had no effect on cell morphology, volume and [Ca2+]i concentration. With 100 microM, however, prochloraz was lethal and dichloroaniline increased baseline [Ca2+]i. These results indicate that the effects observed on gill cells are consistent with the known toxic properties of the molecules tested, thus confirming the validity of primary culture to investigate the toxic effects of

  11. Protolytic Equilibria of Sartans in Micellar Solutions of Differently Charged Surfactants.

    PubMed

    Grujić, Maja; Popović, Marija; Popović, Gordana; Nikolic, Katarina; Agbaba, Danica

    2016-08-01

    Protolytic equilibria of irbesartan, losartan, and valsartan have been investigated in the presence and absence of differently charged anionic (sodium dodecyl sulfate), cationic (cetyltrimethylammonium bromide), and nonionic (4-octylphenol polyethoxylate and polyoxyethylene (23) lauryl ether) surfactants. Ionization constants were determined by potentiometric titration at a constant ionic strength (0.1 M NaCl) and temperature 25°C. The effect of surfactants was estimated, based on a shift in apparent ionization constants (pKa(app)) determined in micellar solutions against the pKa(w) values in water. The anionic surfactant caused an increase in the pKa(app) values of sartans (up to 1.72 pK units), while the cationic surfactant had an opposite effect and caused a reduction in pKa(app) values (up to -1.44 pK units). These results point out to the fact that the ionizable groups of sartans are involved in electrostatic interactions with the charged surface of the ionic micelles. Shift in the pKa(app) values in the presence of nonionic surfactants (from -0.86 to +1.30) is a consequence of the interactions of drugs with the hydrophilic palisade layer. Significant changes in the distribution profiles of the equilibrium forms (from -44% to +80%) are observed at the biopharmaceutically important pH 4.5 value and can be considered in terms of the potential influence on intestinal absorption and bioavailability. PMID:27422089

  12. Anaerobic biodegradation of ether compounds by ether bond-cleaving bacteria and methanogenic consortia

    SciTech Connect

    Dwyer, D.F.

    1989-01-01

    Ether compounds are manufactured for use in nonionic detergents, plastics, pesticides and other products and occur as toxic organic compounds, the most famous being tetrachlorodibenzo-p-dioxin. Ether compounds were considered recalcitrant to anaerobic biodegradation due to the lack of an appropriate oxidant for ether bond-cleavage in reducing environments. Many of these compounds reside in anaerobic environments or are exposed to anaerobic waste treatment processes. Thus, it is of interest to identify: (i) whether ether compounds are anaerobically biodegradable, (ii) the anaerobic microorganisms able to degrade these compounds, and (iii) the mechanism(s) of anaerobic ether bond-cleavage. The ether bonds of polyethylene glycol (PEG; HO-(CH{sub 2}CH{sub 2}-O-){sub n}H), phenyl ether ((C{sub 6}H{sub 5}){sub 2}O), and dibenzo-p-dioxin ((C{sub 6}H{sub 4}){sub 2}O{sub 2}) were shown to be degraded in methanogenic consortia enriched with these compounds and polyethoxylate (nonionic) surfactants as substrates. Two anaerobic microorganisms which used PEGs as sole substrates were isolated and characterized. Desulfovibrio desulfuricans strain DG2 degraded the monomer ethylene glycol and oligomers up to tetraethylene glycol (HO-(CH{sub 2}CH{sub 2}-O-){sub 4}H) in length. Bacteroides sp. strain PG1 degraded diethylene glycol and all other polymer lengths of PEG. PEGs were degraded by Bacteroides sp. strain PG1 via an external depolymerization which was either a hydrolytic or a reductive cleavage of the ether bond. The ether bond of diaryl ethers was apparently cleaved by a reductive mechanism which produced benzene and phenol as products from phenyl ether degradation and benzene and, by indirect analysis, catechol from dibenzo-dioxin.

  13. Layered nanoemulsions as mucoadhesive buccal systems for controlled delivery of oral cancer therapeutics

    PubMed Central

    Gavin, Amy; Pham, Jimmy TH; Wang, Dawei; Brownlow, Bill; Elbayoumi, Tamer A

    2015-01-01

    Oral cavity and oropharyngeal cancers are considered the eighth most common cancer worldwide, with relatively poor prognosis (62% of patients surviving 5 years, after diagnosis). The aim of this study was to develop a proof-of-concept mucoadhesive lozenge/buccal tablet, as a potential platform for direct sustained delivery of therapeutic antimitotic nanomedicines. Our system would serve as an adjuvant therapy for oral cancer patients undergoing full-scale diagnostic and operative treatment plans. We utilized lipid-based nanocarriers, namely nanoemulsions (NEs), containing mixed-polyethoxylated emulsifiers and a tocopheryl moiety–enriched oil phase. Prototype NEs, loaded with the proapoptotic lipophilic drug genistein (Gen), were further processed into buccal tablet formulations. The chitosan polyelectrolyte solution overcoat rendered NE droplets cationic, by acting as a mucoadhesive interfacial NE layer. With approximate size of 110 nm, the positively charged chitosan-layered NE (+25 mV) vs negatively charged chitosan-free/primary aqueous NE (−28 mV) exhibited a controlled-release profile and effective mucoadhesion for liquid oral spray prototypes. When punch-pressed, porous NE-based buccal tablets were physically evaluated for hardness, friability, and swelling in addition to ex vivo tissue mucoadhesion force and retention time measurements. Chitosan-containing NE tablets were found equivalent to primary NE and placebo tablets in compression tests, yet significantly superior in all ex vivo adhesion and in vitro release assays (P≤0.05). Following biocompatibility screening of prototype chitosan-layered NEs, substantial anticancer activity of selected cationic Gen-loaded NE formulations, against two oropahryngeal carcinomas, was observed. The data strongly indicate the potential of such nanomucoadhesive systems as maintenance therapy for oral cancer patients awaiting surgical removal, or postresection of identified cancerous lesions. PMID:25759580

  14. Structures of ionic liquids dictate the conversion and selectivity of enzymatic glycerolysis: theoretical characterization by COSMO-RS.

    PubMed

    Chen, Biqiang; Guo, Zheng; Tan, Tianwei; Xu, Xuebing

    2008-01-01

    Lipase-catalyzed glycerolysis of triolein has been examined using a group of tetraammonium-based ionic liquids (ILs) as media, specifically with functional groups in cation part. The results demonstrated that the reaction evolution and profile specificity of respective IL system could be quantitatively associated with the structural characteristics of the IL by means of quantum chemical and COSMO-RS calculation. Misfit interaction, Van der Waals interaction and chemical potential, etc. derived from COSMO-RS calculation are shown to be effective measures to delineate multiple interactions of ILs and then can be used to understand the effects of ILs on reactions. The hydrophobic substituents in the cation are found to contribute to the increase of triolein solubility and enhancement of initial reaction rate; while strong polar anion and polyethoxyl and free hydroxyl groups in the cation part dictate improved product selectivity through reducing activity coefficients of monoglycerides. Integration of these structures into the same molecule constitutes a promising group of ILs that could produce over 90% monoglyceride with almost 100% triglyceride conversion, as well as bulky productivity, of particular potential for industrial applications. Overall, this work has presented a first attempt to characterize the IL structure-dependency of reaction specificity by associating structural variations of ILs with thermodynamic property changes of resided compounds and subsequent effects on reaction specificity. This might be of general value to help to understand the multiple solvation interaction among IL reaction systems at molecular level and promote the application of IL-mediated reactions to practical interests. PMID:17570709

  15. Effects of Fungicide and Adjuvant Sprays on Nesting Behavior in Two Managed Solitary Bees, Osmia lignaria and Megachile rotundata.

    PubMed

    Artz, Derek R; Pitts-Singer, Theresa L

    2015-01-01

    There is a growing body of empirical evidence showing that wild and managed bees are negatively impacted by various pesticides that are applied in agroecosystems around the world. The lethal and sublethal effects of two widely used fungicides and one adjuvant were assessed in cage studies in California on blue orchard bees, Osmia lignaria, and in cage studies in Utah on alfalfa leafcutting bees, Megachile rotundata. The fungicides tested were Rovral 4F (iprodione) and Pristine (mixture of pyraclostrobin + boscalid), and the adjuvant tested was N-90, a non-ionic wetting agent (90% polyethoxylated nonylphenol) added to certain tank mixtures of fungicides to improve the distribution and contact of sprays to plants. In separate trials, we erected screened cages and released 20 paint-marked females plus 30-50 males per cage to document the behavior of nesting bees under treated and control conditions. For all females in each cage, we recorded pollen-collecting trip times, nest substrate-collecting trip times (i.e., mud for O. lignaria and cut leaf pieces for M. rotundata), cell production rate, and the number of attempts each female made to enter her own or to enter other nest entrances upon returning from a foraging trip. No lethal effects of treatments were observed on adults, nor were there effects on time spent foraging for pollen and nest substrates and on cell production rate. However, Rovral 4F, Pristine, and N-90 disrupted the nest recognition abilities of O. lignaria females. Pristine, N-90, and Pristine + N-90 disrupted nest recognition ability of M. rotundata females. Electroantennogram responses of antennae of O. lignaria females maintained in the laboratory did not differ significantly between the fungicide-exposed and control bees. Our results provide the first empirical evidence that two commonly used fungicides and a non-ionic adjuvant can disrupt nest recognition in two managed solitary bee species. PMID:26274401

  16. Development and evaluation of tocopherol-rich argan oil-based nanoemulsions as vehicles possessing anticancer activity.

    PubMed

    Jordan, Melanie; Nayel, Amy; Brownlow, Bill; Elbayoumi, Tamer

    2012-12-01

    In recent years, diverse nanoemulsion vehicles (NEs) have been developed with vast potential for improving therapeutic index of clinically approved and experimental drugs. Using oils rich in omega-3 and omega-6 polyunsaturated fatty acids (PUFA), several promising nanoemulsion formulations have been developed recently for oral and systemic administration. The aim of our present work is to successfully develop and characterize optimized nanoemulsion platform, using the PUFA-rich argan oil that contain several important anti-inflammatory and antimitotic natural components. Using various emulsifying mixtures of polyethoxylated solutol HS-15 and polyethyleneglucol Vitamin E succinyl ester (TPGS), to form different NEs showing extended shelf-life stability. The physicochemical properties of prototype argan NEs were analyzed and utilizing a 32 full factorial design, followed by biocompatibility screen, using normal vascular myocytes and areolar fibroblasts. While 90-180 day stability of NEs correlated with TPGS:solutol surfactant blend ratios, adverse effects on integrity of test cultures were only noted at high TPGS content in the emulsifier system, exceeding 80%. Finally, the anti-proliferative efficacy of selected stable and acceptably biocompatible nanoscale TPGS-emulsified argan oil formulations was investigated using murine breast and colon carcinoma cells. The IC50 values of the combination of argan oil and TPGS (40-80% wt of emulsifiers) were 5-9 folds lower compared to TPGS-free and argan-oil free control NEs. Argan oil NE, stabilized with Vitamin E TPGS and solutol HS mixtures, demonstrated significant pro-apoptotic effect on both test cancer cell lines, indicating built-in anticancer properties for such NE platform, potentially enhancing overall antineoplastic effects of incorporated candidate chemotherapeutic agents. PMID:23030003

  17. Effects of Fungicide and Adjuvant Sprays on Nesting Behavior in Two Managed Solitary Bees, Osmia lignaria and Megachile rotundata

    PubMed Central

    2015-01-01

    There is a growing body of empirical evidence showing that wild and managed bees are negatively impacted by various pesticides that are applied in agroecosystems around the world. The lethal and sublethal effects of two widely used fungicides and one adjuvant were assessed in cage studies in California on blue orchard bees, Osmia lignaria, and in cage studies in Utah on alfalfa leafcutting bees, Megachile rotundata. The fungicides tested were Rovral 4F (iprodione) and Pristine (mixture of pyraclostrobin + boscalid), and the adjuvant tested was N-90, a non-ionic wetting agent (90% polyethoxylated nonylphenol) added to certain tank mixtures of fungicides to improve the distribution and contact of sprays to plants. In separate trials, we erected screened cages and released 20 paint-marked females plus 30–50 males per cage to document the behavior of nesting bees under treated and control conditions. For all females in each cage, we recorded pollen-collecting trip times, nest substrate-collecting trip times (i.e., mud for O. lignaria and cut leaf pieces for M. rotundata), cell production rate, and the number of attempts each female made to enter her own or to enter other nest entrances upon returning from a foraging trip. No lethal effects of treatments were observed on adults, nor were there effects on time spent foraging for pollen and nest substrates and on cell production rate. However, Rovral 4F, Pristine, and N-90 disrupted the nest recognition abilities of O. lignaria females. Pristine, N-90, and Pristine + N-90 disrupted nest recognition ability of M. rotundata females. Electroantennogram responses of antennae of O. lignaria females maintained in the laboratory did not differ significantly between the fungicide-exposed and control bees. Our results provide the first empirical evidence that two commonly used fungicides and a non-ionic adjuvant can disrupt nest recognition in two managed solitary bee species. PMID:26274401

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

    PubMed

    Iqbal, Munawar; Bhatti, Ijaz Ahmad

    2015-12-15

    Gamma radiation/H2O2 treatment of nonylphenol polyethoxylates (NPEO) was performed and treatment effect was evaluated on the basis of degradation, chemical oxygen demand (COD) and total organic carbon (TOC), and toxicity reduction efficiencies. The radiolytic by-products were determined by Fourier Transform Infrared Spectroscopy (FTIR), High-Performance Liquid Chromatography (HPLC), and Gas Chromatography-Mass Spectrometry (GC-MS) techniques. Low mass carboxylic acids, aldehyde, ketone, and acetic acid were identified as the by-products of the NPEO degradation. NPEO sample irradiated to the absorbed dose of 15 kGy/4.58% H2O2 showed more than 90% degradation. Allium cepa (A. cepa), brine shrimp, heamolytic tests were used for cytotoxicity study, while mutagenicity was evaluated through Ames test (TA98 and TA100 strains) of treated and un-treated NPEO. The reductions in COD and TOC were greater than 70% and 50%, respectively. Gamma radiation/H2O2 treatment revealed a considerable reduction in cytotoxicity and mutagenicity. A. cepa, heamolytic and shrimp assays showed cytotoxicity reduction up to 68.65%, 77%, and 94%, respectively. The mutagenicity reduced up to 62%, 74%, and 79% (TA98) and 68%, 78%, and 82% (TA100), respectively of NPEO-6, NPEO-9, and NPEO-30 irradiated to the absorbed dose of 15 kGy/4.58% H2O2. NPEO-6 detoxified more efficiently versus NPEO-9 and NPEO-30 and results showed that Gamma radiation/H2O2 treatment has the potential to mineralize and detoxify NPEO. PMID:26143198

  19. Distrubution of the Endocrine Disruptor Nonylphenol and the Effects of Topographical Sheilding in an Eastern Sierra Nevada Mountain Drainage

    NASA Astrophysics Data System (ADS)

    Lyons, R. A.; Van de Bittner, K.; Morgan Jones, S.

    2013-12-01

    Nonylphenol is a biodegradation product of nonylphenol polyethoxylates, a pervasive compound used in many industrial processes and notably in pesticides as a surfactant. Nonylphenol has been shown to act as an endocrine disruptor at low concentrations. It causes hermaphrodism, birth defects, and high mortality in fish, frogs and other amphibians. The Sierra Nevada Mountains separate the Central Valley in the west from the high desert of Mono Country on the east side of the state of California. The Central Valley represents some of the most heavily cultivated agricultural land in the United States. San Joaquin County alone had an annual pesticide use of over 8 million pounds in 2009 according to the Pesticide Action Network, compared with 4800 pounds in Mono County the same year. Fragile alpine ecosystems in the Sierra Nevadas may be highly susceptible to the effects of endocrine disruptors like nonylphenol. The distribution of nonylphenol is affected by localized topography in a steep walled montane canyon in the Eastern Sierra Nevada Mountains, Convict Creek canyon. The concentration of nonylphenol in snow and surface water increases as the elevation in Convict Creek canyon decreases in an easterly direction from not detectable at the highest elevations to as much as .01mg/L in water and 1.8 mg/L in snow at the lowest elevations. The steep head wall of Convict Creek canyon, facing southeast, provides shielding to the higher elevation lakes from deposition of compounds and particulate matter. As a canyon becomes less steep and broader, more nonylphenol is deposited. Identifying these deposition patterns may assist in determining amphibian and fish populations that are at higher risk of negative impact from these compounds.

  20. 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

  1. Self-assembled nanoparticles of cholesterol-modified O-carboxymethyl chitosan as a novel carrier for paclitaxel

    NASA Astrophysics Data System (ADS)

    Wang, Yin-song; Jiang, Qian; Li, Rong-shan; Liu, Ling-long; Zhang, Qi-qing; Wang, Yu-mei; Zhao, Jing

    2008-04-01

    Self-assembled nanoparticles of cholesterol-modified O-carboxymethyl chitosan (CCMC) were prepared to be used as a novel carrier for paclitaxel (PTX) in this study. CCMC-6.9 was synthesized by the covalent conjugation of cholesterol to O-carboxymethyl chitosan with the succinyl linkage and the degree of substitution (DS) of the cholesterol moiety was 6.9%. CCMC-6.9 formed self-assembled nanoparticles with a size of 209.5 nm in aqueous media. Paclitaxel-loaded CCMC-6.9 self-assembled nanoparticles were prepared using a dialysis method and their characteristics were analyzed by dynamic laser light scattering (LLS), transmission electron microscopy (TEM) and ultraviolet spectroscopy (UV). PTX-loaded CCMC-6.9 self-assembled nanoparticles were almost spherical in shape and their size increased from 245.6 to 355.3 nm with PTX-loading content increasing from 18.7% to 34.9%. In vitro release of PTX from CCMC-6.9 self-assembled nanoparticles was carried out by the dynamic dialysis method. PTX continuously released in phosphate buffered saline (PBS) solutions for 84 h at 37 °C and its release was sensitive to the pH of the release media. The biodistribution of PTX-loaded CCMC-6.9 self-assembled nanoparticles was studied in female Balb/c mice. Compared with PTX in the solution of Cremophor EL (polyethoxylated castor oil)/ethanol (PTX-Cre), CCMC-6.9 self-assembled nanoparticles significantly increased the uptake of PTX in plasma, liver and spleen, but decreased the uptake in heart and kidney. These results suggest that CCMC-6.9 self-assembled nanoparticles can effectively solubilize PTX and modify its tissue biodistribution, which may be advantageous in enhancing the therapeutic index and reducing the toxicity of PTX.

  2. Response of graywater recycling systems based on hydroponic plant growth to three classes of surfactants

    NASA Technical Reports Server (NTRS)

    Garland, J. L.; Levine, L. H.; Yorio, N. C.; Hummerick, M. E.

    2004-01-01

    Anionic (sodium laureth sulfate, SLES), amphoteric (cocamidopropyl betaine, CAPB) and nonionic (alcohol polyethoxylate, AE) surfactants were added to separate nutrient film technique (NFT) hydroponic systems containing dwarf wheat (Triticum aestivum cv. USU Apogee) in a series of 21 day trials. Surfactant was added either in a (1). temporally dynamic mode (1-3 g surfactant m(-2) growing area d(-1)) as effected by automatic addition of a 300 ppm surfactant solution to meet plant water demand, or (2). continuous mode (2 g surfactant m(-2) growing area d(-1)) as effected by slow addition (10 mLh(-1)) of a 2000 ppm surfactant solution beginning at 4d after planting. SLES showed rapid primary degradation in both experiments, with no accumulation 24 h after initial addition. CAPB and AE were degraded less rapidly, with 30-50% remaining 24 h after initial addition, but CAPB and AE levels were below detection limit for the remainder of the study. No reductions in vegetative growth of wheat were observed in response to SLES, but biomass was reduced 20-25% with CAPB and AE. Microbial communities associated with both the plant roots and wetted hardware surfaces actively degraded the surfactants, as determined by monitoring surfactant levels following pulse additions at day 20 (with plants) and day 21 (after plant removal). In order to test whether the biofilm communities could ameliorate phytotoxicity by providing a microbial community acclimated for CAPB and AE decay, the continuous exposure systems were planted with wheat seeds after crop removal at day 21. Acclimation resulted in faster primary degradation (>90% within 24h) and reduced phytotoxicity. Overall, the studies indicate that relatively small areas (3-5m(2)) of hydroponic plant systems can process per capita production of mixed surfactants (5-10 g x person(-1)d(-1)) with minimal effects on plant growth.

  3. Response of graywater recycling systems based on hydroponic plant growth to three classes of surfactants.

    PubMed

    Garland, J L; Levine, L H; Yorio, N C; Hummerick, M E

    2004-04-01

    Anionic (sodium laureth sulfate, SLES), amphoteric (cocamidopropyl betaine, CAPB) and nonionic (alcohol polyethoxylate, AE) surfactants were added to separate nutrient film technique (NFT) hydroponic systems containing dwarf wheat (Triticum aestivum cv. USU Apogee) in a series of 21 day trials. Surfactant was added either in a (1). temporally dynamic mode (1-3 g surfactant m(-2) growing area d(-1)) as effected by automatic addition of a 300 ppm surfactant solution to meet plant water demand, or (2). continuous mode (2 g surfactant m(-2) growing area d(-1)) as effected by slow addition (10 mLh(-1)) of a 2000 ppm surfactant solution beginning at 4d after planting. SLES showed rapid primary degradation in both experiments, with no accumulation 24 h after initial addition. CAPB and AE were degraded less rapidly, with 30-50% remaining 24 h after initial addition, but CAPB and AE levels were below detection limit for the remainder of the study. No reductions in vegetative growth of wheat were observed in response to SLES, but biomass was reduced 20-25% with CAPB and AE. Microbial communities associated with both the plant roots and wetted hardware surfaces actively degraded the surfactants, as determined by monitoring surfactant levels following pulse additions at day 20 (with plants) and day 21 (after plant removal). In order to test whether the biofilm communities could ameliorate phytotoxicity by providing a microbial community acclimated for CAPB and AE decay, the continuous exposure systems were planted with wheat seeds after crop removal at day 21. Acclimation resulted in faster primary degradation (>90% within 24h) and reduced phytotoxicity. Overall, the studies indicate that relatively small areas (3-5m(2)) of hydroponic plant systems can process per capita production of mixed surfactants (5-10 g x person(-1)d(-1)) with minimal effects on plant growth. PMID:15087176

  4. Transport and retention of fullerene (C60) nanoparticles in natural soils

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Li, Y.; Abriola, L. M.; Pennell, K. D.

    2008-12-01

    Although several column studies have investigated the transport and deposition of fullerene (C60) nanoparticles in ideal porous media, such as washed quartz sands and glass beads, far less attention has been directed toward natural soils. To address this issue, a series of column experiments was performed to quantify the transport and retention of C60 nanoparticles in a borosilicate glass column (10 cm length x 2.5 cm dia.) packed with either Appling soil or Webster soil. Introduction of a C60 suspension containing 1 mM calcium chloride as background electrolyte for up to 65 pore volumes resulted in 100 percent retention of injected mass. Retained C60 nanoparticles were concentrated within 6 cm of the column from inlet, with solid phase concentrations approaching 130 μg/g. The presence of Suwannee River humic acid (20 mg/L) in the C60 suspension slightly enhanced mobility of nC60, although effluent breakthrough was not observed. However, when mixed with 1,000 mg/L polyethoxylate (20) sorbitan monooleate (Tween 80), C60 nanoparticles were readily transported through Appling soil, with less than 40 percent of injected mass retained. Retentions profiles of nC60 exhibited gradual ascent and descent, but not symmetrically, with distance from inlet. A mathematic transport model incorporating classical filtration theory, non-linear sorption process, and straining was utilized to capture C60 effluent breakthrough curves and retention profiles observed in the column experiments. These findings indicate that Appling soil and Webster soil exhibit large retention capacity for C60 nanoparticle, and that transport of C60 is greatly enhanced in the presence of stabilizing agents.

  5. Determination of nonylphenol isomers in landfill leachate and municipal wastewater using steam distillation extraction coupled with comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry

    USGS Publications Warehouse

    Zhang, Caixiang; Eganhouse, Robert P.; Pontolillo, James; Cozzarelli, Isabelle M.; Wang, Yanxin

    2012-01-01

    4-Nonylphenols (4-NPs) are known endocrine disruptors and by-products of the microbial degradation of nonylphenol polyethoxylate surfactants. One of the challenges to understanding the toxic effects of nonylphenols is the large number of isomers that may exist in environmental samples. In order to attribute toxic effects to specific compounds, a method is needed for the separation and quantitation of individual nonylphenol isomers. The pre-concentration methods of solvent sublimation, solid-phase extraction or liquid–liquid extraction prior to chromatographic analysis can be problematic because of co-extraction of thousands of compounds typically found in complex matrices such as municipal wastewater or landfill leachate. In the present study, steam distillation extraction (SDE) was found to be an effective pre-concentration method for extraction of 4-NPs from leachate and wastewater, and comprehensive two-dimensional gas chromatography (GC × GC) coupled with fast mass spectral data acquisition by time-of-flight mass spectrometry (ToFMS) enhanced the resolution and identification of 4-NP isomers. Concentrations of eight 4-NP isomers were determined in leachate from landfill cells of different age and wastewater influent and effluent samples. 4-NP isomers were about 3 times more abundant in leachate from the younger cell than the older one, whereas concentrations in wastewater effluent were either below detection limits or <1% of influent concentrations. 4-NP isomer distribution patterns were found to have been altered following release to the environment. This is believed to reflect isomer-specific degradation and accumulation of 4-NPs in the aquatic environment.

  6. The effects of 4-nonylphenol in rats: a multigeneration reproduction study.

    PubMed

    Chapin, R E; Delaney, J; Wang, Y; Lanning, L; Davis, B; Collins, B; Mintz, N; Wolfe, G

    1999-11-01

    The alkylphenol breakdown products of alkylphenol ethoxylates have been shown in in vitro studies to be weakly estrogenic, but few in vivo data address this issue in mammals. Because estrogens have been found to be most potent during developmental/perinatal exposures, this study maximized developmental exposure to nonylphenol (NP) by treating 3.5 generations of Sprague-Dawley rats to NP in diet at 200, 650, and 2000 ppm to determine the range and severity of any toxicity. Dose rate was higher for younger rats; calculated dose ranges were 9-35, 30-100, and 100-350 mg/kg/d for the low (200NP), middle (650NP), and high (2000NP) dose groups, respectively. There were adult (F0, F1, F2) and postnatal day (pnd) 21 (F1, F2, F3) necropsies; the oldest F3 rats were killed on pnd 55-58. Body weight gain was reduced by 8-10% in the 650NP and 2000NP groups. Vaginal opening was accelerated by approximately 2 days (650NP) and approximately 6 days (2000NP) in F1, F2, and F3 generations. Uterine weights at pnd 21 were increased in 650NP (14%) and 2000NP (50%) F1 females, but not in other generations. Testis descent, anogenital distance, and preputial separation were not consistently changed. No consistent changes were seen in pup number, weight or viability, litter indices, or other functional reproductive measures. Relative ovary weight in F2 adults was decreased at 650NP and 2000NP by 12%; relative ovary was unchanged in other generations. Follicle counts were unchanged in F2 adults. Sperm indices, including CASA measures, were unchanged in F0 and F1 males. In F2 rats, epididymal sperm density was reduced by 8% and 13% at 650NP and 2000NP, respectively. Testicular spermatid count was reduced by 13% in 2000NP F2 males; testis and epididymis weights were unchanged. Erosion of gastric and duodenal mucosa was monitored grossly and microscopically, and never found. Kidney weights were increased in 650NP and 2000NP males, and renal medullary tubular dilatation and cyst formation were

  7. 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

  8. Occurrence of endocrine-disrupting phenols and estrogens in water and sediment of the Songhua river, northeastern China.

    PubMed

    Zhang, Zifeng; Ren, Nanqi; Kannan, Kurunthachalam; Nan, Jun; Liu, Liyan; Ma, Wanli; Qi, Hong; Li, Yifan

    2014-04-01

    Concentrations of six phenolic endocrine-disrupting chemicals [4-tert-octylphenol (OP), 4-t-nonylphenol (4-t-NP), 4-n-nonylphenol (4-n-NP), nonylphenol mono- to di-ethoxylates (NP1EO, NP2EO), and bisphenol A (BPA)] and five estrogens [estrone (E1), β-estradiol (E2), estriol (E3) 17α-ethynylestradiol (EE2), and diethylstilbestrol (DES)] were determined in surface water and sediment samples collected from the Songhua River in northeast China. Concentrations of sum of five alkylphenols and alkylphenol ethoxylates (ΣOP, 4-n-NP, 4-t-NP, NP1EO, NP2EO) were 117-1,030 ng L(-1) (mean 296) in water samples and 25.5-386 ng g(-1) (mean 67.3 ng g(-1) dry weight (dw)) in sediments. Concentrations of BPA in water and sediments were 8.24-263 ng L(-1) (mean 52.0) and 1.60-17.3 ng g(-1) dw (mean 4.90 dw), respectively. Concentrations in water were 0.840-20.8 ng L(-1) (mean 5.03) for the sum of three natural steroidal estrogens (ΣE1, E2, E3) and below detection limit (BDL) at -1.38 ng L(-1) (average 0.200) for the sum of two synthetic estrogens (EE2, ΣDES). Among estrogens, only E1 was detected in all of the sediment samples in the range of 0.100-3.00 ng g(-1) dw. Concentrations of Σphenolic EDCs and Σestrogens in water and sediments and their correlations with total organic carbon indicated that these contaminants originate from similar sources, such as municipal wastewater. In situ [Formula: see text] values and sediment-water fugacity fraction were calculated for the target chemicals, and the results indicated that these chemicals were, in general, supersaturated in sediments relative to those in water. PMID:24468970

  9. 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

  10. 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

  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. PMID:26986763

  12. 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. PMID:26507734

  13. Occurrence of halogenated transformation products of selected pharmaceuticals and personal care products in secondary and tertiary treated wastewaters from southern California.

    PubMed

    Bulloch, Daryl N; Nelson, Eric D; Carr, Steve A; Wissman, Chris R; Armstrong, Jeffrey L; Schlenk, Daniel; Larive, Cynthia K

    2015-02-17

    Final effluent samples from 10 southern California (United States) wastewater treatment facilities, employing four distinct treatment schemes, were surveyed for selected pharmaceuticals, personal care products (PPCPs), alkylphenols, and 21 of their halogenated disinfection byproducts. Chlorinated and brominated standards and isotopically labeled internal standards were synthesized and purified to confirm and more accurately quantify selected disinfection byproducts of salicylic acid, bisphenol A, gemfibrozil, naproxen, diclofenac, technical 4-nonylphenol, and 4-tert-octylphenol using high-performance liquid chromatography and tandem mass spectrometry. Concentrations of parent compounds ranged from <10 to 3830 ng/L (gemfibrozil), and those of chloro/bromo byproducts ranged from <4 to 370 ng/L (dibromo nonylphenol). The highest concentrations of parent compounds were measured in effluent that was not subjected to tertiary treatment. The chlorinated and brominated byproduct concentration may be affected by the influent concentration of parent compounds, hydraulic retention times, and chlorine contact times. Salicylic acid was readily halogenated, which is evident from the ratio of halogenated to nonhalogenated species. There were no measured chlorinated byproducts of bisphenol A despite occasionally high concentrations of the parent compound. Not surprisingly, higher concentrations of most brominated species were measured in the treatment plant with the highest bromide concentrations. These results demonstrate the occurrence of novel halogenated byproducts of PPCPs that have limited toxicological data and significant uncertainty with regard to their risk to ecological systems. PMID:25611547

  14. 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. PMID:25546459

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

    USGS Publications Warehouse

    Bradley, Paul M.; Journey, Celeste A.

    2014-01-01

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

  16. 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. PMID:27312331

  17. 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. PMID:20970168

  18. Binding of Estrogenic Compounds to Recombinant Estrogen Receptor-α: Application to Environmental Analysis

    PubMed Central

    Pillon, Arnaud; Boussioux, Anne-Marie; Escande, Aurélie; Aït-Aïssa, Sélim; Gomez, Elena; Fenet, Hélène; Ruff, Marc; Moras, Dino; Vignon, Françoise; Duchesne, Marie-Josèphe; Casellas, Claude; Nicolas, Jean-Claude; Balaguer, Patrick

    2005-01-01

    Estrogenic activity in environmental samples could be mediated through a wide variety of compounds and by various mechanisms. High-affinity compounds for estrogen receptors (ERs), such as natural or synthetic estrogens, as well as low-affinity compounds such as alkylphenols, phthalates, and polychlorinated biphenyls are present in water and sediment samples. Furthermore, compounds such as polycyclic aromatic hydrocarbons, which do not bind ERs, modulate estrogen activity by means of the aryl hydrocarbon receptor (AhR). In order to characterize compounds that mediate estrogenic activity in river water and sediment samples, we developed a tool based on the ER-αligand-binding domain, which permitted us to estimate contaminating estrogenic compound affinities. We designed a simple transactivation assay in which compounds of high affinity were captured by limited amounts of recombinant ER-αand whose capture led to a selective inhibition of transactivation. This approach allowed us to bring to light that water samples contain estrogenic compounds that display a high affinity for ERs but are present at low concentrations. In sediment samples, on the contrary, we showed that estrogenic compounds possess a low affinity and are present at high concentration. Finally, we used immobilized recombinant ER-αto separate ligands for ER and AhR that are present in river sediments. Immobilized ER-α, which does not retain dioxin-like compounds, enabled us to isolate and concentrate ER ligands to facilitate their further analysis. PMID:15743715

  19. 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. PMID:22777343

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

    PubMed

    Bolling, Bradley W; Chen, C-Y Oliver; McKay, Diane L; Blumberg, Jeffrey B

    2011-12-01

    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 are not. The phytochemical content of tree nuts can vary considerably by nut type, genotype, pre- and post-harvest conditions, as well as storage conditions. Genotype affects phenolic acids, flavonoids, stilbenes and phytosterols, but data are lacking for many other phytochemical classes. During the roasting process, tree nut isoflavones, flavanols and flavonols were found to be more resistant to heat than the anthocyanins, PAC and trans-resveratrol. The choice of solvents used for extracting polyphenols and phytosterols significantly affects their quantification, and studies validating these methods for tree nut phytochemicals are lacking. The phytochemicals found in tree nuts have been associated with antioxidant, anti-inflammatory, anti-proliferative, antiviral, chemopreventive and hypocholesterolaemic actions, all of which are known to affect the initiation and progression of several pathogenic processes. While tree nut phytochemicals are bioaccessible and bioavailable in humans, the number of intervention trials conducted to date is limited. The objectives of the present review are to summarise tree nut: (1) phytochemicals; (2) phytochemical content included in nutrient databases and current publications; (3) phytochemicals affected by pre- and post-harvest conditions and analytical methodology; and (4) bioactivity and health benefits in humans. PMID:22153059

  1. 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.

  2. Development and validation of a GC-MS method for the evaluation of 17 endocrine disruptor compounds, including phytoestrogens and sitosterol, in coastal waters - their spatial and seasonal levels in Porto costal region (Portugal).

    PubMed

    Rocha, Maria João; Cruzeiro, Catarina; Rocha, Eduardo

    2013-06-01

    A gas chromatography with mass spectrometric detection (GC-MS) method was developed and optimized for the determination of 17 endocrine disrupting compounds (EDCs) in coastal water samples. The evaluated EDCs were from different origins and included estrogens, bisphenol A, alkylphenolethoxylates, alkylphenols, phytoestrogens and sitosterol (SITO). The EDCs were extracted from samples using Oasis HLB (Hydrophilic-Lipophilic Balance) cartridges and derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) added with 1% trimethylchlorosilane (TMCS). The validation parameters revealed that this method was highly specific for all assayed compounds (>99%) and the linearity of the calibration curves showed a correlation higher than 0.99. The detection limits were at low ng/L level and the recovery rates were higher than 70%. The performance of the method was checked using coastal water samples taken every 2 months during 2009-2010 from the Douro River estuary and the Porto coastline (Portugal). These data revealed that approximately 98.0% of the analyzed compounds showed levels above their limits of detection (LODs). The measured estrogens (2-20 ng/L) and industrial pollutants (up to 1.1 μg/L) were in biologic hazardous concentrations. Besides, a clear seasonal pattern of fluctuation was established for phytoestrogens and SITO. The physicochemical data, namely the amounts of nitrates, nitrites and phosphorous, confirmed the low water quality of this area. PMID:23708576

  3. Methods development for separation of inorganic anions, organic acids and bases, and neutral organic compounds by ion chromatography and capillary electrophoresis

    SciTech Connect

    Li, J.

    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.

  4. Biodegradation of naphthalene in aqueous nonionic surfactant systems.

    PubMed Central

    Liu, Z; Jacobson, A M; Luthy, R G

    1995-01-01

    The principal objective of this study was to quantify the bioavailability of micelle-solubilized naphthalene to naphthalene-degrading microorganisms comprising a mixed population isolated from contaminated waste and soils. Two nonionic surfactants were used, an alkylethoxylate, Brij 30 (C12E4), and an alkylphenol ethoxylate, Triton X-100 (C8PE9.5). Batch experiments were used to evaluate the effects of aqueous, micellized nonionic surfactants on the microbial mineralization of naphthalene and salicylic acid, an intermediate compound formed in the pathway of microbial degradation of naphthalene. The extent of solubilization and biodegradation under aerobic conditions was monitored by radiotracer and spectrophotometric techniques. Experimental results showed that surfactant concentrations above the critical micelle concentration were not toxic to the naphthalene-degrading bacteria and that the presence of surfactant micelles did not inhibit mineralization of naphthalene. Naphthalene solubilized by micelles of Brij 30 or Triton X-100 in liquid media was bioavailable and degradable by the mixed culture of bacteria. PMID:7887597

  5. Oxidation of nonionic detergents by cytochrome P450 enzymes.

    PubMed

    Hosea, N A; Guengerich, F P

    1998-05-15

    Nonionic phenolic detergents are commonly used in the purification of membrane-associated proteins. Triton N-101 was shown to be oxidized by NADPH-fortified human liver microsomes and recombinant human cytochromes P450 (P450). Oxidation was monitored using HPLC and the fluorescence properties of Triton N-101 and other alkylphenol ethoxylate detergents, which are similar to those of anisole. Human liver microsomes and recombinantly expressed reconstituted P450 3A4-oxidized Triton N-101 in a concentration-dependent manner which could be inhibited by ketoconazole, a P450 3A4-selective inhibitor. Triton N-101 inhibition of testosterone oxidation by human liver microsomes was of a mixed nature but mainly non-competitive. Electrospray ionization mass spectrometry and tandem mass spectrometry indicated that the major product formed was hydroxylated on the alkyl moiety. Human liver microsomes also oxidized other Tritons (X-100 and X-114), Emulgens 911 and 913, and Tergitol NP-10 to a similar extent. P450s 1A1, 1A2, and 2C9 also oxidized Triton N-101 but to a lesser extent than P450 3A4. We conclude that Triton N-101 and similar nonionic detergents are oxidized by P450 3A4 and some other P450s. PMID:9606971

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Impact of environmental chemicals on the thyroid hormone function in pituitary rat GH3 cells.

    PubMed

    Ghisari, Mandana; Bonefeld-Jorgensen, Eva C

    2005-12-01

    Endocrine disrupting chemicals (EDCs) are widespread in the environment and suspected to interfere with the function of thyroid hormones (THs). We investigated the TH disrupting activity of different classes of EDCs including plasticizers (bisphenol A, bisphenol A dimethacrylate), alkylphenols (4-n-nonylphenol, 4-octylphenol), pesticides (prochloraz, iprodion, chlorpyrifos), PCB metabolites (OH-PCB 106, OH-PCB 121, OH-PCB 69) and brominated flame-retardants (tetrabromobisphenol A). The ED potential of a chemical was determined by its effect on the cell proliferation of TH-dependent rat pituitary GH3 cell line. All tested chemicals significantly interfered with the cell proliferation alone or upon co-treatment with T3. The growth of GH3 cells was stimulated by all tested chemicals, but 4-n-nonylphenol, 4-octylphenol, prochloraz and iprodion elicited an inhibitory effect on cell growth. In conclusion, these EDCs have the potential to exert TH disruption increasing the risk or a negative impact on fetal brain development, resulting in cognitive dysfunctions. PMID:16221524

  11. Rapid crystallization and morphological adjustment of zeolite ZSM-5 in nonionic emulsions

    SciTech Connect

    Zhang Ying; Jin Chao

    2011-01-15

    Zeolite ZSM-5 was synthesized for the first time in a nonionic emulsion composed of polyoxyethylated alkylphenol, butanol, cyclohexane and tetraethylammonium hydroxide (TEAOH)-containing zeolite synthesis mixture. The crystallization kinetics in the emulsion was investigated and the ZSM-5 product was characterized in detail by XRD, SEM, FT-IR, TG, N{sub 2} adsorption and CHN analysis techniques. Compared with the conventionally hydrothermal synthesis with the same structure directing agent TEAOH, the emulsion system allows rapid crystallization of ZSM-5. The ZSM-5 product exhibits unusual agglomerated structure and possesses larger specific surface area. The FT-IR, TG results plus CHN analysis show the encapsulation of a trace of emulsion components in the emulsion ZSM-5. Control experiments show the emulsion system exerts the crystallization induction and morphological adjustment effects mainly during the aging period. The effects are tentatively attributed to the confined space domains, surfactant-water interaction as well as surfactant-growing crystals interaction existing in the emulsion. -- Graphical abstract: The nonionic emulsion synthesis allows rapid crystallization and morphological adjustment of zeolite ZSM-5 compared with the conventional hydrothermal synthesis. Display Omitted

  12. 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.

  13. 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. PMID:12939494

  14. 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. PMID:24629940

  15. 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. PMID:25648473

  16. 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. PMID:24119441

  17. 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. PMID:24754392

  18. 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. PMID:20338632

  19. Occurrence and fate of relevant substances in wastewater treatment plants regarding Water Framework Directive and future legislations.

    PubMed

    Martin Ruel, S; Choubert, J-M; Budzinski, H; Miège, C; Esperanza, M; Coquery, M

    2012-01-01

    The next challenge of wastewater treatment is to reliably remove micropollutants at the microgram per litre range. During the present work more than 100 substances were analysed through on-site mass balances over 19 municipal wastewater treatment lines. The most relevant substances according to their occurrence in raw wastewater, in treated wastewater and in sludge were identified, and their fate in wastewater treatment processes was assessed. About half of priority substances of WFD were found at concentrations higher than 0.1 μg/L in wastewater. For 26 substances, potential non-compliance with Environmental Quality Standard of Water Framework Directive has been identified in treated wastewater, depending on river flow. Main concerns are for Cd, DEHP, diuron, alkylphenols, and chloroform. Emerging substances of particular concern are by-products, organic chemicals (e.g. triclosan, benzothiazole) and pharmaceuticals (e.g. ketoprofen, diclofenac, sulfamethoxazole, carbamazepine). About 80% of the load of micropollutants was removed by conventional activated sludge plants, but about two-thirds of removed substances were mainly transferred to sludge. PMID:22437014

  20. 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. PMID:22643422

  1. 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. PMID:24888621

  2. 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. PMID:26378656

  3. A confirmatory method for the determination of phenolic endocrine disruptors in honey using restricted-access material-liquid chromatography-tandem mass spectrometry.

    PubMed

    Rodríguez-Gonzalo, E; García-Gómez, D; Carabias-Martínez, R

    2010-10-01

    The present work describes the development and validation of an analytical method based on liquid chromatography (LC), coupled with tandem mass spectrometry (MS/MS) that allows the determination and confirmation of several endocrine-disrupting chemicals (EDCs) in honey. The EDCs studied were nine phenols of different nature: chlorophenols (2,4-dichlorophenol, 2,4,5-trichlorophenol, and pentachlorophenol), alkylphenols (4-tert-butylphenol, 4-tert-octylphenol, and 4-n-octylphenol) bisphenols (bisphenol-A and bisphenol-F), and 4-tert-butylbenzoic acid. The method incorporates a restricted-access material (RAM), coupled on-line to the LC-MS/MS system, which allows direct injection of the matrix into the RAM-LC-MS/MS system. The optimized method developed, RAM-LC-MS/MS, was applied to fortified honey samples, affording detection limits in the 0.6-7.2 ng g(-1) range, calculated for a signal-to-noise ratio of 3. In addition, the method was validated as a quantitative confirmatory method according to European Union Decision 2002/657/EC. The validation criteria evaluated were linearity, repeatability, reproducibility, recovery, decision limits, detection capabilities, specificity, and ruggedness. Repeatability and within-laboratory reproducibility were evaluated at two concentration levels, being +/-11% or below at 20 ng g(-1). The decision limits (CC(alpha)) and detection capabilities (CC(beta)) were in the 1.7-12.6 and 2.8-21.6 ng g(-1) range, respectively. PMID:20336451

  4. Evaluation of a Screening System for Obesogenic Compounds: Screening of Endocrine Disrupting Compounds and Evaluation of the PPAR Dependency of the Effect

    PubMed Central

    Pereira-Fernandes, Anna; Demaegdt, Heidi; Vandermeiren, Karine; Hectors, Tine L. M.; Jorens, Philippe G.; Blust, Ronny; Vanparys, Caroline

    2013-01-01

    Recently the environmental obesogen hypothesis has been formulated, proposing a role for endocrine disrupting compounds (EDCs) in the development of obesity. To evaluate this hypothesis, a screening system for obesogenic compounds is urgently needed. In this study, we suggest a standardised protocol for obesogen screening based on the 3T3-L1 cell line, a well-characterised adipogenesis model, and direct fluorescent measurement using Nile red lipid staining technique. In a first phase, we characterised the assay using the acknowledged obesogens rosiglitazone and tributyltin. Based on the obtained dose-response curves for these model compounds, a lipid accumulation threshold value was calculated to ensure the biological relevance and reliability of statistically significant effects. This threshold based method was combined with the well described strictly standardized mean difference (SSMD) method for classification of non-, weak- or strong obesogenic compounds. In the next step, a range of EDCs, used in personal and household care products (parabens, musks, phthalates and alkylphenol compounds), were tested to further evaluate the obesogenicity screening assay for its discriminative power and sensitivity. Additionally, the peroxisome proliferator activated receptor γ (PPARγ) dependency of the positive compounds was evaluated using PPARγ activation and antagonist experiments. Our results showed the adipogenic potential of all tested parabens, several musks and phthalate compounds and bisphenol A (BPA). PPARγ activation was associated with adipogenesis for parabens, phthalates and BPA, however not required for obesogenic effects induced by Tonalide, indicating the role of other obesogenic mechanisms for this compound. PMID:24155963

  5. The association between some endocrine disruptors and hypospadias in biological samples.

    PubMed

    Choi, Haemin; Kim, Joohoon; Im, Yeongjae; Lee, Sanghouck; Kim, Yunje

    2012-01-01

    Hypospadias is a birth defect found in boys in which the urinary tract opening is not at the tip of the penis. The etiology of hypospadias is still unidentified, but endocrine disruptors are considered as one possible cause of hypospadias. In this study, target endocrine disruptor compounds were established for an assay. The target compounds included 5 phthalates (di-(2-ethylhexyl)phthalate (DEHP), di-n-butyl-phthalate (DBP), mono-(2- ethylhexyl) phthalate (MEHP), mono-n-butyl-phthalate (MBP) and phthalic acid (PA)), 2 alkylphenols (n-nonylphenol (n-NP) and t-octylphenol (t-OP)) and bisphenol A. The association between these 8 endocrine disruptors and hypospadias was studied. The levels of endocrine disruptors in the urine and plasma of a control group were compared with those of a patient group. DEHP (P = 0.006) and n-NP (P = 7.26e-6) in the urine samples and PA (P = 0.009) and BPA (P = 7.22e-10) in the plasma samples showed a significant association with hypospadias. The levels of endocrine disruptors in the urine and plasma of the mothers were also compared to those of the patients to investigate the metastasis of the endocrine disruptors from the mother. These levels did not, however, show a relationship with hypospadias (R(2) = 0.001-0.563). PMID:22871016

  6. Association of exposure to phenols and idiopathic male infertility.

    PubMed

    Chen, Minjian; Tang, Rong; Fu, Guangbo; Xu, Bin; Zhu, Pengfei; Qiao, Shanlei; Chen, Xiaojiao; Xu, Bo; Qin, Yufeng; Lu, Chuncheng; Hang, Bo; Xia, Yankai; Wang, Xinru

    2013-04-15

    Widespread human exposure to phenols has been documented recently, and some phenols which are potential endocrine disruptors have demonstrated adverse effects on male reproduction in animal and in vitro studies. However, implications about exposure to phenols and male infertility are scarce in humans. Case-control study of 877 idiopathic infertile men and 713 fertile controls was conducted. Urinary levels of bisphenol A, benzophenone-3, pentachlorophenol, triclosan, 4-tert-octylphenol (4-t-OP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP) and semen parameters were measured. After multivariate adjustment, we found 4-t-OP, 4-n-OP and 4-n-NP exposure was associated with idiopathic male infertility (p-value for trend: <0.0001, 0.014 and 0.001, respectively). Aside from these associations, 4-t-OP and 4-n-NP exposure was also associated with idiopathic male infertility with abnormal semen parameters. Moreover, we observed significant associations between sum alkylphenols (APs) exposure and idiopathic male infertility. There were no relationships between exposure to other phenols and idiopathic male infertility in the present study. Our study provides the first evidence that exposure to APs (4-t-OP, 4-n-OP and 4-n-NP) is associated with idiopathic male infertility. PMID:23435201

  7. 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. PMID:24645486

  8. A broad cocktail of environmental pollutants found in eggs of three seabird species from remote colonies in Norway.

    PubMed

    Huber, Sandra; Warner, Nicholas A; Nygård, Torgeir; Remberger, Mikael; Harju, Mikael; Uggerud, Hilde T; Kaj, Lennart; Hanssen, Linda

    2015-06-01

    Eggs of 3 seabird species, common eider (Somateria mollisima), European shag (Phalacrocorax aristotelis aristotelis), and European herring gull (Larus argentatus), were surveyed for a broad range of legacy and emerging pollutants to assess chemical mixture exposure profiles of seabirds from the Norwegian marine environment. In total, 201 chemical substances were targeted for analysis ranging from metals, organotin compounds, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and associated metabolites, chlorinated paraffins, chlorinated and nonchlorinated organic pesticides, per- and polyfluoroalkyl substances (PFAS), dechlorane plus, octachlorostyrene, brominated flame retardants (BFRs), organophosphorous compounds, brominated and alkyl phenols, cyclic siloxanes, and phthalates. Of the chemicals targeted, 149 substances were found above the detection limits, with metals dominating the contaminant profile and comprising 60% of the total contaminant load. Polychlorinated biphenyls, pesticides, organophosphorous compounds, and PFAS were the dominant contaminant classes of organic pollutants found within the seabird species, with the highest loads occurring in herring gulls, followed by shag, and common eider. New generation pollutants (e.g., PFAS, organophosphorous compounds, and alkylphenols) were detected at similar or higher concentrations than the legacy persistent organic pollutants (POPs). Time trends of reported concentrations of legacy POPs appear to have decreased in recent decades from the Norwegian coastal environment. Concentrations of detected pollutants do not appear to have a negative effect on seabird population development within the sampling area. Additional stress caused by pollutants, however, may affect seabird health more at the individual level. PMID:25728907

  9. 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.

  10. 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. PMID:24731372

  11. 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)). PMID:26475722

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

    PubMed

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

    2011-12-15

    The hypothesis regarding preferential biodegradation of surfactants applied for enhancement of microbial hydrocarbons degradation was studied. At first the microbial degradation of sole Triton X-100 by soil isolated hydrocarbon degrading bacterial consortium was confirmed under both full and limited aeration with nitrate as an electron acceptor. Triton X-100 (600 mg/l) was utilized twice as fast for aerobic conditions (t(1/2)=10.3h), compared to anaerobic conditions (t(1/2)=21.8h). HPLC/ESI-MS analysis revealed the preferential biodegradation trends in both components classes of commercial Triton X-100 (alkylphenol ethoxylates) as well as polyethylene glycols. The obtained results suggest that the observed changes in the degree of ethoxylation for polyethylene glycol homologues occurred as a consequence of the 'central fission' mechanism during Triton X-100 biodegradation. Subsequent experiments with Triton X-100 at approx. CMC concentration (150 mg/l) and diesel oil supported our initial hypothesis that the surfactant would become the preferred carbon source even for hydrocarbon degrading bacteria. Regardless of aeration regimes Triton X-100 was utilized within 48-72 h. Efficiency of diesel oil degradation was decreased in the presence of surfactant for aerobic conditions by approx. 25% reaching 60 instead of 80% noted for experiments without surfactant. No surfactant influence was observed for anaerobic conditions. PMID:21996621

  14. Effects of porous media, macrophyte type and hydraulic retention time on the removal of organic load and micropollutants in constructed wetlands.

    PubMed

    Herrera-Cárdenas, Jorge; Navarro, Amado E; Torres, Eduardo

    2016-04-15

    The performance of horizontal subsurface flow constructed wetlands in the removal of micropollutants from a wastewater treatment plant effluent was evaluated at mesocosm level. Fifteen mesocosms were studied following a modified Latin Square experimental design with six additional points. Three variables at three levels were studied: porous media -PM- (river gravel, fine volcanic gravel and coarse volcanic gravel), macrophyte type -M- (Thypa latiffolia, Phragmites australis, and Cyperus papyrus) and hydraulic retention time -HRT- (1, 3 and 5 days). As response variables the removal percentages of the total organic load of the effluent (BOD5) and the loads of several micropollutants (caffeine, galaxolide, tonalide, alkylphenols and their monoethoxylates and diethoxylates, methyl dihydrojasmonate, sunscreen UV-15 and parsol) were used. The results showed that the systems remove between 70% and 75% of the organic load and that all the micropollutants were degraded at different extents, from 55% to 99%. The HRT was the variable that showed major effects on the treatment process, while M and PM showed no statistically significant differences in the used experimental conditions. PMID:26817393

  15. 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.

  16. Evaluation of the presence of endocrine-disrupting compounds in dissolved and solid wastewater treatment plant samples of Gran Canaria Island (Spain).

    PubMed

    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

  17. 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.

  18. The nonionic surfactant pollution profile of Israel Mediterranean Sea coastal water.

    PubMed

    Zoller, U; Hushan, M

    2001-01-01

    Anionic and nonionic surfactants, as core components of detergent formulations, contribute significantly to the pollution profile of sewage and wastewaters of all kinds. In Israel about 15% of the total amount of ca. 4 x 10(8) m3/year of sewage is discharged, directly, or via receiving streams/rivers, into the Mediterranean Sea. Based on our previous findings that about 85% of the nonionic surfactants in the country's sewage are nonbiodegradable alkylphenol-based ethoxylates, we have undertaken this study, aiming at mapping the receiving eastern Mediterranean seawater with respect to its nonionic surfactant pollution profile. The total concentrations of nonionic surfactants were found--via reverse phase HPLC determinations--to be within the range of 4.2-25.0 ppb in seawater samples taken 2-3 m off the coastline at those locations where sewage-containing streams flow into the sea. Thus, neither the existing sewage treatment facilities nor natural biodegradation processes in receiving surface water systems are capable of avoiding this coastal water pollution. The potential estrogenic health risk of such concentrations of the anthropogenic EPEOs is dependent, among other things, on their specific homological distribution, biodegradation rate (slower for those having > 10 EO units) and survival. PMID:11379138

  19. 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. PMID:26829069

  20. 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. PMID:27080878

  1. Surfactant-coated aluminum hydroxide for the rapid removal and biodegradation of hydrophobic organic pollutants in water.

    PubMed

    Saitoh, Tohru; Yamaguchi, Masato; Hiraide, Masataka

    2011-02-01

    The removal of hydrophobic organic pollutants in water to surfactant-coated aluminum hydroxide [surfactant-Al(OH)(3)] was investigated. Anionic surfactants such as sodium dodecyl sulfate (SDS), sodium bis(2-ethylhexyl)sulfosuccinate (AOT), and sodium oleate were sorbed on positively charged aluminum hydroxide at pH 7 and formed hydrophobic aggregates that can incorporate hydrophobic organic pollutants in water. Because of the hydrophobic interaction and decrease in the positive charge, surfactant-Al(OH)(3) was coagulated into precipitates that can readily be separated from water. Hydrophobic organic pollutants such as alkylphenols, polycyclic aromatic hydrocarbons, estrogens, chlorinated antifungals, and pesticides were well collected to the precipitates and thus efficiently removed from water. The collection of hydrophobic organic pollutants was correlated to their aqueous-octanol distribution coefficient. The decomposition of hydrophobic organic pollutants was examined using a bacterial agent (Bacillus subtilis). Hydrophobic organic compounds collected to AOT-Al(OH)(3) or sodium oleate-Al(OH)(3) were insufficiently decomposed. On the other hand, nonylphenol, octylphenol, and pendimethalin collected to SDS-Al(OH)(3) were decomposed within 1 week. The decomposition was accelerated by the collection to SDS-Al(OH)(3). PMID:21193213

  2. An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands.

    PubMed

    Vethaak, A Dick; Lahr, Joost; Schrap, S Marca; Belfroid, Angélique C; Rijs, Gerard B J; Gerritsen, Anton; de Boer, Jacob; Bulder, Astrid S; Grinwis, Guy C M; Kuiper, Raoul V; Legler, Juliette; Murk, Tinka A J; Peijnenburg, Willie; Verhaar, Henk J M; de Voogt, Pim

    2005-04-01

    An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects. PMID:15788174

  3. Determination of selected endocrine disrupting chemicals in Lake Van, Turkey.

    PubMed

    Oğuz, Ahmet R; Kankaya, Ertuğrul

    2013-09-01

    In the present study, we investigated the distribution of 17β-estradiol (E2), 17α-ethynylestradiol (EE2), alkylphenol ethoxylates (APEs) and organochlorine pesticides (DDE/DDT) in water and sediment samples in the Eastern Anatolia of Turkey, Lake Van, which is the largest soda lake in the world. The procedure consisted of solid phase extraction performed with OASIS HLB cartridges followed by non-competitive enzyme-linked immunosorbent assays (ELISA). The endocrine disrupting compounds E2, EE2, and DDT/DDE were detected in most of the lake samples with mean concentrations of 0.996 ± 0.304, 0.050 ± 0.022, and 0.749 ± 0.658 ng/L in water, respectively. Mean concentrations of E2, EE2 and DDT/DDE in sediment were 0.098 ± 0.053, 0.091 ± 0.072, and 1.281 ± 0.754 ng/g, respectively. APEs were not measured in the sediment samples. The EDCs levels in surface water and sediment samples were lower than that of other countries. The EDCs were also found in effluent and influent municipal sewage samples. Van city municipal wastewater treatment plant has no removal efficiency for EDCs. PMID:23771312

  4. Effects of produced water on reproductive parameters in prespawning Atlantic cod (Gadus morhua).

    PubMed

    Sundt, Rolf C; Björkblom, Carina

    2011-01-01

    Produced water (PW) discharged from offshore oil industry activities contains substances that are known to contribute to a range of mechanisms of toxicity. In the present study selected reproductive biomarkers were studied in prespawning Atlantic cod (Gadus morhua) exposed to PW. The fish were exposed for 12 wk within a continuous flow-through system at realistic environmental near-field concentrations. Concentrations of polyaromatic hydrocarbon (PAH) and alkylphenol (AP) compounds were analyzed by gas chromatography with mass spectrometric detection measurement, as were PAH and AP metabolites in fish bile for verification of exposure conditions and presence of compounds in PW. A suite of reproductive biomarkers (vitellogenin, zona radiata protein, and plasma steroid concentrations) and histological alterations of the gonads were determined. Results showed that exposure to sufficiently high levels of PW produced an increase in vitellogenin levels in female fish compared to the control. Impaired oocyte development and reduced estrogen levels were also observed in PW-exposed female fish. In male fish testicular development was altered, showing a rise in amount of spermatogonia and primary spermatocytes and a reduction in quantity of mature sperm in the PW-exposed fish compared to control. Data indicate that sufficiently high levels of PW have the potential to adversely affect the reproductive fitness of cod. PMID:21391097

  5. Spatial-temporal distribution and potential ecological risk assessment of nonylphenol and octylphenol in riverine outlets of Pearl River Delta, China.

    PubMed

    Chen, Ru; Yin, Pinghe; Zhao, Ling; Yu, Qiming; Hong, Aihua; Duan, Shunshan

    2014-11-01

    The aquatic environments of the Pearl River Delta in Southern China are subjected to contamination with various industrial chemicals from local industries. In this paper, the occurrence, seasonal variation and spatial distribution of alkylphenol octylphenol (OP) and nonylphenol (NP) in river surface water and sediments in the runoff outlets of the Pearl River Delta were investigated. NP and OP were detected in all water and sediment samples and their mean concentrations in surface water during the dry season ranged from 810 to 3366 ng/L and 85.5 to 581 ng/L, respectively, and those in sediments ranged from 14.2 to 95.2 ng/g dw and 0.4 to 3.0 ng/g dw, respectively. In surface water, much higher concentrations were detected in the dry season than those in the wet season. In sediments, the concentrations in the dry season were also mostly higher. High concentrations of NP and OP were found in Humen outlet, likely due to high levels of domestic and industrial wastewater discharges. An ecological risk assessment with the use of hazard quotient (HQ) was also carried out and the HQ values ranged from 3.6×10(-5) to 35 and 64% of samples gave a HQ>1, indicating that the current levels of NP and OP pose a significant risk to the relevant aquatic organisms in the region. PMID:25458690

  6. Reduction in the estrogenic activity of a treated sewage effluent discharge to an English river as a result of a decrease in the concentration of industrially derived surfactants.

    PubMed

    Sheahan, David A; Brighty, Geoff C; Daniel, Mic; Jobling, Susan; Harries, Jule E; Hurst, Mark R; Kennedy, Joe; Kirby, Sonia J; Morris, Steven; Routledge, Edwin J; Sumpter, John P; Waldock, Michael J

    2002-03-01

    As a result of the introduction of tighter discharge limits and effluent treatment processes at source, the concentration of alkylphenol ethoxylates and nonylphenol present in the final effluent discharge from a sewage treatment works that treats trade effluent from the textiles industry was reduced. The estrogenic effects of the final effluent discharge to the Aire River were compared over a four-year period during which various treatment measures were introduced. Male rainbow trout exposed to the effluent on four occasions in consecutive years (1994-1997) showed a reduction in the level of induced vitellogenesis between 1994 and 1997. A marked decrease in gonadosomatic index (GSI) and increase in heptaosomatic index (HSI) was measured in fish exposed to the effluent in 1994. In successive years, these differences diminished, and in the case of the GSI no measurable difference was observed between fish exposed to the final effluent or those in the control group in 1997. However, an increase in HSI was still measurable in 1997 in fish exposed to the final effluent and at sites farther downstream. The reduction in the effects of the effluent paralleled the reduction in the concentration of nonylphenol as well as its mono- and diethoxylates, which have been demonstrated to produce estrogenic effects in trout exposed to these compounds in the laboratory. This study demonstrates that the setting of more restricted discharge limits for known estrogenic chemicals of industrial origin can lead to significant reductions in the estrogenic activity of the watercourses into which the effluents are discharged. PMID:11878464

  7. 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. PMID:17258235

  8. 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

  9. Sustainable risk management of emerging contaminants in municipal wastewaters.

    PubMed

    Martin, O V; Voulvoulis, N

    2009-10-13

    The presence of emerging contaminants in municipal wastewaters, particularly endocrine-disrupting compounds such as oestrogenic substances, has been the focus of much public concern and scientific attention in recent years. Due to the scientific uncertainty still surrounding their effects, the Precautionary Principle could be invoked for the interim management of potential risks. Therefore, precautionary prevention risk-management measures could be employed to reduce human exposure to the compounds of concern. Steroid oestrogens are generally recognized as the most significant oestrogenically active substances in domestic sewage effluent. As a result, the UK Environment Agency has championed a 'Demonstration Programme' to investigate the potential for removal of steroid oestrogens and alkylphenol ethoxylates during sewage treatment. Ecological and human health risks are interdependent, and ecological injuries may result in increased human exposures to contaminants or other stressors. In this context of limiting exposure to potential contaminants, examining the relative contribution of various compounds and pathways should be taken into account when identifying effective risk-management measures. In addition, the explicit use of ecological objectives within the scope of the implementation of the EU Water Framework Directive poses new challenges and necessitates the development of ecosystem-based decision tools. This paper addresses some of these issues and proposes a species sensitivity distribution approach to support the decision-making process related to the need and implications of sewage treatment work upgrade as risk-management measures to the presence of oestrogenic compounds in sewage effluent. PMID:19736227

  10. Effluents from oil production activities contain chemicals that interfere with normal function of intra- and extra-cellular estrogen binding proteins.

    PubMed

    Tollefsen, Knut-Erik; Finne, Eivind Farmen; Romstad, Randi; Sandberg, Cecilie

    2006-07-01

    Some environmental pollutants have the ability to alter the endocrine function in fish through interaction with the estrogen receptor (ER). Many of these chemicals are also able to interfere with the endocrine system through other mechanisms of action, however. The plasma sex steroid-binding protein (SBP), which is involved in regulating circulating levels of endogenous sex steroids, has recently been proposed to contribute to pollutant induced disruption of endocrine homeostasis. The objective of the present work was to determine whether industrial effluents contain chemicals that are able to modulate the endocrine system through interference with the function of the ER and SBP using in vitro biological assays (bioassays) from rainbow trout. The results show that solid phase extracts of process water (produced water) from an oil production facility in the North Sea and a land-based oil refinery contain chemicals that are able to induce estrogenic effects as well as displace natural sex steroid 17beta-estradiol from the SBP. The bioactive chemicals were found to be partly resistant to biological degradation, but the identity of the chemicals was not determined. The alkylphenol 4-tert-butylphenol, which is known to occur in effluents from various oil production facilities, was found to be estrogenic and displace 17beta-estradiol from the SBP and may thus contribute to the observed endocrine disrupting activity. PMID:16697461

  11. 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. PMID:23736740

  12. Endocrine disrupters: a human risk?

    PubMed

    Waring, R H; Harris, R M

    2005-12-01

    Endocrine disrupters (EDs) alter normal hormonal regulation and may be naturally occurring or environmental contaminants. Classically, EDs act genomically, with agonistic or antagonistic effects on steroid receptors and may alter reproductive function and/or cause feminisation by binding to oestrogen or androgen receptors; their binding to the thyroid receptor may dysregulate the neuroendocrine system. Recently, it has been shown that EDs can also act by non-genomic mechanisms, altering steroid synthesis (inhibition of cytochrome P450 isoforms) or steroid metabolism. The alkylphenol and phthalate plasticisers inhibit the inactivation of oestrogens by sulphation (via SULT 1A1 and 1E1 isoforms) and so cause a rise in levels of the free active endogenous oestrogens. A range of ED effects have been shown in mammals, fish, birds, reptiles, amphibia and aquatic invertebrates but it is not yet clear whether these processes also occur in human beings. It is evident that EDs, as well as altering reproduction, can cause changes in neurosteroid levels and so have the potential to affect immune function, behaviour and memory. This may be of long-term concern since traces of EDs such as plasticisers, brominated fire retardants, sunscreen agents and cosmetic ingredients are widely distributed in the environment and in human biofluids. PMID:16271281

  13. Occurrence and behavior of wastewater indicators in the Santa Ana River and the underlying aquifers.

    PubMed

    Ding, W H; Wu, J; Semadeni, M; Reinhard, M

    1999-11-01

    The occurrence and behavior of wastewater indicator compounds in the Santa Ana River (SAR) water and the underlying aquifer recharged by the SAR has been studied. The SAR contains a high proportion of tertiary treated wastewater effluents, up to 100% during summer and fall. The following water quality parameters were quantified: four specific wastewater indicator compounds, ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), a naphthalene dicarboxylate (NDC) isomer, alkylphenol polyethoxy carboxylates (APECs), and selected haloacetic acids (HAAs), nitrate, dissolved oxygen (DO), DOC, total carbohydrate, and phenolic substances. Statistical analysis indicated that normal distribution was adequate to describe the probability distribution of the constituents in most cases. In the river, the concentrations of wastewater indicator compounds decreased as the fraction of storm runoff increased. EDTA and NDC were detected in a monitoring well near the river and in two production wells 1.8 and 2.7 km down gradient with little apparent attenuation. By contrast, NTA, APECs, bromochloro- and dibromoacetic acids appeared to be attenuated significantly during infiltration of river water and groundwater transport. PMID:10533715

  14. 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. PMID:23815555

  15. 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. PMID:26884138

  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. 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. PMID:22204938

  18. Development of a multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography-tandem mass spectrometry.

    PubMed

    Sánchez-Avila, Juan; Fernandez-Sanjuan, María; Vicente, Joana; Lacorte, Silvia

    2011-09-23

    This study describes the development of a multiresidue method based on gas chromatography-electron ionization-tandem mass spectrometry (GC-EI-MS/MS) for the detection of sixteen polycyclic aromatic hydrocarbons (PAHs), five phthalate esters (PEs), seven polychlorinated biphenyls (PCBs), six polybrominated diphenyl ethers (PBDEs), six alkylphenols (APs), three organochlorined pesticides and their isomers or degradation products (OCPs) and bisphenol A in seawater, river water, wastewater treatment plant (WWTP) effluents, sediments and mussels. Solid phase extraction (SPE) was used for the extraction of target analytes in aqueous samples, and ultrasound assisted extraction for solid samples. GC-EI-MS/MS acquisition conditions in selected reaction monitoring (SRM) using two transitions per compound were optimized. In this way, quantification and unequivocal identification of organic micropollutants were performed in compliance with the Decision 2002/657/EC. Good linearity responses with coefficients of determination higher than 0.99 were obtained. Methodological detection limits (MDLs) in seawater ranged from 0.1 to 6 ng L(-1); in river water from 0.1 to 4.8 ng L(-1); in WWTP effluents from 1 to 75 ng L(-1); in sediments from 1 to 150 ng g(-1) and in mussels from 1 to 125 ng g(-1). MDLs and recovery yields were compared with other published methods and similarities or even improvements were achieved. The optimized method was applied to analyze five samples from each matrix collected in coastal areas, showing its potential use for marine pollution monitoring. PMID:21824622

  19. 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.

  20. Analysis of phenolic compounds in the dissolved and suspended phases of Lake Balaton water by gas chromatography-tandem mass spectrometry.

    PubMed

    Faludi, T; Balogh, C; Serfőző, Z; Molnár-Perl, I

    2015-08-01

    As a novel approach to characterize the phenolic pollutants of Lake Balaton (Central Europe, western Hungary), 26 endocrine disrupting phenols (chlorophenols, nitrophenols, alkylphenols, triclosan, bisphenol-A) were quantified in dissolved and suspended particulate matter (SPM) phases, alike. Sample collection was performed in the western and eastern basins, at 20 sites in April and October 2014. Solid-phase and ultrasound-assisted extractions to withdraw target phenols from dissolved and suspended phases were employed. Compounds were derivatized with hexamethyldisilazane and trifluoroacetic acid for their quantification as trimethylsilyl derivatives by gas chromatography-tandem mass spectrometry. In Lake Balaton's dissolved phase, 2-chlorophenol (103-164 ng/L), 4-chlorophenol (407-888 ng/L), 2,4-dichlorophenol (20.2-72.0 ng/L), 2,4,6-trichlorophenol (10.4-38.1 ng/L), 2-nitrophenol (31.0-66.5 ng/L), 4-nitrophenol (31.5-94.1 ng/L), and bisphenol-A (20.6-112 ng/L), while in its SPM, 4-chlorophenol (

  1. Formation of insoluble, nonhydrolyzable, sulfur-rich macromolecules via incorporation of inorganic sulfur species into algal carbohydrates

    NASA Astrophysics Data System (ADS)

    Kok, Marika D.; Schouten, Stefan; Sinninghe Damsté, Jaap S.

    2000-08-01

    The process of sulfur incorporation into organic matter was simulated in the laboratory by sulfurization of cell material of the prymnesiophyte alga Phaeocystis in sea water with inorganic polysulfides at 50°C. Flash pyrolysis of the residue, obtained after extraction and several hydrolysis steps, yielded mainly C 1-C 4 alkylbenzenes and C 1-C 4 alkylphenols and, in contrast to control and blank experiments, relatively high amounts of C 0-C 4 alkylthiophenes. The distribution of the thiophenes is very similar to that in pyrolysates of type II-S kerogens. The formation of high-molecular-weight sulfur-rich macromolecules co-occurs with a marked drop in the content of hydrolyzable carbohydrates. This indicates that sulfurization results in the preservation of algal carbohydrate carbon in a macromolecular structure composed of (poly)sulfidic cross-linked carbohydrate skeletons, which upon pyrolysis yields alkylthiophenes. Sulfurization of glucose under similar conditions resulted in the formation of a nonhydrolyzable, solid material, which yielded high amounts of organic sulfur compounds upon pyrolysis, mainly short-chain alkylthiophenes, although with a different distribution than that in the pyrolysate of the sulfurized algal material. The carbon numbers of these organic sulfur compounds extend beyond six, indicating that the length of the carbon skeleton of the pyrolysis products is not limited by the length of the carbon skeleton of the substrate. These results suggest that the sulfurization of carbohydrates may be an important pathway in the preservation of organic matter in euxinic depositional environments.

  2. Toxicity of N-substituted aromatics to acetoclastic methanogenic activity in granular sludge.

    PubMed Central

    Donlon, B A; Razo-Flores, E; Field, J A; Lettinga, G

    1995-01-01

    N-substituted aromatics are important priority pollutants entering the environment primarily through anthropogenic activities associated with the industrial production of dyes, explosives, pesticides, and pharmaceuticals. Anaerobic treatment of wastewaters discharged by these industries could potentially be problematical as a result of the high toxicity of N-substituted aromatics. The objective of this study was to examine the structure-toxicity relationships of N-substituted aromatic compounds to acetoclastic methanogenic bacteria. The toxicity was assayed in serum flasks by measuring methane production in granular sludge. Unacclimated cultures were used to minimize the biotransformation of the toxic organic chemicals during the test. The nature and the degree of the aromatic substitution were observed to have a profound effect on the toxicity of the test compound. Nitroaromatic compounds were, on the average, over 500-fold more toxic than their corresponding aromatic amines. Considering the facile reduction of nitro groups by anaerobic microorganisms, a dramatic detoxification of nitroaromatics towards methanogens can be expected to occur during anaerobic wastewater treatment. While the toxicity exerted by the N-substituted aromatic compounds was closely correlated with compound apolarity (log P), it was observed that at any given log P, N-substituted phenols had a toxicity that was 2 orders of magnitude higher than that of chlorophenols and alkylphenols. This indicates that toxicity due to the chemical reactivity of nitroaromatics is much more important than partitioning effects in bacterial membranes. PMID:8526501

  3. Occurrence of priority and emerging organic compounds in fishes from the Rhone River (France).

    PubMed

    Miège, C; Peretti, A; Labadie, P; Budzinski, H; Le Bizec, B; Vorkamp, K; Tronczyński, J; Persat, H; Coquery, M; Babut, M

    2012-11-01

    The main objective of this study was to collect new data on the occurrence, levels of priority and emerging organic compounds in freshwater fish sampled in the Rhone River. The 34 studied contaminants included alkylphenols, bisphenol A, polybromodiphenylethers (PBDE), perfluorinated compounds, hexabromocyclododecanes (HBCD), hexachlorobenzene and hexachlorobutadiene (HCBD). About 50 fish samples (individual specimens or pooled fish) were collected from three sites located upstream and downstream of the Lyon metropolitan area in the Rhone River (France). Four species were caught at each site, namely: the barbel (Barbus barbus), the common bream (Abramis brama), the white bream (Blicca bjoerkna) and the chub (Squalius cephalus). Some contaminants were quantified in all the 32 fish samples analysed: 4-nonylphenol, α-HBCD, the six PBDE congeners (28, 47, 99, 100, 153, 154), perfluorooctanesulfonate (PFOS) and perfluorodecanoic acid. Twenty three of the 32 samples had a concentration of PFOS above the Environmental Quality Standards (EQS) (up to six times higher than the EQS), and all the 32 samples had concentrations of PBDE above the EQS (up to 4,000 times higher, with the sum of six PBDE varying from 4.5 to 182 ng/g dry weight). Clearly, the interest to consider PFOS and HBCD as new priority substances is confirmed. In contrast, the pertinence of a priority status for HCBD, which was never quantified in our study, might have to be reconsidered in the future. PMID:22760502

  4. Endocrine disrupting chemicals-Linking internal exposure to vitellogenin levels and ovotestis in Abramis brama from Dutch surface waters.

    PubMed

    Reinen, Jelle; Suter, Marc J-F; Vögeli, A Christiane; Fernandez, Mariana F; Kiviranta, Hannu; Eggen, Rik I L; Vermeulen, Nico P E

    2010-11-01

    The exposure of male bream from three Dutch freshwater locations to endocrine disrupting compounds (EDCs) and corresponding effects are described in this study. Fish specimen displaying reproductive disorders associated with high levels of plasma vitellogenin (VTG) concentrations and occurrence of ovotestis (OT) were investigated. To provide information on the full spectrum of EDCs in fish tissue, adipose tissue samples of individual fish were analyzed for nearly 130 chemicals targeting different compound classes (bisphenols, alkylphenols, pesticides, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), polybrominated diphenyl ethers (PBDEs) and biphenyls (PBBs)) and steroid hormones. To establish whether tissue from specimen with reproductive disorders shows a spectrum of EDCs that is qualitatively and quantitatively different from that of controls free of symptoms, bioassay-directed fractionation was performed using the recombinant yeast estrogen screen (YES), the E-Screen bioassay, the human sulfotransferase 1E1 (SULT1E1) inhibition assay, and the coumestrol-based estrogen receptor α (ERα) high resolution screening (HRS) assay. No differences in estrogenicity could be observed between the cases and controls and steroidal estrogens accounted for the majority of estrogenicity found in the complex mixtures. In this study, the combination of the different assays employed to measure total estrogenicity and the SULT1E1 inhibition does not predict the outcome of unwanted physiological effects, however, it can be used to determine the presence of EDCs in fish samples and their estrogenic effects. PMID:21787654

  5. Evaluation of the cytotoxic and mutagenic potential of three ginkgolic acids.

    PubMed

    Berg, Kerstin; Braun, Christine; Krug, Isabel; Schrenk, Dieter

    2015-01-01

    Ginkgolic acids (GAs) are alkylphenols which can be found in the fruits and leaves of Ginkgo biloba L. (Ginkgoaceae) used in herbal teas, drugs and food supplements. Standardized leaf extracts of G. biloba are widely used in the therapy of cognitive decline including Alzheimer's diseases. However, GAs are known to have cytotoxic and allergenic potential and are suspected to possess genotoxic properties. Therefore, we examined in this study the cytotoxicity and mutagenicity of three major GAs with different alkyl or alkenyl groups (13:0, 15:1, 17:1). Cytotoxicity was assessed in male Chinese hamster lung fibroblasts (V79 cells) using the resazurin reduction assay. The substances showed concentration dependent cytotoxic effects after 24h of incubation at concentrations of 50μM and higher. Mutagenicity was determined by using the Ames fluctuation assay in different Salmonella typhimurium strains (TA97a, TA98, TA100 and TA102) with and without exogenous metabolic activation (S9 mix). Furthermore, we analyzed the mutagenic potency of the three major GAs in V79 cells by performing the hypoxanthine phosphoribosyl transferase (HPRT) assay which detects gene mutations at the HPRT locus. None of the mutagenic assays showed any increase in mutagenicity above background. Therefore, these data provide evidence that the GAs tested have some cytotoxic potency but are not mutagenic. Thus, our findings contribute to the risk assessment of preparations containing plant extracts from G. biloba. PMID:25448085

  6. The use of monitoring data in EU chemicals management--experiences and considerations from the German environmental specimen bank.

    PubMed

    Koschorreck, Jan; Heiss, Christiane; Wellmitz, Jörg; Fliedner, Annette; Rüdel, Heinz

    2015-02-01

    Since the 1970s, environmental specimen banks (ESB) have emerged in many countries. Their highly standardised sampling and archiving strategies make them a valuable tool in tracing time trends and spatial distributions of chemicals in ecosystem compartments. The present article intends to highlight the potential of ESBs for regulatory agencies in the European Union (EU). The arguments are supported by examples of retrospective monitoring studies conducted under the programme of the German ESB. These studies have evaluated the success of regulatory and industry provisions for substances of concern (i.e. PCB, polybrominated diphenyl ethers, perfluorinated compounds, alkylphenol compounds, organotin compounds, triclosan/methyl-triclosan, musk fragrances). Time trend studies revealed for example that levels of organotin compounds in marine biota from German coastal waters decreased significantly after the EU had decided on a total ban of organotin-based antifoulings in 2003. Similarly, concentrations of commercially relevant congeners of polybrominated diphenyl ethers decreased in herring gull eggs from the North Sea only after an EU-wide ban in 2004. The data presented demonstrate the usefulness of ESB samples for (retrospective) time trend monitoring and underline the benefit of a more intensive cooperation between chemicals management and specimen banking. PMID:24770983

  7. Uptake calibration of polymer-based passive samplers for monitoring priority and emerging organic non-polar pollutants in WWTP effluents.

    PubMed

    Posada-Ureta, Oscar; Olivares, Maitane; Zatón, Leire; Delgado, Alejandra; Prieto, Ailette; Vallejo, Asier; Paschke, Albrecht; Etxebarria, Nestor

    2016-05-01

    The uptake calibration of more than 12 non-polar organic contaminants by 3 polymeric materials is shown: bare polydimetilsiloxane (PDMS, stir-bars), polyethersulfone tubes and membranes (PES) and polyoxymethylene membranes (POM), both in their free form and membrane-enclosed sorptive coating (MESCO). The calibration process was carried out exposing the samplers to a continuous flow of contaminated water at 100 ng mL(-1) for up to 28 days, and, consequently, the sampling rates (Rs, mL day(-1)) of several organic microcontaminants were provided for the first time. In situ Rs values were also determined disposing the samplers in the effluent of a wastewater treatment plant. Finally, these passive samplers were applied to monitor the effluents of two wastewater treatment plants. This application lead to the confirmation of the presence of galaxolide, tonalide and 4-tert-octylphenol at high ng mL(-1) levels, as well as the identification of compounds like some phthalates and alkylphenols at levels below the detection limits for active sampling methods. PMID:26892638

  8. 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

  9. 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.

  10. 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

  11. Identification of petrogenic produced water components as acetylcholine esterase inhibitors.

    PubMed

    Froment, Jean; Langford, Katherine; Tollefsen, Knut Erik; Bråte, Inger Lise N; Brooks, Steven J; Thomas, Kevin V

    2016-08-01

    Effect-directed analysis (EDA) was applied to identify acetylcholine esterase (AChE) inhibitors in produced water. Common produced water components from oil production activities, such as polycyclic aromatic hydrocarbons (PAHs), alkylphenols, and naphthenic acids were tested for AChE inhibition using a simple mixture of PAHs and naphthenic acids. Produced water samples collected from two offshore platforms in the Norwegian sector of the North Sea were extracted by solid phase extraction and fractionated by open-column liquid solid chromatography and high-performance liquid chromatography (HPLC) before being tested using a high-throughput and automated AChE assay. The HPLC fractions causing the strongest AChE inhibition were analysed by gas chromatography coupled to a high-resolution time-of-flight mass spectrometry (GC-HR-ToF-MS). Butylated hydroxytoluene and 4-phenyl-1,2-dihydronaphthalene were identified as two produced water components capable of inhibiting AChE at low concentrations. In order to assess the potential presence of such compounds discharged into aquatic ecosystems, AChE activity in fish tissues was measured. Saithe (Pollachius virens) caught near two offshore platforms showed lower enzymatic activity than those collected from a reference location. Target analysis of saithe did not detected the presence of these two putative AChE inhibitors and suggest that additional compounds such as PAHs, naphthenic acids and yet un-identified compounds may also contribute to the purported AChE inhibition observed in saithe. PMID:27176761

  12. Distributions of the particle/gas and dust/gas partition coefficients for seventy-two semi-volatile organic compounds in indoor environment.

    PubMed

    Wei, Wenjuan; Mandin, Corinne; Blanchard, Olivier; Mercier, Fabien; Pelletier, Maud; Le Bot, Barbara; Glorennec, Philippe; Ramalho, Olivier

    2016-06-01

    Particle/gas and dust/gas partition coefficients (Kp and Kd) are two key parameters that address the partitioning of semi-volatile organic compounds (SVOCs) between gas-phase, airborne particles, and settled dust in indoor environment. A number of empirical equations to calculate the values of Kp and Kd have been reported in the literature. Therefore, the difficulty lies in the selection of a specific empirical equation in a given situation. In this study, we retrieved from the literature 38 empirical equations for calculating Kp and Kd values from the SVOC saturation vapor pressure and octanol/air partition coefficient. These values were calculated for 72 SVOCs: 9 phthalates, 9 polybrominated diphenyl ethers (PBDEs), 11 polychlorinated biphenyls (PCBs), 22 biocides, 14 polycyclic aromatic hydrocarbons (PAHs), 3 alkylphenols, 2 synthetic musks, tributylphosphate, and bisphenol A. The mean and median values of log10Kp or log10Kd for most SVOCs were of the same order of magnitude. The distribution of log10Kp values was fitted to either a normal distribution (for 27 SVOCs) or a log-normal distribution (for 45 SVOCs). This work provides a reference distribution of the log10Kp for 72 SVOCs, and its use may reduce the bias associated with the selection of a specific value or equation. PMID:27016817

  13. 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.

  14. Solid waste deposits as a significant source of contaminants of emerging concern to the aquatic and terrestrial environments - a developing country case study from Owerri, Nigeria.

    PubMed

    Arukwe, Augustine; Eggen, Trine; Möder, Monika

    2012-11-01

    isomers), metabolites of non-ionic surfactants (nonylphenol-polyethoxylates), UV-filter compound ethyl methoxy cinnamate (EHMC) and bisphenol A (BPA) were particularly determined in the sediment samples at high μg/kg dry weight concentration. Measuring contaminants in such areas will help in increasing governmental, societal and industrial awareness on the extent and seriousness of the contamination both at waste disposal sites and surrounding terrestrial and aquatic environments. PMID:22975307

  15. Design of lipid-based delivery systems for improving lymphatic transport and bioavailability of delta-tocopherol and nobiletin

    NASA Astrophysics Data System (ADS)

    Xia, Chunxin

    overcome these problems, an O/W nanoemulsion was developed for NOB delivery with the presence of cremophor EL (a polyethoxylated excipient). The developed formulation can achieve a high NOB loading (0.5 wt%) with significantly reduced crystallinity and excellent physical stability. NOB's bioaccessibility and permeation rate across the enterocytes were demonstrated to be significantly improved by the in vitro digestion model and Caco-2 cell monolayer, respectively. It is thus predictable that NOB's bioavailability can be improved with our developed nanoemulsion formulation.

  16. A comparison of two factorial designs, a complete 3 x 3 factorial and a central composite rotatable design, for use in binomial response experiments in aquatic toxicology.

    PubMed

    Edginton, Andrea N; Sheridan, Patrick M; Boermans, Herman J; Thompson, Dean G; Holt, John D; Stephenson, Gerald R

    2004-02-01

    Using an amphibian toxicity testing protocol, comparative studies were conducted to assess the predictive precision, degree of similarity of results and efficiency of a central composite rotatable design (CCRD) in relation to a conventional complete 3x3 factorial design. Data were treated with response surface analysis using generalized linear models (glm) and application of profile deviance to generate confidence intervals. Design comparisons were based on studies conducted using the Frog Embryo Teratogenesis Assay-Xenopus (FETAX) protocol to examine the interaction of three toxicants at pH levels ranging from 4.5 to 8.5. Test substances included two commercial herbicide formulations based on glyphosate ([N-phosphonomethyl]glycine) isopropylamine salt (Vision, Rodeo) as well as a polyethoxylated tallow amine surfactant blend (MON 0818), which is a key component of the Vision formulation. The generated models from both the CCRD and the factorial designs produced toxicity estimates similar to each other and to previously published results. Trends were also similar to published results in that the surfactant, MON 0818, was comparatively more toxic than Vision, which was more toxic than Rodeo. Further, all toxicants induced higher mortality under alkaline as opposed to acidic conditions. The CCRD was between 66 and 124% more efficient in the Vision and Rodeo experiments in comparison to the complete 3x3 factorial. Thus, the factorial experiment would have required at least 66% more observations to obtain the same precision. There appeared to be no efficiency gain with the use of the CCRD for MON 0818. The CCRD had tighter confidence intervals in 9 of 12 cases across all test substances. Computer simulations using the experimental data for Vision demonstrated that the LCalpha estimates generated from the 1,000 simulated data sets were very close to the "true" value for both designs. This was based on small bias and mean squared error calculations. Coverage

  17. Degradation and environmental risk of surfactants after the application of compost sludge to the soil

    SciTech Connect

    Gonzalez, M.M.; Martin, J.; Camacho-Munoz, D.; Santos, J.L.; Aparicio, I.

    2012-07-15

    Highlights: Black-Right-Pointing-Pointer Degradation of surfactants in soil amended with sewage sludge during 100 days. Black-Right-Pointing-Pointer Temperature influences on the degradation of the studied compounds. Black-Right-Pointing-Pointer Overall, the LAS degradation is faster than the NP compounds degradation. Black-Right-Pointing-Pointer Therefore, the LAS presented lower environmental risk than the NP compounds. - Abstract: In this work, the degradation of anionic and non-ionic surfactants in agricultural soil amended with sewage sludge is reported. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10-13 carbon alkylic chain, and nonylphenolic compounds (NPE), including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO and NP2EO). The degradation studies were carried out under winter (12.7 Degree-Sign C) and summer (22.4 Degree-Sign C) conditions in Andalusia region. The concentration of LAS was reduced to 2% of the initial concentration 100 day after sludge-application to the soil. The half-life time measured for LAS homologues were ranged between 4 and 14 days at 12.7 Degree-Sign C and between 4 and 7 days at 22.4 Degree-Sign C. With regard to NPE compounds, after 8 and 4 days from the beginning of the experiment at 12.7 and 22.4 Degree-Sign C, respectively, their concentration levels were increased to 6.5 and 13.5 mg/kg dm (dry matter) as consequence of the degradation of nonylphenol polyethoxylates. These concentration levels were reduced to 5% after 63 and 70 days for 12.7 Degree-Sign C and 22.4 Degree-Sign C, respectively. The half-life times measured for NPEs were from 8 to 16 days at 12.7 Degree-Sign C and from 8 to 18 days at 22.4 Degree-Sign C. Environmental risk assessment revealed that for LAS homologues no environment risk could be expected after 7 and 8 days of sludge application to the soil for 22.4 and 12.7 Degree-Sign C, respectively; however, potential toxic effects could be

  18. WETTABILITY AND PREDICTION OF OIL RECOVERY FROM RESERVOIRS DEVELOPED WITH MODERN DRILLING AND COMPLETION FLUIDS

    SciTech Connect

    Jill S. Buckley; Norman R. Morrow

    2003-10-01

    In this report we focus on surface studies of the wetting effects of SBM components; three areas of research are covered. First we present results of tests of interfacial properties of some commercial emulsifiers that are routinely used in both oil-based and synthetic oil-based drilling fluids. These products fall into two main groups, based on their CMC and IFT trends with changing pH. All can alter the wetting of mica, but measurements vary widely depending on the details of exposure and observation protocols. Non-equilibrium effects appear to be responsible for these variations, with equilibrated fluids generally giving lower contact angles than those observed with fluids that have not been pre-equilibrated. Addition of small amounts of emulsifier can increase the tendency of a crude oil to alter wetting of mica surfaces. The effects of similar amounts of these emulsifiers can be detected in interfacial tension measurements. Next, we report on the preliminary results of a study of polyethoxylated amines of varying structures on the wetting of mica surfaces. Contact angles have been measured for unequilibrated and pre-equilibrated fluids. Reduction in contact angles was generally observed when the surfaces were washed with toluene after exposure to surfactant solutions. Atomic forces microscopy is also being used to observe the interactions between these surfactants and mica surfaces. Finally, we show the results of a study of asphaltene stability in the presence of synthetic base oils. Most of the base oils in current use are paraffinic or olefinic--the aromatic content is minimized for environmental reasons--and they destabilize asphaltenes. Tests with two crude oils show onset conditions for base oils that are comparable to n-heptane and n-pentadecane in terms of the solubility conditions at the onset. Two ester-based products, Petrofree and Petrofree LV, did not cause asphaltene flocculation in these tests. A meeting of the research groups from New Mexico

  19. Basic surface-active properties in the homologous series of β-alkyl (C12H25/C18H37) polyethyleneoxy (n = 0-20) propionamides

    PubMed Central

    2013-01-01

    Background Heterogeneous β-Alkyl (C12H25/C18H37) polyethyleneoxy (n = 0-20) propionamides [R(EO)nPD] represent new “hybrid” nonionic-ionic colloidal structures in the field of surface-active products (technical products). These “niche” compounds have three structural and compositional characteristics that also define their basic colloidal properties: mixture of R and PEO chain homologues; specific conformations due to the PEO chains; and the presence of side products from the addition of higher alcohols, polyethyleneglycols and traces of water to acrylamide. The proposed major objective of this paper is the basic informative colloidal characterization (functional classification, HLB balance, surface tension, critical micelle concentration) in direct correlation with the structural changes in the homologous series of LM(EO)nPD and CS(EO)nPD. The structures were obtained either indirectly by cyanoethylation followed by partial acid hydrolysis of the corresponding β-propionitriles, or directly by the nucleophilic addition under alkaline catalysis of linear higher alcohols C12H25/C14H29 (7/3) (LM) and C16H33/C18H37 (CS) as such and heterogeneous polyethoxylated (n = 3-20) to acrylamide monomer, through an adapted classic reaction scheme. Results In the series of basic colloidal characteristics investigated the structure-surface activity dependence is confirmed. Their indicative character for R(EO)nPD is based on the assumption that the structures studied are not unitary (heterogeneous) because: a) the hydrophobic chains C12H25/C18H37 have been grouped in two variants, C12H25/C14H29 (LM); C16H33/C18H37 (CS), each with an internal mass ratio of 7/3; b) the hydrophilic polyoxyethylene chains (n = 3-20) have polydisperse character; the meaning and value the oligomerization degree, n, is that of weighted average. In these conditions the surface tension increases proportionally with the oligomerization degree of the polyoxyethylene chain, while the

  20. In vivo and in vitro effects of the herbicide Roundup(®) on developmental stages of the trematode Echinostoma paraensei.

    PubMed

    Monte, Tainá C de C; Garcia, Juberlan; Gentile, Rosana; de Vasconcellos, Maurício Carvalho; Souza, Joyce; Braga, Brunna V; Maldonado, Arnaldo

    2016-10-01

    The exposure of wildlife and humans to toxic residues of Roundup(®) through agricultural practices or the food chain has been reported since the herbicide was found contaminating rivers. Glyphosate, N-(phosphonomethyl)glycine acid, is a nonselective post-emergent herbicide and is formulated as an isopropylamine salt with the surfactant taloamine polyethoxylate (POEA) representing the commercial formulation of Roundup(®). There is little knowledge about the effects of the herbicide on helminth parasites, particularly those whose life cycle is related to water bodies. Here we investigated the effects of the Roundup(®) on the food-borne trematode Echinostoma paraensei in experimental conditions using different developmental stages (eggs, miracidia, cercariae, metacercariae, newly excysted larvae (NEL), helminths at seven days and helminths at fourteen days). Three different herbicide concentrations were tested based on concentrations typically applied in the field: 225, 450 and 900 mg/L. Specimens were analyzed in vitro for hatching miracidia, mortality and excystment rate of metacercariae and in vivo for parasitic load and egg production. There was a significant difference in the hatching miracidia rate only for the newly embryonated eggs. The mortality of specimens and excystment rate of metacercariae were concentration-dependent. There was a significant difference in the miracidia mortality with respect to concentration until 56.3 mg/L. The same effect was observed for cercariae, and mortality was observed from 15 min onwards at concentrations of 225-900 mg/L. At low concentrations, mortality was detected after 30 min. The effects of the herbicide concentration on NEL and on helminths at seven and fourteen days showed a significant difference after 24 h. There was no significant difference in parasitic load and egg production after infection of rodents with exposed metacercariae. All developmental stages of the trematode E. paraensei were affected by

  1. Effects of polar oil related hydrocarbons on steroidogenesis in vitro in H295R cells.

    PubMed

    Knag, Anne Christine; Verhaegen, Steven; Ropstad, Erik; Mayer, Ian; Meier, Sonnich

    2013-06-01

    Oil pollution from various sources, including exploration, production and transportation, is a growing global concern. Of particular concern is the environmental impact of produced water (PW), the main waste discharge from oil and gas platforms. In this study, we have investigated the potential of polar hydrocarbon pollutants to disrupt or modulate steroidogenesis in vitro, using a human adrenocortical carcinoma cell line, the H295R assay. Effects of two of the major groups of compounds found in the polar fraction of crude oil and PW; alkylphenols (C(2)- and C(3)-AP) and naphthenic acids (NAs), as well as the polar fraction of PW as a whole has been assessed. Endpoints include hormone (cortisol, estradiol, progesterone, testosterone) production at the functional level and key genes for steroidogenesis (17β-HSD1, 17β-HSD4, 3β-HSD2, ACTHR, CYP11A1, CYP11B1, CYP11B2, CYP17, CYP19, CYP21, DAX1, EPHX, HMGR, SF1, STAR) and metabolism (CYP1A) at the molecular level. All compounds induced the production of both estradiol and progesterone in exposed H295R cells, while the C(3)-AP and NAs decreased the production of testosterone. Exposure to C(2)-AP caused an up-regulation of DAX1 and EPHX, while exposure to NAs caused an up-regulation of ACTHR. All compounds caused an up-regulation of CYP1A1. The results indicated that these hydrocarbon pollutants, including PW, have the potential to disrupt the vitally important process of steroidogenesis. PMID:23561572

  2. Occurrence and air/sea-exchange of novel organic pollutants in the marine environment

    NASA Astrophysics Data System (ADS)

    Ebinghaus, R.; Xie, Z.

    2006-12-01

    A number of studies have demonstrated that several classes of chemicals act as biologically relevant signalling substances. Among these chemicals, many, including PCBs, DDT and dioxins, are semi-volatile, persistent, and are capable of long-range atmospheric transport via atmospheric circulation. Some of these compounds, e.g. phthalates and alkylphenols (APs) are still manufactured and consumed worldwide even though there is clear evidence that they are toxic to aquatic organisms and can act as endocrine disruptors. Concentrations of NP, t-OP and NP1EO, DMP, DEP, DBP, BBP, and DEHP have been simultaneously determined in the surface sea water and atmosphere of the North Sea. Atmospheric concentrations of NP and t-OP ranged from 7 to 110 pg m - 3, which were one to three orders of magnitude below coastal atmospheric concentrations already reported. NP1EO was detected in both vapor and particle phases, which ranged from 4 to 50 pg m - 3. The concentrations of the phthalates in the atmosphere ranged from below the method detection limit to 3.4 ng m - 3. The concentrations of t-OP, NP, and NP1EO in dissolved phase were 13-300, 90-1400, and 17-1660 pg L - 1. DBP, BBP, and DEHP were determined in the water phase with concentrations ranging from below the method detection limit to 6.6 ng L - 1. This study indicates that atmospheric deposition of APs and phthalates into the North Sea is an important input pathway. The net fluxes indicate that the air sea exchange is significant and, consequently the open ocean and polar areas will be an extensive sink for APs and phthalates.

  3. Phenylphenols, biphenols, bisphenol-A and 4-tert-octylphenol exhibit alpha and beta estrogen activities and antiandrogen activity in reporter cell lines.

    PubMed

    Paris, Françoise; Balaguer, Patrick; Térouanne, Béatrice; Servant, Nadège; Lacoste, Caroline; Cravedi, Jean-Pierre; Nicolas, Jean-Claude; Sultan, Charles

    2002-07-31

    We previously demonstrated the interactions of different chemical compounds with estrogen receptors ERalpha and ERbeta and the androgen receptor (AR) using different reporter cell lines. In this study, we characterize the ERalpha, ERbeta and AR activity of different biphenyls using the same tools. We provide evidence that several phenyl derivatives present both estrogenic and antiandrogenic activity. The extent of hydroxylation and the position of the hydroxyl function were important in determining their estrogenicity and antiandrogenicity. Of the tested compounds, bisphenol-A and 4,4' biphenol had very high estrogenic activity, although it was lower than that of the strong estrogenic alkylphenol, 4-tert-octylphenol. Bisphenol-A and 4,4' biphenol were able to activate ERs at concentrations lower than 1 microM, whereas the other compounds only activated at concentrations above 1 microM. Interestingly, 4,4' biphenol was a better agonist for ERbeta than for ERalpha. No androgenic activity was detected for any of these compounds. Bisphenol-A, 3-OH phenylphenol, 4-OH phenylphenol and 4,4' biphenol exhibited antiandrogenic activity close to that of 4-tert-octylphenol (IC(50) approximately 5 microM). In whole cell binding assays, these compounds displaced [3H] R1881 with Ki = 10 microM. Although these Ki values seem high in comparison with that of hydroxyflutamide (0.4 microM), one must keep in mind that environmental chemicals can accumulate in adipose tissues for several years. In conclusion, these environmental chemicals may have a negative impact on androgen action during fetal and post-natal life. PMID:12161000

  4. Endocrine-Disrupting Potential of Bisphenol A, Bisphenol A Dimethacrylate, 4-n-Nonylphenol, and 4-n-Octylphenol in Vitro: New Data and a Brief Review

    PubMed Central

    Bonefeld-Jørgensen, Eva C.; Long, Manhai; Hofmeister, Marlene V.; Vinggaard, Anne Marie

    2007-01-01

    Background An array of environmental compounds is known to possess endocrine disruption (ED) potentials. Bisphenol A (BPA) and bisphenol A dimethacrylate (BPA-DM) are monomers used to a high extent in the plastic industry and as dental sealants. Alkylphenols such as 4-n-nonylphenol (nNP) and 4-n-octylphenol (nOP) are widely used as surfactants. Objectives We investigated the effect in vitro of these four compounds on four key cell mechanisms including transactivation of a) the human estrogen receptor (ER), b) the human androgen receptor (AR), c) the aryl hydrocarbon receptor (AhR), and d) aromatase activity. Results All four compounds inhibited aromatase activity and were agonists and antagonists of ER and AR, respectively. nNP increased AhR activity concentration-dependently and further increased the 2,3,7,8-tetrachlorodibenzo-p-dioxin AhR action. nOP caused dual responses with a weak increased and a decreased AhR activity at lower (10−8 M) and higher concentrations (10−5–10−4 M), respectively. AhR activity was inhibited with BPA (10−5–10−4 M) and weakly increased with BPA-DM (10−5 M), respectively. nNP showed the highest relative potency (REP) compared with the respective controls in the ER, AhR, and aromatase assays, whereas similar REP was observed for the four chemicals in the AR assay. Conclusion Our in vitro data clearly indicate that the four industrial compounds have ED potentials and that the effects can be mediated via several cellular pathways, including the two sex steroid hormone receptors (ER and AR), aromatase activity converting testosterone to estrogen, and AhR; AhR is involved in syntheses of steroids and metabolism of steroids and xenobiotic compounds. PMID:18174953

  5. 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.

  6. Defeminization in Daphnia magna: A screening test for endocrine-disruptors in the environment?

    SciTech Connect

    Gerritsen, A.A.M.; Hoeven, N. van der

    1995-12-31

    Long term consequences associated with exposure to endocrine disrupting chemicals in the environment have been found in mammals, birds, fish, turtles and gastropods. Despite their important role, however, hardly any attention has been paid to the long term effects of such chemicals on crustaceans. Experiments originally carried out to quantify the ability of Daphnia magna to recover from short term exposure to para-tert-pentylphenol, revealed the endocrine disrupting properties of the test compound. During one of the experiments animals were divided into six (8 hour) age groups between 0 and 48 hours and exposed to 6 mg of para-tert-pentylphenol 1{sup {minus}1} for a period of 8 hours. Within the age groups of 16 to 24 and of 24 to 32 hours old 51 and 70% of the females respectively lag-fed behind in growth and showed reduced fertility. In addition to this, about 37 and 16% of these females showed malformations suggesting defeminization. The males showed no delay in growth and had no malformations. Furthermore, in terms of survival the males were shown to be less sensitive towards the test compound than the females. The type of effects in females and the sharp distinction between the effects on males and females are indicative for the estrogenicity of para-tert-pentylphenol. The estrogenic effects of a number alkylphenols, including para-tert-pentylphenol, were demonstrated in rats and confirmed in tests with the human breast cell MCF7. To the best of knowledge estrogenicity has not been recorded before for any chemical for any crustacean. The observation of estrogenic effects in D. magna opens up the way to a standardized test for screening chemicals with potentially endocrine disrupting properties. Such a test may be a valuable tool in environmental risk assessment and conservation of environmental and human health.

  7. Comparison of produced water toxicity to Arctic and temperate species.

    PubMed

    Camus, L; Brooks, S; Geraudie, P; Hjorth, M; Nahrgang, J; Olsen, G H; Smit, M G D

    2015-03-01

    Produced water is the main discharge stream from oil and gas production. For offshore activities this water is usually discharged to the marine environment. Produced water contains traces of hydrocarbons such as polycyclic aromatic hydrocarbons as well as alkylphenols, which are relatively resistant to biodegradation and have been reported to cause adverse effects to marine organisms in laboratory studies. For management of produced water, risk-based tools have been developed using toxicity data for mainly non-Arctic species. Reliable risk assessment approaches for Arctic environments are requested to manage potential impacts of produced water associated with increased oil and gas activities in Arctic regions. In order to assess the applicability of existing risk tools for Arctic areas, basic knowledge on the sensitivity of Arctic species has to be developed. In the present study, acute and chronic toxicity of artificial produced water for 6 Arctic and 6 temperate species was experimentally tested and evaluated. The hazardous concentrations affecting 5% and 50% of the species were calculated from species sensitivity distribution curves. Hazardous concentrations were compared to elucidate whether temperate toxicity data used in risk assessment are sufficiently representative for Arctic species. From the study it can be concluded that hazardous concentration derived from individual species' toxicity data of temperate and Arctic species are comparable. However, the manner in which Arctic and non-Arctic populations and communities respond to exposure levels above established thresholds remains to be investigated. Hence, responses at higher levels of biological organization should be studied to reveal potential differences in sensitivities to produced water between Arctic and non-Arctic ecosystems. PMID:25521339

  8. Semi-volatile organic compounds in the particulate phase in dwellings: A nationwide survey in France

    NASA Astrophysics Data System (ADS)

    Mandin, Corinne; Mercier, Fabien; Ramalho, Olivier; Lucas, Jean-Paul; Gilles, Erwann; Blanchard, Olivier; Bonvallot, Nathalie; Glorennec, Philippe; Le Bot, Barbara

    2016-07-01

    Sixty-six semi-volatile organic compounds (SVOCs)-phthalates, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), one pyrethroid, organochlorine and organophosphorous pesticides, alkylphenols, synthetic musks, tri-n-butylphosphate and triclosan-were measured on PM10 filters collected over 7 days during a nationwide survey of 285 French dwellings, representative of nearly 25 million housing units. Thirty-five compounds were detected in more than half of the dwellings. PAHs, phthalates and triclosan were the major particle-bound SVOCs, with a median concentration greater than 1 ng m-3 for butylbenzyl phthalate (BBP) (median: 1.6 ng m-3), di(2-ethylhexyl) phthalate (DEHP) (46 ng m-3) and di-iso-nonyl phthalate (DiNP) (7.9 ng m-3), and greater than 0.1 ng m-3 for triclosan (114 pg m-3), benzo(a)pyrene (138 pg m-3), benzo(b)fluoranthene (306 pg m-3), benzo(g,h,i)perylene (229 pg m-3), and indeno(1,2,3-c,d)pyrene (178 pg m-3). For most of the SVOCs, higher concentrations were found in the dwellings of smokers and during the heating season. The concentrations of banned SVOCs-namely, PCBs and organochlorine pesticides-were correlated. Permethrin, 4-tert-butylphenol and bisphenol-A showed no correlation with the other SVOCs and seemed to have their own specific sources. Most SVOCs were positively associated with PM10 concentration, suggesting that any factor that raises the mass of indoor airborne particles also increases the exposure to SVOCs through inhalation.

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

    USGS Publications Warehouse

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

    2016-01-01

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

  10. 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

    2002-07-01

    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. PMID:12109482

  11. Presence of endocrine disruptors in freshwater in the northern Antarctic Peninsula region.

    PubMed

    Esteban, S; Moreno-Merino, L; Matellanes, R; Catalá, M; Gorga, M; Petrovic, M; López de Alda, M; Barceló, D; Silva, A; Durán, J J; López-Martínez, J; Valcárcel, Y

    2016-05-01

    The increasing human presence in Antarctica and the waste it generates is causing an impact on the environment at local and border scale. The main sources of anthropic pollution have a mainly local effect, and include the burning of fossil fuels, waste incineration, accidental spillage and wastewater effluents, even when treated. The aim of this work is to determine the presence and origin of 30 substances of anthropogenic origin considered to be, or suspected of being, endocrine disruptors in the continental waters of the Antarctic Peninsula region. We also studied a group of toxic metals, metalloids and other elements with possible endocrine activity. Ten water samples were analyzed from a wide range of sources, including streams, ponds, glacier drain, and an urban wastewater discharge into the sea. Surprisingly, the concentrations detected are generally similar to those found in other studies on continental waters in other parts of the world. The highest concentrations of micropollutants found correspond to the group of organophosphate flame retardants (19.60-9209ngL(-1)) and alkylphenols (1.14-7225ngL(-1)); and among toxic elements the presence of aluminum (a possible hormonal modifier) (1.7-127µgL(-1)) is significant. The concentrations detected are very low and insufficient to cause acute or subacute toxicity in aquatic organisms. However, little is known as yet of the potential sublethal and chronic effects of this type of pollutants and their capacity for bioaccumulation. These results point to the need for an ongoing system of environmental monitoring of these substances in Antarctic continental waters, and the advisability of regulating at least the most environmentally hazardous of these in the Antarctic legislation. PMID:26882535

  12. Characterization and distribution of trace organic contaminants in sediment from Masan Bay, Korea. 2: In vitro gene expression assays

    SciTech Connect

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

    1999-12-01

    Extracts of sediment collected from Masan Bay, Korea were fractionated using Florisil columns, Fractions were screened for their ability to induce estrogen- and dioxini-like gene expression in vitro using NVLN and H2IIE-luc cells, respectively, both before and after acid treatment. Florisil fraction 1 (F1), which was shown to contain polychlorinated biphenyls, induced very little response in either assay. The midpolarity Florisil fraction (F2) was the most active fraction. Twenty-seven of 28 F2 samples induced significant estrogenic activity, and all 28 samples induced significant dioxin-like activity. Twelve of the F2 samples produced magnitudes of response in the dioxin-responsive H2IIIE-luc cells similar to those induced by a 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) standard, Acid treatment did not markedly diminish the activity of F2 samples. These results suggested the presence of unidentified, acid stable, aryl hydrocarbon receptor (AhR) and estrogen receptor (ER) agonists in F2. Twenty-three of the 28 most polar florisil fractions (F3) were either cytotoxic or caused morphological changes in estrogen-responsive NVLN cells, while over half of the F3 samples caused similar effects in H2IIE-luc cells. Empirical evidence suggested that acid labile compounds contributed to both the estrogenic and cytotoxic responses of the NVLN cells. Mass balance suggested that known concentrations of alkylphenols and bisphenol A may account for a portion of the estrogenic response but were not great enough to account for the toxicity. Acid labile compounds also contributed substantially to the dioxin-like activity of F3 samples. This adds to a growing body of evidence which suggests the presence of unidentified, relatively polar, aryl hydrocarbon receptor agonists in sediment from some areas.

  13. LC-MS analysis in the aquatic environment and in water treatment technology--a critical review. Part II: Applications for emerging contaminants and related pollutants, microorganisms and humic acids.

    PubMed

    Zwiener, Christian; Frimmel, Fritz H

    2004-02-01

    Environmental contaminants of recent concern are pharmaceuticals, estrogens and other endocrine disrupting chemicals (EDC) such as degradation products of surfactants, algal and cyanobacterial toxins, disinfection by-products (DBPs) and metalloids. In addition, pesticides (especially their transformation products), microorganisms, and humic substances (HS), in their function as vehicles for contaminants and as precursors for by-products in water treatment, traditionally play an important role. The present status of the application of LC-MS techniques for these water constituents are discussed and examples of application are given. Solid-phase extraction with various non-selective materials in combination with liquid chromatography (LC) on reversed-phase columns have been the most widely used methods for sample preconcentration and separation for different compound classes like pesticides, pharmaceuticals or estrogens. Electrospray ionization (ESI) and atmospheric pressure ionization (APCI) are the most frequently used ionization techniques for polar and ionic compounds, as well as for less polar non-ionic ones. The facilities of LC-MS have been successfully demonstrated for different compound classes. Polar compounds from pharmaceuticals used as betablockers, iodinated X-ray contrast media, or estrogens have been determined without derivatization down to ultratrace concentrations. LC-MS can be viewed as a prerequisite for the determination of algal and cyanobacterial toxins and the homologues and oligomers of alkylphenol ethoxylates and their metabolites. Tandem mass spectrometric techniques and the use of diagnostic ions reveal their usefulness for compound-class specific screening and unknown identification, and are also valid for the analysis of pesticides and especially for their transformation products. Structural information has been gained by the application of LC-MS methods to organometallic species. New insights into the structural variety of humic

  14. Endocrine disrupting compounds in gaseous and particulate outdoor air phases according to environmental factors.

    PubMed

    Teil, Marie-Jeanne; Moreau-Guigon, Elodie; Blanchard, Martine; Alliot, Fabrice; Gasperi, Johnny; Cladière, Mathieu; Mandin, Corinne; Moukhtar, Sophie; Chevreuil, Marc

    2016-03-01

    This study investigated, for the first time in France, the spatial and temporal patterns of 55 endocrine disrupting chemicals (EDCs) in ambient air at three sites (urban, suburban and forest) under two climatic periods (warm/cold) for 2 successive years. All EDCs, except tetrabromobisphenol A (TBBPA), were encountered with various frequencies of up to 100%. Phthalate diesters (PAEs) were the most abundant chemicals with total concentrations as the sum of compounds, ranging from 10 to 100 ng m(-3) of total air, followed by alkylphenols (APs) and polycyclic aromatic hydrocarbons (PAHs), which were both approximately 1 ng m(-3). Polychlorinated biphenyl (PCBs) and bisphenol A (BPA) concentrations were notably lower (approximately 0.1 ng m(-3)). Air concentrations, depending on the considered compounds, were from 1.2 to 2 times higher in the urban than the suburban area and from 2 to 5 times higher in the urban than the forest site. PAH emissions were higher in the cold period, due to combustion processes. This finding is contrary to the other EDCs that are more abundant in the summer and governed by volatilisation. Most of the EDCs were largely distributed in the gaseous phase (>80% in the summer). The octanol/air partition coefficient (KOA) and vapour pressure (Vp) were relevant parameters for predicting EDC partitioning and direct relationships (p < 0.001) were observed i) between log K particle/gas partitioning (log Kp) and log KOA and ii) between EDC ratios in the gaseous phase and log vapour pressure (log Vp). PMID:26714291

  15. Molecular characterisation of the dissolved organic matter of wastewater effluents by MSSV pyrolysis GC-MS and search for source markers.

    PubMed

    Greenwood, P F; Berwick, L J; Croué, J-P

    2012-04-01

    Microscale sealed vessel pyrolysis (MSSVpy) was used to characterise the hydrophobic (HPO) and colloid (COL) fractions of dissolved organic matter (DOM) from the effluents (EFFs) of two waste water treatment plants (WWTPs) and several primary source waters (SWs). The EFFs showed a large range of anthropogenically sourced organics - including the metabolites of industrial chemicals (e.g., dioxanes, n- and sec-alkyl substituted benzenes and long chain alkyl phenols), pharmaceuticals (e.g., N- and S-heterocycles) and human waste (e.g., S- and N-organics, steranes/sterenes) - as well as high concentrations of alkyl aromatic and N-organic products (e.g., alkyl indoles, carbazoles and β-carbolines) attributed to the treatment biota. Some anthropogenic chemicals are potentially toxic at even trace levels, whilst the N-organics may be precursors for toxic N-disinfection by-products. Much lower concentrations of just a few of the anthropogenic and N-organic products were detected by more traditional flash pyrolysis (Flash-py) of the EFF samples, reflecting the higher sensitivity of MSSVpy to many chemical functionalities. Few of these products were detected in the corresponding MSSVpy analysis of the SWs, but these samples did show relatively high abundances of lignin (e.g., alkylphenols) and carbohydrate (e.g., furans) derived products. Their lower EFF abundances are consistent with efficient removal by the water treatment procedures applied. Conversely, the detection of the anthropogenics in the treated EFFs reflects their general resistance to treatment. Their occurrence in the HPO fractions isolated by XAD resin separation suggests a potential relationship with the structurally stable macromolecular fraction of the DOM. PMID:22261369

  16. A review of thermolysis studies of model compounds relevant to processing of coal

    SciTech Connect

    Poutsma, M.L.

    1987-11-01

    The bond breaking, bond making, rearrangement, and hydrogen transfer reactions that occur in coal at approx.350 to 1000/sup 0/C largely involve transient free radicals as reactive intermediates. However, the structural complexity and heterogeneity of coal has hampered development of detailed reaction mechanisms at the molecular level. Studies of the thermolysis and hydrogenolysis of model compounds, chosen to represent individual structural units in coal, provide very useful input toward that goal. These are selectively and critically reviewed in this report. Emphasis is placed on recent quantitative studies of product composition and kinetic behavior that have been carried out at low extents of conversion. The classes of organic structures covered are alkanes; aromatic hydrocarbons; alkylaromatics; ..cap alpha..,..omega..-diphenylalkanes, Ph(CH/sub 2/)/sub n/Ph (n = 0 to 4), and their analogs with a CH/sub 2/ group replaced by O, S, or NH; hydroaromatics; phenols, alkylphenols, and aryl ethers; and carbonyl compounds. Thermal behavior of pure model compounds is reviewed along with its perturbation by added hydroaromatics or molecular hydrogen. Structure-reactivity patterns within each class are illustrated whenever possible. Coverage is divided arbitrarily into a ''low-temperature regime,'' approx.300 to 450/sup 0/C and a ''high-temperature regime,'' approx.600 to 900/sup 0/C dominated by gas-phase studies. Extensive use is made of the methodology of thermochemical kinetics. Several discrepancies between literature data or suggested mechanisms and predictions based on currently accepted thermochemistry of free radicals and kinetic expressions for prototypical elementary free radical reactions are pointed out. Inversely, certain mechanistic hypotheses offered herein require experimental evaluation. 303 refs., 19 tabs.

  17. Cadmium-coordinated supramolecule suppresses tumor growth of T-cell leukemia in mice

    PubMed Central

    Zhou, Xiaoping; Koizumi, Yukio; Zhang, Muxin; Natsui, Miyuki; Koyota, Souichi; Yamada, Manabu; Kondo, Yoshihiko; Hamada, Fumio; Sugiyama, Toshihiro

    2015-01-01

    Cadmium is a toxic pollutant with occupational and environmental significance, due to its diverse toxic effects. Supramolecules that conjugate and decontaminate toxic metals have potential for use in treatment of cadmium intoxication. In addition, metal-coordinating ability has been postulated to contribute to the cytotoxic effects of anti-tumor agents such as cisplatin or bleomycin. Thiacalixarenes, cyclic oligomers of p-alkylphenol bridged by sulfur atoms, are supramolecules known to have potent coordinating ability to metal ions. In this study, we show that cadmium-coordinated thiacalix[4]arene tetrasulfate (TC4ATS-Cd) exhibits an anti-proliferative effect against T-cell leukemia cells. Cadmium exhibited cytotoxicity with IC50 values ranging from 36 to 129 μM against epithelia-derived cancer cell lines, while TC4ATS-Cd elicited no significant cytotoxicity (IC50 > 947 μM). However, a number of T-cell leukemia cell lines exhibited marked sensitivity to TC4ATS-Cd. In Jurkat cells, toxicity of TC4ATS-Cd occurred with an IC50 of 6.9 μM, which is comparable to that of 6.5 μM observed for cadmium alone. TC4ATS-Cd induced apoptotic cell death through activation of caspase-3 in Jurkat cells. In a xenograft model, TC4ATS-Cd (13 mg/kg) treatment significantly suppressed the tumor growth of Jurkat cells in mice. In addition, TC4ATS-Cd-treated mice exhibited significantly less cadmium accumulation in liver and kidney compared to equimolar cadmium-treated mice. These results suggest that cadmium-coordinated supramolecules may have therapeutic potential for treatment of T-cell leukemia. PMID:25735932

  18. Occurrence and spatial distribution of EDCs and related compounds in waters and sediments of Iberian rivers.

    PubMed

    Gorga, Marina; Insa, Sara; Petrovic, Mira; Barceló, Damià

    2015-01-15

    The environmental presence of chemicals capable of affecting the endocrine system has become a matter of scientific and public concern after certain endocrine disruptor compounds (EDCs) have been detected in the aquatic environment. In this work, 31 different EDCs and related compounds (suspect EDCs) belonging to different contaminant classes were studied: 10 estrogens, natural and synthetic, 8 alkylphenolic compounds, bisphenol A, triclosan and triclorocaraban, 4 parabens, 2 benzotriazoles, 3 organophosphorous flame retardants and the chemical marker caffeine, in river water and sediment of four Iberian rivers (Ebro, Llobregat, Júcar and Guadalquivir). An extensive sampling has been undertaken in two monitoring campaigns (2010 and 2011). A total of 77 samples of water and 75 sediments were collected. For this propose two different multiresidue analytical methods were applied, using the automated online EQuan/TurboFlow™ liquid chromatography coupled to mass spectrometry detection in tandem. In terms of concentrations the compounds found at the highest average concentrations were: nonylphenol monocarboxylate (NP1EC), tolyltriazole (TT), tris(chloroisopropyl)phosphate (TCPP) found at average concentrations above 100 ng/L, followed by 1H-benzotriazole and tris(butoxyethyl)phosphate (TBEP) found at average concentration higher than 50 ng/L. Natural and synthetic hormones were found at low levels not exceeding 16 ng/L and 7 ng/g for water and sediment, respectively, however they contributed to more than 80% of the total estrogenicity of the samples (expressed as the equivalents of estradiol EEQ, ng/L). Regarding the spatial distribution of these contaminants, the Llobregat river was found to be the most contaminated river basin, having sites near the mouth of the river the ones with the highest contaminant load. In the Ebro river basin several hot spots were identified and Júcar showed to be the least contaminated. Overall, the study confirmed the presence of

  19. Homologous expression and biochemical characterization of the arylsulfatase from Kluyveromyces lactis and its relevance in milk processing.

    PubMed

    Stressler, Timo; Leisibach, Desirée; Lutz-Wahl, Sabine; Kuhn, Andreas; Fischer, Lutz

    2016-06-01

    The industrial manufacturing process of lactose-free milk products depends on the application of commercial β-galactosidase (lactase) preparations. These preparations are often obtained from Kluyveromyces lactis. There is a gene present in the genome of K. lactis which should encode for an enzyme called arylsulfatase (EC 3.1.6.1). Therefore, this enzyme could also be present in β-galactosidase preparations. The arylsulfatase is suspected of being responsible for an unpleasant "cowshed-like" off-flavor resulting from the release of p-cresol from milk endogenous alkylphenol sulfuric esters. So far, no gene/functionality relationship is described. In addition, no study is available which has shown that arylsulfatase from K. lactis is truly responsible for the flavor generation. In this study, we cloned the putative arylsulfatase gene from K. lactis GG799 into the commercially available vector pKLAC2. The cloning strategy chosen resulted in a homologous, secretory expression of the arylsulfatase. We showed that the heretofore putative arylsulfatase has the desired activity with the synthetic substrate p-nitrophenyl sulfate and with the natural substrate p-cresol sulfate. The enzyme was biochemically characterized and showed an optimum temperature of 45-50 °C and an optimum pH of 9-10. Additionally, the arylsulfatase was activated by Ca(2+) ions and was inactivated by Zn(2+) ions. Moreover, the arylsulfatase was inhibited by p-cresol and sulfate ions. Finally, the enzyme was added to ultra-heat treated (UHT) milk and a sensory triangle test verified that the arylsulfatase from K. lactis can cause an unpleasant "cowshed-like" off-flavor. PMID:26875879

  20. Biodegradation of phenolic compounds by Basidiomycota and its phenol oxidases: A review.

    PubMed

    Martínková, L; Kotik, M; Marková, E; Homolka, L

    2016-04-01

    The phylum Basidiomycota include organisms with enormous bioremediation potential. A variety of processes were proposed at the lab scale for using these fungi and their phenol oxidases in the degradation of phenolics. Here we present a survey of this topic using literature published mostly over the last 10 years. First, the sources of the enzymes are summarized. The laccase and tyrosinase were mainly from Trametes versicolor and Agaricus bisporus, respectively. Recently, however, new promising wild-type producers of the enzymes have emerged and a number of recombinant strains were also constructed, based mainly on yeasts or Aspergillus strains as hosts. The next part of the study summarizes the enzyme and whole-cell applications for the degradation of phenols, polyphenols, cresols, alkylphenols, naphthols, bisphenols and halogenated (bis)phenols in model mixtures or real wastewaters from the food, paper and coal industries, or municipal and hospital sewage. The enzymes were applied as free (crude or purified) enzymes or as enzymes immobilized in various supports or CLEAs, and optionally recycled or used in continuous mode. Alternatively, growing cultures or harvested mycelia were used instead. The products, which were characterized as quinones and their polymers in some cases, could be eliminated by filtration, flocculation or adsorption onto chitosan. The purity of a treated wastewater was monitored using a sensitive aquatic organism. It is concluded that low-cost sources of these enzymes should be searched for and the benefits of enzymatic, biological and physico-chemical methods could be combined to make the processes fit for industrial use. PMID:26874626

  1. Dynamics of fecal indicator bacteria, bacterial pathogen genes, and organic wastewater contaminants in the Little Calumet River: Portage Burns Waterway, Indiana

    USGS Publications Warehouse

    Haack, Sheridan K.; Duris, Joseph W.

    2013-01-01

    Little information exists on the co-occurrence of fecal indicator bacteria (FIB), bacterial pathogens, and organic wastewater-associated chemicals (OWCs) within Great Lakes tributaries. Fifteen watershed sites and one beach site adjacent to the Little Calumet River–Portage Burns Waterway (LCRPBW) on Lake Michigan were tested on four dates for pH, dissolved oxygen, specific conductance, chloride, color, ammonia- and nitrate-nitrogen, soluble phosphorus, sulfate, turbidity, and atrazine; for concentrations of FIB; and for genes indicating the presence of human-pathogenic enterococci (ENT) and of Shiga-toxin producing Escherichia coli (EC) from various animal sources. Nineteen samples were also tested for 60 OWCs. Half of the watershed samples met EC recreational water quality standards; none met ENT standards. Human-wastewater-associated OWC detections were correlated with human-influence indicators such as population/km2, chloride concentrations, and the presence of WWTP effluents, but EC and ENT concentrations were not. Bacterial pathogen genes indicated rural human and several potential animal sources. OWCs of human or ecosystem health concern (musk fragrances AHTN and HHCB, alkylphenols, carbamazepine) and 3 bacterial pathogen genes were detected at the mouth of the LCRPBW, but no such OWCs and only 1 pathogen gene were detected at the beach. The LCRPBW has significant potential to deliver FIB, potential bacterial pathogens, and OWCs of human or ecosystem health concern to the nearshore of Lake Michigan, under conditions enhancing nearshore transport of the river plume. Nearshore mixing of lake and river water, and the lack of relationship between OWCs and FIB or pathogen genes, pose numerous challenges for watershed and nearshore assessment and remediation.

  2. Selective nickel-catalyzed conversion of model and lignin-derived phenolic compounds to cyclohexanone-based polymer building blocks.

    PubMed

    Schutyser, Wouter; Van den Bosch, Sander; Dijkmans, Jan; Turner, Stuart; Meledina, Maria; Van Tendeloo, Gustaaf; Debecker, Damien P; Sels, Bert F

    2015-05-22

    Valorization of lignin is essential for the economics of future lignocellulosic biorefineries. Lignin is converted into novel polymer building blocks through four steps: catalytic hydroprocessing of softwood to form 4-alkylguaiacols, their conversion into 4-alkylcyclohexanols, followed by dehydrogenation to form cyclohexanones, and Baeyer-Villiger oxidation to give caprolactones. The formation of alkylated cyclohexanols is one of the most difficult steps in the series. A liquid-phase process in the presence of nickel on CeO2 or ZrO2 catalysts is demonstrated herein to give the highest cyclohexanol yields. The catalytic reaction with 4-alkylguaiacols follows two parallel pathways with comparable rates: 1) ring hydrogenation with the formation of the corresponding alkylated 2-methoxycyclohexanol, and 2) demethoxylation to form 4-alkylphenol. Although subsequent phenol to cyclohexanol conversion is fast, the rate is limited for the removal of the methoxy group from 2-methoxycyclohexanol. Overall, this last reaction is the rate-limiting step and requires a sufficient temperature (>250 °C) to overcome the energy barrier. Substrate reactivity (with respect to the type of alkyl chain) and details of the catalyst properties (nickel loading and nickel particle size) on the reaction rates are reported in detail for the Ni/CeO2 catalyst. The best Ni/CeO2 catalyst reaches 4-alkylcyclohexanol yields over 80 %, is even able to convert real softwood-derived guaiacol mixtures and can be reused in subsequent experiments. A proof of principle of the projected cascade conversion of lignocellulose feedstock entirely into caprolactone is demonstrated by using Cu/ZrO2 for the dehydrogenation step to produce the resultant cyclohexanones (≈80 %) and tin-containing beta zeolite to form 4-alkyl-ε-caprolactones in high yields, according to a Baeyer-Villiger-type oxidation with H2 O2 . PMID:25881563

  3. Determination of endocrine disrupting compounds in fish liver, brain, and muscle using focused ultrasound solid-liquid extraction and dispersive solid phase extraction as clean-up strategy.

    PubMed

    Ros, Oihana; Vallejo, Asier; Olivares, Maitane; Etxebarria, Nestor; Prieto, Ailette

    2016-08-01

    This study describes a new method for the simultaneous extraction of several endocrine disrupting compounds, including alkylphenols (APs), estrogen, bisphenol-A (BPA) and one phthalate metabolite (mono-2-ethylhexyl ester, MEHP) in fish liver, brain, and muscle. Parameters affecting the extraction (extraction solvent and temperature) and the clean-up (dispersive phase nature and amount) steps were evaluated. The extraction was performed by means of focused ultrasound solid-liquid extraction (FUSLE) using 10 mL of n-hexane:acetone (50:50, v/v) for 5 min at ~0 °C, and the clean-up was done by means of dispersive solid phase extraction (dSPE) using 100 mg of ENVI-CARB and 100 mg of MgSO4 for the cleaning of brain and muscle extracts together with 100 mg of PSA in the case of liver extracts. Good apparent recoveries were obtained in the case of liver (62-132 %), brain (66-120 %), and muscle (74-129 %), relative standard deviation (RSD%) was always below 26 %, and the method detection limits (MDLs) were at low ng/g level. The developed method was applied to fish captured in Urdaibai estuary (Bay of Biscay) in December 2015, and the concentrations obtained were in the range MDL-1115 ng/g in brain, MDL-962 ng/g in muscle, and MDL-672 ng/g in liver. In general, the highest concentrations were measured in liver, followed by brain and muscle. In addition, diethylstilbestrol was only detected in fish brain. Graphical Abstract MS method scheme for the/MS method scheme for the determination of EDCs in fish liver, brain and muscle. PMID:27342793

  4. 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). PMID:27156752

  5. Temporal trends of persistent organic pollutants in dated sediment cores: Chemical fingerprinting of the anthropogenic impacts in the Seine River basin, Paris.

    PubMed

    Lorgeoux, C; Moilleron, R; Gasperi, J; Ayrault, S; Bonté, P; Lefèvre, I; Tassin, B

    2016-01-15

    Persistent organic pollutants (POPs) were extensively produced and used throughout the last century. In the early 1980s, a rising concern on the environmental impact of these chemicals has led to the establishment of regulations and changes of use including bans. Long term monitoring of the environmental impacts of these emissions and regulations is a challenge because regular monitoring was not mandatory at the beginning of the first emissions. Moreover, the analytical methods have been strongly improved over the decades. To overcome the lack of monitoring and accurate data, sediment cores are powerful tools to construct contamination records. In this study, a high resolution record was constructed for four POPs families (13 polycyclic aromatic hydrocarbons (PAHs), 15 polychlorinated biphenyls (PCBs), 3 alkylphenols (APs) and 8 polybromodiphenyl ethers (PBDEs)) to establish their historical trends in a long-term urbanized and industrialized environment: the Seine River basin, France. These specific families were selected because they had different sources, uses and histories. The results showed concentrations up to 90 mg/kg for ∑PAHs, 2.3mg/kg for ∑PCB, 1.2mg/kg for ∑APs and 0.06 mg/kg for ∑PBDE. The vertical distribution profiles were different from one family to another and presented a good correlation with uses (e.g. transition from coal to natural gas for PAHs), and regulation implementation (e.g., AP ban after "OSPAR Convention" in 1992). The study of compounds distribution provided original information on sources, e.g. temporal variations in PAH uses. This study demonstrates the usefulness and accuracy of sedimentary archives in floodplain to assess the fate of POPs through time in continental hydrosystems. These first results give a comprehensive overview of the contamination in the Seine River basin downstream of Paris Megacity. They were in good agreement with previous studies dedicated to European areas and highlighted specificities of this basin

  6. 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.

  7. Polydopamine-coated magnetic nanoparticles for isolation and enrichment of estrogenic compounds from surface water samples followed by liquid chromatography-tandem mass spectrometry determination.

    PubMed

    Capriotti, Anna Laura; Cavaliere, Chiara; La Barbera, Giorgia; Piovesana, Susy; Samperi, Roberto; Zenezini Chiozzi, Riccardo; Laganà, Aldo

    2016-06-01

    Estrogens, phytoestrogens, and mycoestrogens may enter into the surface waters from different sources, such as effluents of municipal wastewater treatment plants, industrial plants, and animal farms and runoff from agricultural areas. In this work, a multiresidue analytical method for the determination of 17 natural estrogenic compounds, including four steroid estrogens, six mycoestrogens, and seven phytoestrogens, in river water samples has been developed. (Fe3O4)-based magnetic nanoparticles coated by polydopamine (Fe3O4@pDA) were used for dispersive solid-phase extraction, and the final extract was analyzed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry. The Fe3O4 magnetic nanoparticles were prepared by a co-precipitation procedure, coated by pDA, and characterized by scanning electron microscopy, infrared spectroscopy, and elemental analysis. The sample preparation method was optimized in terms of extraction recovery, matrix effect, selectivity, trueness, precision, method limits of detection, and method limits of quantification (MLOQs). For all the 17 analytes, recoveries were >70 % and matrix effects were below 30 % when 25 mL of river water sample was treated with 90 mg of Fe3O4@pDA nanoparticles. Selectivity was tested by spiking river water samples with 50 other compounds (mycotoxins, antibacterials, conjugated hormones, UV filters, alkylphenols, etc.), and only aflatoxins and some benzophenones showed recoveries >60 %. This method proved to be simple and robust and allowed the determination of natural estrogenic compounds belonging to different classes in surface waters with MLOQs ranging between 0.003 and 0.1 μg L(-1). Graphical Abstract Determination of natural estrogenic compounds in water by magnetic solid phase extraction followed by liquid chromatography-tandem mass spectrometry analysis. PMID:27032407

  8. Characterisation of microcontaminants in Darwin Harbour, a tropical estuary of northern Australia undergoing rapid development.

    PubMed

    French, Veronica A; King, Susan Codi; Kumar, Anu; Northcott, Grant; McGuinness, Keith; Parry, David

    2015-12-01

    The detection of microcontaminants in aquatic environments raises concerns about their potential to exert ecotoxicological effects and impact human health. In contrast to freshwater habitats, little information is available on environmental concentrations in urban estuarine and marine environments. This study investigated an extensive range of organic and inorganic microcontaminants in the Darwin Harbour catchment, a tropical estuary in northern Australia undergoing rapid urbanisation and industrial development. We sampled wastewater effluent and surface water from seven sites in Darwin Harbour for pharmaceuticals and personal care products, alkylphenols, hormones, pesticides, herbicides and metals. In vitro bioassays were used to estimate the (anti)estrogenic and (anti)androgenic activities of samples. Seventy-nine of 229 organic microcontaminants analysed were detected at concentrations ranging from 0.01 to 20 μg/L, with acesulfame, paracetamol, cholesterol, caffeine, DEET and iopromide detected at the highest concentrations in wastewater effluent (20 μg/L, 17 μg/L, 11 μg/L, 11 μg/L, 10 μg/L and 7.6 μg/L, respectively). Levels of estrogenic activity ranged from estradiol equivalency quotients (EEQs) of <0.10 to 6.29±0.16 ng/L while levels of androgenic activity ranged from dihydrotestosterone equivalency quotients (DHTEQs) of <3.50 to 138.23±3.71 ng/L. Environmental concentrations of organic microcontaminants were comparable to ranges reported from aquatic environments worldwide with sewage effluent discharges representing the dominant source of entry into Darwin Harbour. The measured concentration range of DEET was higher than ranges reported in previous studies. PMID:26247692

  9. The characterization of eight maceral concentrates by means of Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Nip, Margriet; De Leeuw, J. W.; Schenck, P. A.

    1988-03-01

    In order to study the relationships between the chemical structures of coals, coal macerals and their precursors (plant tissues), eight coal macerals originating from the Yorkshire coal basin (U.K.) were studied by Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry. The samples were selected on the basis of a previous study of a large set of macerals. The macerals were studied in order to relate structural moieties of the macerals, as reflected by their pyrolysis products, to structural elements of their likely precursors, plant tissues. The maceral pyrolysates mainly consist of alkylbenzenes, alkylnaphthalenes, alkylphenols and series of straight-chain alk-l-enes and alkanes over a wide molecular weight range. The relative contribution of the (hydroxy)aromatic pyrolysis products and of the straight-chain alk-l-enes and alkanes to each maceral pyrolysate was calculated, although the internal distribution patterns of the alkyl derivatives of these pyrolysis products exhibited to a certain extent dissimilarities. Differences between the relative contributions of these pyrolysis products to the pyrolysates of different macerals with the same coal rank and to those of similar macerals with different coal rank depend on differences in precursor material and the chemical modification of these precursors upon increasing coalification. Multivariate data treatment by means of factor analysis was chosen to compare the pyrolysis data - represented by these histograms - with the petrographic data and the proximate and ultimate analysis values of the macerals. In addition, similar analyses was performed on the macerals using such a low Curie temperature (358°C), that from some of the macerals "thermal extracts" were obtained, containing a series of n-alkanes and some isoprenoids such as pristane and phytane. Although these thermal extracts represent only a low percentage by weight of the maceral samples, their existence

  10. Pan-European survey on the occurrence of selected polar organic persistent pollutants in ground water.

    PubMed

    Loos, Robert; Locoro, Giovanni; Comero, Sara; Contini, Serafino; Schwesig, David; Werres, Friedrich; Balsaa, Peter; Gans, Oliver; Weiss, Stefan; Blaha, Ludek; Bolchi, Monica; Gawlik, Bernd Manfred

    2010-07-01

    This study provides the first pan-European reconnaissance of the occurrence of polar organic persistent pollutants in European ground water. In total, 164 individual ground-water samples from 23 European Countries were collected and analysed (among others) for 59 selected organic compounds, comprising pharmaceuticals, antibiotics, pesticides (and their transformation products), perfluorinated acids (PFAs), benzotriazoles, hormones, alkylphenolics (endocrine disrupters), Caffeine, Diethyltoluamide (DEET), and Triclosan. The most relevant compounds in terms of frequency of detection and maximum concentrations detected were DEET (84%; 454 ng/L), Caffeine (83%; 189 ng/L), PFOA (66%; 39 ng/L), Atrazine (56%; 253 ng/L), Desethylatrazine (55%; 487 ng/L), 1H-Benzotriazole (53%; 1032 ng/L), Methylbenzotriazole (52%; 516 ng/L), Desethylterbutylazine (49%; 266 ng/L), PFOS (48%, 135 ng/L), Simazine (43%; 127 ng/L), Carbamazepine (42%; 390 ng/L), nonylphenoxy acetic acid (NPE(1)C) (42%; 11 microg/L), Bisphenol A (40%; 2.3 microg/L), PFHxS (35%; 19 ng/L), Terbutylazine (34%; 716 ng/L), Bentazone (32%; 11 microg/L), Propazine (32%; 25 ng/L), PFHpA (30%; 21 ng/L), 2,4-Dinitrophenol (29%; 122 ng/L), Diuron (29%; 279 ng/L), and Sulfamethoxazole (24%; 38 ng/L). The chemicals which were detected most frequently above the European ground water quality standard for pesticides of 0.1 microg/L were Chloridazon-desphenyl (26 samples), NPE(1)C (20), Bisphenol A (12), Benzotriazole (8), N,N'-Dimethylsulfamid (DMS) (8), Desethylatrazine (6), Nonylphenol (6), Chloridazon-methyldesphenyl (6), Methylbenzotriazole (5), Carbamazepine (4), and Bentazone (4). However, only 1.7% of all single analytical measurements (in total 8000) were above this threshold value of 0.1 microg/L; 7.3% were > than 10 ng/L. PMID:20554303

  11. Priority pollutants in wastewater and combined sewer overflow.

    PubMed

    Gasperi, Johnny; Garnaud, Stéphane; Rocher, Vincent; Moilleron, Régis

    2008-12-15

    Implementation of the European Water Framework Directive and its affiliated directives requires Member States to improve their understanding of priority pollutants (PPs) in urban areas and obviously within wastewater systems. As a direct consequence, this study is intended to furnish data on both PP occurrence and the significance of concentrations in wastewater during dry and wet periods within combined sewers. Various sampling sites within the Paris combined sewer network were selected; for each sample, a total of 66 determinants, including metals, polycyclic aromatic hydrocarbons (PAHs), pesticides, organotins, volatile organic compounds, chlorobenzenes, phthalates and alkylphenols, were analysed. A broad range of PPs was observed in wastewater during dry as well as wet weather periods. Of the 66 elements investigated, 33 and 40 priority substances could be observed in raw sewage and wet weather effluent, respectively. As expected, a majority of metals were present in all samples, reflecting their ubiquitous nature. For both periods, chlorobenzenes and most of the pesticides always remained below the limit of quantification, while the majority of other organic pollutants assessed were identified within the microg l(-1) range. As highlighted by the larger number of substances detected in wet weather samples and the significance of their concentrations, runoff via atmospheric inputs and/or surface leaching was found to induce a wider range of PPs (n=40) and lead to higher concentrations of certain metals, PAHs, pesticides and other individual compounds. The data generated during this survey, which constitutes one of the first studies conducted in Europe to report concentrations for a variety of priority substances in wastewater within combined sewers, may be used in the future to identify PPs of potential significance for dry and wet weather periods and targeted for further investigation. PMID:18814902

  12. Combinations of physiologic estrogens with xenoestrogens alter calcium and kinase responses, prolactin release, and membrane estrogen receptor trafficking in rat pituitary cells

    PubMed Central

    2010-01-01

    Background Xenoestrogens such as alkylphenols and the structurally related plastic byproduct bisphenol A have recently been shown to act potently via nongenomic signaling pathways and the membrane version of estrogen receptor-α. Though the responses to these compounds are typically measured individually, they usually contaminate organisms that already have endogenous estrogens present. Therefore, we used quantitative medium-throughput screening assays to measure the effects of physiologic estrogens in combination with these xenoestrogens. Methods We studied the effects of low concentrations of endogenous estrogens (estradiol, estriol, and estrone) at 10 pM (representing pre-development levels), and 1 nM (representing higher cycle-dependent and pregnancy levels) in combinations with the same levels of xenoestrogens in GH3/B6/F10 pituitary cells. These levels of xenoestrogens represent extremely low contamination levels. We monitored calcium entry into cells using Fura-2 fluorescence imaging of single cells. Prolactin release was measured by radio-immunoassay. Extracellular-regulated kinase (1 and 2) phospho-activations and the levels of three estrogen receptors in the cell membrane (ERα, ERβ, and GPER) were measured using a quantitative plate immunoassay of fixed cells either permeabilized or nonpermeabilized (respectively). Results All xenoestrogens caused responses at these concentrations, and had disruptive effects on the actions of physiologic estrogens. Xenoestrogens reduced the % of cells that responded to estradiol via calcium channel opening. They also inhibited the activation (phosphorylation) of extracellular-regulated kinases at some concentrations. They either inhibited or enhanced rapid prolactin release, depending upon concentration. These latter two dose-responses were nonmonotonic, a characteristic of nongenomic estrogenic responses. Conclusions Responses mediated by endogenous estrogens representing different life stages are vulnerable to very

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

    PubMed Central

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

    2011-01-01

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

  14. Optimization and Simultaneous Determination of Alkyl Phenol Ethoxylates and Brominated Flame Retardants in Water after SPE and Heptafluorobutyric Anhydride Derivatization followed by GC/MS.

    PubMed

    Chokwe, Tlou B; Okonkwo, Jonathan O; Sibali, Linda L; Ncube, Esper J

    2012-10-01

    A gas chromatography-mass spectrometry (GC-MS) method was investigated for the simultaneous analysis of two types of endocrine disrupting compounds (EDCs), i.e., alkylphenol ethoxylates and brominated flame retardants (BFRs), by extraction and derivatization followed by GC-MS. Different solid phase extraction (SPE) cartridges (Cleanert PestiCarb, C18, Cleanert-SAX and Florosil), solvents (toluene, tetrahydrofuran, acetone, acetonitrile and ethyl acetate) and bases (NaHCO3, triethylamine and pyridine) were tested and the best chromatographic analysis was achieved by extraction with Strata-X (33 μm, Reverse Phase) cartridge and derivatization with heptafluorobutyric anhydride at 55 °C under Na2CO3 base in hexane. It was observed that APE together with lower substituted PBBs (PBB1, PBB10, PBB18 and PBB49), HBCD and TBBPA can be determined simultaneously under the same GC conditions. This simple and reliable analytical method was applied to determining trace amounts of these compounds from wastewater treatment plant samples. The recoveries of the target compounds from simulated water were above 60 %. The limit of detection ranged from 0.01 to 0.15 μg L(-1) and the limit of quantification ranged from 0.05 to 0.66 μg L(-1). There were no appreciable differences between filtered and unfiltered wastewater samples from Leeuwkil treatment plant although concentration of target analytes in filtered influent was slightly lower than the concentration of target analytes in unfiltered influent water. The concentrations of the target compounds from the wastewater treatment were determined from LOQ upwards. PMID:23864736

  15. Monitoring of environmental phenolic endocrine disrupting compounds in treatment effluents and river waters, Korea.

    PubMed

    Ko, Eun-Joung; Kim, Kyoung-Woong; Kang, Seo-Young; Kim, Sang-Don; Bang, Sun-Baek; Hamm, Se-Yeong; Kim, Dong-Wook

    2007-10-15

    The last two decades have witnessed growing scientific and public concerns over endocrine disrupting compounds (EDCs) that have the potential to alter the normal structure or functions of the endocrine system in wildlife and humans. In this study, the phenolic EDCs such as alkylphenol, chlorinated phenol and bisphenol A were considered. They are commonly found in wastewater discharges and in sewage treatment plant. In order to monitor the levels and seasonal variations of phenolic EDCs in various aquatic environments, a total of 15 water samples from the discharged effluent from sewage and wastewater treatment plants and river water were collected for 3 years. Ten environmental phenolic EDCs were determined by GC-MS and laser-induced fluorescence (LIF). GC-MS analysis revealed that most abundant phenolic EDCs were 4-n-heptylphenol, followed by nonlyphenol and bisphenol A during 2002-2003, while 4-t-butylphenol and 4-t-octylphenol were newly detected in aquatic environments in 2004. The category of phenolic EDCs showed similar fluorescence spectra and nearly equal fluorescence decay time. This makes it hard to distinguish each phenolic EDC from the EDCs mixture by LIF. Therefore, the results obtained from LIF analysis were expressed in terms of the fluorescence intensity of the total phenolic EDCs rather than that of the individual EDC. However, LIF monitoring and GC-MS analysis showed consistent result in that the river water samples had lower phenolic EDCs concentration compared to the effluent sample. This revealed a lower fluorescence intensity and the phenolic EDCs concentration in summer was lower than that in winter. For the validation of LIF monitoring for the phenolic EDCs, the correlation between EDCs concentration acquired from GC-MS and fluorescence intensity from LIF was obtained (R=0.7379). This study supports the feasibility of the application of LIF into EDCs monitoring in aquatic systems. PMID:19073088

  16. Combinations of Physiologic Estrogens with Xenoestrogens Alter ERK Phosphorylation Profiles in Rat Pituitary Cells

    PubMed Central

    Jeng, Yow-Jiun; Watson, Cheryl S.

    2011-01-01

    Background Estrogens are potent nongenomic phospho-activators of extracellular-signal–regulated kinases (ERKs). A major concern about the toxicity of xenoestrogens (XEs) is potential alteration of responses to physiologic estrogens when XEs are present simultaneously. Objectives We examined estrogen-induced ERK activation, comparing the abilities of structurally related XEs (alkylphenols and bisphenol A) to alter ERK responses induced by physiologic concentrations (1 nM) of estradiol (E2), estrone (E1), and estriol (E3). Methods We quantified hormone/mimetic-induced ERK phosphorylations in the GH3/B6/F10 rat pituitary cell line using a plate immunoassay, comparing effects with those on cell proliferation and by estrogen receptor subtype-selective ligands. Results Alone, these structurally related XEs activate ERKs in an oscillating temporal pattern similar (but not identical) to that with physiologic estrogens. The potency of all estrogens was similar (active between femtomolar and nanomolar concentrations). XEs potently disrupted physiologic estrogen signaling at low, environmentally relevant concentrations. Generally, XEs potentiated (at the lowest, subpicomolar concentrations) and attenuated (at the highest, picomolar to 100 nM concentrations) the actions of the physiologic estrogens. Some XEs showed pronounced nonmonotonic responses/inhibitions. The phosphorylated ERK and proliferative responses to receptor-selective ligands were only partially correlated. Conclusions XEs are both imperfect potent estrogens and endocrine disruptors; the more efficacious an XE, the more it disrupts actions of physiologic estrogens. This ability to disrupt physiologic estrogen signaling suggests that XEs may disturb normal functioning at life stages where actions of particular estrogens are important (e.g., development, reproductive cycling, pregnancy, menopause). PMID:20870566

  17. 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

  18. Investigation of the estrogenic risk to feral male brown trout (Salmo trutta) in the Shannon International River Basin District of Ireland.

    PubMed

    Kelly, Miriam A; Reid, Antoinette M; Quinn-Hosey, Kathryn M; Fogarty, Andrew M; Roche, James J; Brougham, Concepta A

    2010-10-01

    The estrogenic potential of sewage treatment effluents and their receiving waters in the Shannon International River Basin District (SIRBD) of Ireland was investigated. An integrated approach, combining biological and chemical methods, was conducted to assess 11 rivers adjacent to sewage treatment plants (STPs) and their possible interference with the endocrine system of feral brown trout (Salmo trutta). Hepatosomatic index, gonadosomatic index, condition factor, histological (intersexuality) and endocrine (vitellogenin induction) parameters were assessed in a sample size of 10 at each location. The estrogenic burden was determined using an in vitro recombinant yeast assay containing the human estrogen receptor (YES assay). In addition, endocrine disrupting chemicals (EDCs) were quantitatively identified through a selection of pre-concentration techniques combined with chromatographic analysis at or near the selected locations. Chemical analysis of representative site samples identified phthalates and an alkylphenol in water and sediments in μg/L and mg/kg concentrations, respectively. There were no significant difference in somatic indices or the condition factor between upstream control and downstream test sites, and there was no evidence of reproductive alterations or the presence of intersex in studied male brown trout. However, raised vitellogenin (vtg) levels were detected in the blood plasma samples of male brown trout at 8 of the 11 sites. Significant levels were reported at 3 of the positive sites (p ≤ 0.05). In one particular location, vtg induction was observed in 100% of the male brown trout sampled downstream. These findings were supported by the YES assay, where estrogenic activity was detected in the same upstream and downstream sites giving 17β-estradiol equivalency factor (EEF) values of up to 2.67 ng/L. This study represents an integrated assessment approach, confirming the presence of estrogens in rivers of the SIRBD of Ireland, thus

  19. Analysis of thiabendazole, 4-tert-octylphenol and chlorpyrifos in waste and sewage water by direct injection – micellar liquid chromatography.

    PubMed

    Romero-Cano, Ricard; Kassuha, Diego; Peris-Vicente, Juan; Roca-Genovés, Pasqual; Carda-Broch, Samuel; Esteve-Romero, Josep

    2015-03-01

    A micellar liquid chromatographic method has been developed for the simultaneous quantification of the pesticides thiabendazole and chlorpyrifos, as well as an alkylphenol, which is included in pesticide formulations, i.e., 4-tert-octylphenol, in water. A sample was filtered and directly injected, avoiding large extraction steps using toxic solvents, thus expediting the experimental procedure. The contaminants were eluted without interferences in <17 min, using a mobile phase of 0.15 M sodium dodecyl sulfate – 6% 1-pentanol buffered at pH 3, running through a C18 column at 1 mL min(-1) under the isocratic mode. This optimal mobile phase was selected using a statistical approach, which considers the retention factor, efficiency and peak shape of the analytes measured in only a few mobile phases. The detection was carried out by measuring absorbance at 220 nm. The method was successfully validated in terms of specificity, calibration range (0.5-10 mg L(-1)), linearity (r(2) > 0.994), limit of detection and quantification (0.2-0.3; and 0.5-0.8 mg L(-1), respectively), intra- and interday accuracy (95.2-102.9%), precision (<8.3%), and ruggedness (<9.3%). The stability in storage conditions (at least 14 days) was studied. The method was safe, inexpensive, produced little pollutant and has a short analysis time, thus it is useful for the routine analysis of samples. Finally, the method was applied to analyse wastewater from the fruit-processing industry, wastewater treatment plants, and in sewage water belonging to the Castelló area (Spain). The results were similar to those obtained by an already reliable method. PMID:25604004

  20. Selective determination of estrogenic compounds in water by microextraction by packed sorbents and a molecularly imprinted polymer coupled with large volume injection-in-port-derivatization gas chromatography-mass spectrometry.

    PubMed

    Prieto, A; Vallejo, A; Zuloaga, O; Paschke, A; Sellergen, B; Schillinger, E; Schrader, S; Möder, M

    2011-10-01

    A fully automated protocol consisting of microextraction by packed sorbents (MEPS) coupled with large volume injection-in-port-derivatization-gas chromatography-mass spectrometry (LVI-derivatization-GC-MS) was developed to determine endocrine disrupting compounds (EDCs) such as alkylphenols, bisphenol A, and natural and synthetic hormons in river and waste water samples. During method optimization, the extraction parameters as ion strength of the water sample, the MEPS extraction regime, the volume of organic solvent used for the elution/injection step, the type of elution solvents and the selectivity of the sorbents were studied. For optimum in-port-derivatization, 10 μL of the derivatization reagent N,O-bis(trimethylsilyl)triufloroacetamide with 1% of trimethylchlorosilane (BSTFA+1% TMCS) was used. 17β-Estradiol-molecularly imprinted polymer (MIP) and silica gel (modified with C-18) sorbents were examined for the enrichment of the target analytes from water samples and the obtained results revealed the high selectivity of the MIP material for extraction of substances with estrogen-like structures. Recovery values for most of the analytes ranged from 75 to 109% for the C18 sorbent and from 81 to 103% for the MIP material except for equilin (on C18 with only 57-66% recovery). Precision (n=4) of the entire analysis protocol ranged between 4% and 22% with both sorbents. Limits of detection (LODs) were at the low ngL(-1) level (0.02-87, C18 and 1.3-22, MIP) for the target analytes. PMID:21843673

  1. Transcriptional responses, metabolic activity and mouthpart deformities in natural populations of Chironomus riparius larvae exposed to environmental pollutants.

    PubMed

    Planelló, Rosario; Servia, María J; Gómez-Sande, Pablo; Herrero, Óscar; Cobo, Fernando; Morcillo, Gloria

    2015-04-01

    Biomarkers are an important tool in laboratory assays that link exposure or effect of specific toxicants to key molecular and cellular events, but they have not been widely used in invertebrate populations exposed to complex mixtures of environmental contaminants in their natural habitats. The present study focused on a battery of biomarkers and their comparative analysis in natural populations of the benthic larvae of Chironomus riparius (Diptera), sampled in three differentially polluted rivers (the Con, Sar, and Louro in Galicia, Spain). In our study, some parameters were identified, such as hsp70 gene activity, GST enzymatic activity, total glycogen content and mouthpart deformities, which showed significant differences among populations from the three rivers that differed in the levels and types of sedimentary contaminants analyzed (metals, organic-chlorine pesticides, alkylphenols, pharmaceutical, and personal care products). In contrast to these sensitive biomarkers, other parameters showed no significant differences (hsc70 gene, EcR gene, P450 gene, RNA:DNA ratio, total protein content), and were stable even when comparing field and nonexposed laboratory populations. The hsp70 gene seems to be particularly sensitive to conditions of pollutant exposure, while its constitutive counterpart hsc70 showed invariable expression, suggesting that the hsc70/hsp70 ratio may be a potential indicator of polluted environments. Although further studies are required to understand the correlation between molecular responses and the ecological effects of pollutants on natural populations, the results provide new data about the biological responses to multiple-stressor environments. This field study adds new molecular endpoints, including gene expression, as suitable tools that, complementing other ecotoxicological parameters, may help to improve the methodologies of freshwater monitoring under the increasing burden of xenobiotics. PMID:23893657

  2. Development of an Enzyme-linked Immunosorbent Assay Using Vitellin for Vitellogenin Measurement in the Pale Chub, Zacco platypus

    PubMed Central

    Lim, Eun-Suk; Lee, Eun Hee; Kim, Myung Hee; Han, Chang-Hee; Lee, Sung-Kyu

    2013-01-01

    Objectives Fish vitellogenin (VTG) is produced in the female liver during oogenesis through the estradiol cycle and produced in the male liver by endocrine disrupting chemicals (EDCs) such as alkylphenols. In this study, we propose that the VTG concentration in the pale chub could be detected using monoclonal antibodies and polyclonal antibodies against vitellin (Vn) in a VTG enzyme-linked immunosorbent assay (ELISA) system. Methods Monoclonal antibodies and polyclonal antibodies were produced using the Vn extracted from the matured ovum of the ovary. The VTG was extracted from the plasma of the male pale chub. The Vn and VTG were confirmed by measuring the molecular weight of their proteins using sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and the specificity of the antibodies was checked through western blotting methods. The assay system was validated with respect to optimal assay concentrations, specificity, recovery, and intra- and inter-assay variations. Results The Vn consisted of two protein bands with apparent molecular weights of 64 and 37 kDa. The SDS-PAGE indicated protein weights of 146 and 77 kDa in the VTG. The assay range was 15.6 ng/mL to 2,000 ng/mL, and the value of the intra- and inter-assay variations were within 10.0% and 14.7%, respectively. The recovery rate was 99.5±5.5%. Conclusions A sandwich ELISA was developed that could be used to qualify the VTG of pale chub in screening for EDCs. Pale chub is an ideal species for observing estrogen activity in the environment because of its extensive habitat and extensive food chain. The ELISA developed here would be more favorable than those for other species for determining the effect of long-term food chain accumulation of EDCs in aquatic environments. PMID:24498593

  3. Endocrine disrupting chemicals in indoor and outdoor air

    PubMed Central

    Rudel, Ruthann A.; Perovich, Laura J.

    2009-01-01

    The past 50 years have seen rapid development of new building materials, furnishings, and consumer products and a corresponding explosion in new chemicals in the built environment. While exposure levels are largely undocumented, they are likely to have increased as a wider variety of chemicals came into use, people began spending more time indoors, and air exchange rates decreased to improve energy efficiency. As a result of weak regulatory requirements for chemical safety testing, only limited toxicity data are available for these chemicals. Over the past 15 years, some chemical classes commonly used in building materials, furnishings, and consumer products have been shown to be endocrine disrupting chemicals—that is they interfere with the action of endogenous hormones. These include PCBs, used in electrical equipment, caulking, paints and surface coatings; chlorinated and brominated flame retardants, used in electronics, furniture, and textiles; pesticides, used to control insects, weeds, and other pests in agriculture, lawn maintenance, and the built environment; phthalates, used in vinyl, plastics, fragrances, and other products; alkylphenols, used in detergents, pesticide formulations, and polystyrene plastics; and parabens, used to preserve products like lotions and sunscreens. This paper summarizes reported indoor and outdoor air concentrations, chemical use and sources, and toxicity data for each of these chemical classes. While industrial and transportation-related pollutants have been shown to migrate indoors from outdoor sources, it is expected that indoor sources predominate for these consumer product chemicals; and some studies have identified indoor sources as the predominant factor influencing outdoor ambient air concentrations in densely populated areas. Mechanisms of action, adverse effects, and dose-response relationships for many of these chemicals are poorly understood and no systematic screening of common chemicals for endocrine disrupting

  4. The E-SCREEN assay as a tool to identify estrogens: an update on estrogenic environmental pollutants.

    PubMed Central

    Soto, A M; Sonnenschein, C; Chung, K L; Fernandez, M F; Olea, N; Serrano, F O

    1995-01-01

    Estrogens are defined by their ability to induce the proliferation of cells of the female genital tract. The wide chemical diversity of estrogenic compounds precludes an accurate prediction of estrogenic activity on the basis of chemical structure. Rodent bioassays are not suited for the large-scale screening of chemicals before their release into the environment because of their cost, complexity, and ethical concerns. The E-SCREEN assay was developed to assess the estrogenicity of environmental chemicals using the proliferative effect of estrogens on their target cells as an end point. This quantitative assay compares the cell number achieved by similar inocula of MCF-7 cells in the absence of estrogens (negative control) and in the presence of 17 beta-estradiol (positive control) and a range of concentrations of chemicals suspected to be estrogenic. Among the compounds tested, several "new" estrogens were found; alkylphenols, phthalates, some PCB congeners and hydroxylated PCBs, and the insecticides dieldrin, endosulfan, and toxaphene were estrogenic by the E-SCREEN assay. In addition, these compounds competed with estradiol for binding to the estrogen receptor and increased the levels of progesterone receptor and pS2 in MCF-7 cells, as expected from estrogen mimics. Recombinant human growth factors (bFGF, EGF, IGF-1) and insulin did not increase in cell yields. The aims of the work summarized in this paper were a) to validate the E-SCREEN assay; b) to screen a variety of chemicals present in the environment to identify those that may be causing reproductive effects in wildlife and humans; c) to assess whether environmental estrogens may act cumulatively; and finally d) to discuss the reliability of this and other assays to screen chemicals for their estrogenicity before they are released into the environment. PMID:8593856

  5. 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.

  6. Endocrine disrupting chemicals in indoor and outdoor air

    NASA Astrophysics Data System (ADS)

    Rudel, Ruthann A.; Perovich, Laura J.

    The past 50 years have seen rapid development of new building materials, furnishings, and consumer products and a corresponding explosion in new chemicals in the built environment. While exposure levels are largely undocumented, they are likely to have increased as a wider variety of chemicals came into use, people began spending more time indoors, and air exchange rates decreased to improve energy efficiency. As a result of weak regulatory requirements for chemical safety testing, only limited toxicity data are available for these chemicals. Over the past 15 years, some chemical classes commonly used in building materials, furnishings, and consumer products have been shown to be endocrine disrupting chemicals - that is they interfere with the action of endogenous hormones. These include PCBs, used in electrical equipment, caulking, paints and surface coatings; chlorinated and brominated flame retardants, used in electronics, furniture, and textiles; pesticides, used to control insects, weeds, and other pests in agriculture, lawn maintenance, and the built environment; phthalates, used in vinyl, plastics, fragrances, and other products; alkylphenols, used in detergents, pesticide formulations, and polystyrene plastics; and parabens, used to preserve products like lotions and sunscreens. This paper summarizes reported indoor and outdoor air concentrations, chemical use and sources, and toxicity data for each of these chemical classes. While industrial and transportation-related pollutants have been shown to migrate indoors from outdoor sources, it is expected that indoor sources predominate for these consumer product chemicals; and some studies have identified indoor sources as the predominant factor influencing outdoor ambient air concentrations in densely populated areas. Mechanisms of action, adverse effects, and dose-response relationships for many of these chemicals are poorly understood and no systematic screening of common chemicals for endocrine disrupting

  7. Sorption behaviour of nonylphenol and nonylphenol monoethoxylate in soils.

    PubMed

    Milinovic, J; Lacorte, S; Rigol, A; Vidal, M

    2015-11-01

    Sorption behaviour of two alkylphenolic compounds (APCs), nonylphenol (NP) and nonylphenol monoethoxylate (NP1EO), was studied in five soils with contrasting characteristics. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions containing different initial concentrations of NP or NP1EO. Linear fitting was generally appropriate for describing the sorption behaviour of NP and NP1EO in the soils, with the exception of two cases, for which the Freundlich model was more suitable for describing the sorption pattern of NP1EO. Solid-liquid distribution coefficients derived from sorption isotherms (Kd) varied from 24 to 1059 mL g(-1) for NP and from 51 to 740 mL g(-1) for NP1EO. For most soils, sorption Kd values were higher for NP than for NP1EO due to the higher hydrophobicity of NP. Sorption reversibility of NP and NP1EO was also tested from desorption isotherms. Desorption solid-liquid distribution coefficients (Kd,des), obtained from linear fitting, were between 130 and 1467 mL g(-1) for NP and between 24 and 1285 mL g(-1) for NP1EO. Kd,des values were higher than Kd values, which demonstrated that target compounds were irreversibly sorbed into soils, with the exception of the high desorption yield (45%) of NP1EO in the soil with the lowest content of organic matter. The fraction of soil organic carbon (FOC) was a key parameter that influenced the sorption of NP and NP1EO in soils, with logKOC values of 4.0 and 3.8, respectively. PMID:25595537

  8. Screening of endocrine-disrupting phenols, herbicides, steroid estrogens, and estrogenicity in drinking water from the waterworks of 35 Italian cities and from PET-bottled mineral water.

    PubMed

    Maggioni, Silvia; Balaguer, Patrick; Chiozzotto, Claudia; Benfenati, Emilio

    2013-03-01

    We investigated contamination by endocrine-disrupting chemicals in drinking water from 35 major Italian cities and five popular Italian brands of bottled mineral water. The quality of Italian drinking water was assessed by combing chemical analysis with bioassay to quantify specific estrogenic contaminants and to characterize the actual biological effect of the mixture of chemicals present in drinking water including the contribution of not targeted compounds. The selected contaminants were natural and synthetic steroid estrogens, alkylphenols and bisphenol A, linuron, triazine herbicides, and their metabolites. A specific analytical method was developed based on solid phase extraction of 1 L of water and concentration to 100 μL for quantification by electrospray ionization liquid chromatography tandem mass spectrometry, achieving quantification limits of 0.05-0.36 ng/L for herbicides and 0.64-7.70 ng/L for steroids and phenols. No steroid estrogens were detected in any of the samples, while bisphenol A and nonylphenols were detected in the ranges of 0.82-102.00 and 10.30-84.00 ng/L respectively. Herbicides and their degradation products, when present, were found from slightly above the quantification limits up to 49.91 ng/L, mainly from cities in northern Italy. Chemical analyses were complemented by the performance of a bioassay for the determination of the estrogenic activity in the extracts based on the transactivation of estrogen receptor α-transfected reporter HeLa-ERE-Luciferase-Neomycin cell line. Activity was generally low with maximum estrogenicity of 13.6 pg/L estradiol equivalents. PMID:22821279

  9. Endocrine Disruptors and Asthma-Associated Chemicals in Consumer Products

    PubMed Central

    Nishioka, Marcia; Standley, Laurel J.; Perovich, Laura J.; Brody, Julia Green; Rudel, Ruthann A.

    2012-01-01

    Background: Laboratory and human studies raise concerns about endocrine disruption and asthma resulting from exposure to chemicals in consumer products. Limited labeling or testing information is available to evaluate products as exposure sources. Objectives: We analytically quantified endocrine disruptors and asthma-related chemicals in a range of cosmetics, personal care products, cleaners, sunscreens, and vinyl products. We also evaluated whether product labels provide information that can be used to select products without these chemicals. Methods: We selected 213 commercial products representing 50 product types. We tested 42 composited samples of high-market-share products, and we tested 43 alternative products identified using criteria expected to minimize target compounds. Analytes included parabens, phthalates, bisphenol A (BPA), triclosan, ethanolamines, alkylphenols, fragrances, glycol ethers, cyclosiloxanes, and ultraviolet (UV) filters. Results: We detected 55 compounds, indicating a wide range of exposures from common products. Vinyl products contained > 10% bis(2-ethylhexyl) phthalate (DEHP) and could be an important source of DEHP in homes. In other products, the highest concentrations and numbers of detects were in the fragranced products (e.g., perfume, air fresheners, and dryer sheets) and in sunscreens. Some products that did not contain the well-known endocrine-disrupting phthalates contained other less-studied phthalates (dicyclohexyl phthalate, diisononyl phthalate, and di-n-propyl phthalate; also endocrine-disrupting compounds), suggesting a substitution. Many detected chemicals were not listed on product labels. Conclusions: Common products contain complex mixtures of EDCs and asthma-related compounds. Toxicological studies of these mixtures are needed to understand their biological activity. Regarding epidemiology, our findings raise concern about potential confounding from co-occurring chemicals and misclassification due to variability in

  10. Fate and metabolism of the brominated flame retardant tetrabromobisphenol A (TBBPA) in rice cell suspension culture.

    PubMed

    Wang, Songfeng; Cao, Siqi; Wang, Yongfeng; Jiang, Bingqi; Wang, Lianhong; Sun, Feifei; Ji, Rong

    2016-07-01

    Tetrabromobisphenol A (TBBPA) is the brominated flame retardant with the highest production volume and its bioaccumulation in environment has caused both human health and environmental concerns, however the fate and metabolism of TBBPA in plants is unknown. We studied the fate, metabolites, and transformation of (14)C-labeled TBBPA in rice cell suspension culture. During the incubation for 14 days, TBBPA degradation occurred continuously in the culture, accompanied by formation of one anisolic metabolite [2,6-dibromo-4-(2-(2-hydroxy)-propyl)-anisole] (DBHPA) (50% of the degraded TBBPA) and cellular debris-bound residues (46.4%) as well as mineralization (3.6%). The cells continuously accumulated TBBPA in the cytoplasm, while a small amount of DBHPA (2.1% of the initially applied TBBPA) was detectable inside the cells only at the end of incubation. The majority of the accumulated residues in the cells was attributed to the cellular debris-bound residues, accounting for 70-79% of the accumulation after the first incubation day. About 5.4% of the accumulation was associated with cell organelles, which contributed 7.5% to the cellular debris-bound residues. Based on the fate and metabolism of TBBPA in the rice cell suspension culture, a type II ipso-substitution pathway was proposed to describe the initial step for TBBPA degradation in the culture and balance the fate of TBBPA in the cells. To the best of our knowledge, our study provides for the first time the insights into the fate and metabolism of TBBPA in plants and points out the potential role of type II ipso-hydroxylation substitution in degradation of alkylphenols in plants. Further studies are required to reveal the mechanisms for the bound-residue formation (e.g., binding of residues to specific cell wall components), nature of the binding, and toxicological effects of the bound residues and DBHPA. PMID:27105166

  11. Physical, chemical, and biological characteristics of Sturgeon Lake, Goodhue County, Minnesota, 2003-04

    USGS Publications Warehouse

    Lee, Kathy E.; Sanocki, Christopher A.; Montz, Gary R.

    2005-01-01

    The U.S. Geological Survey, in cooperation with the Prairie Island Indian Community and the Minnesota Department of Natural Resources, conducted a study of Sturgeon Lake (a backwater lake in Navigation Pool 3 of the Mississippi River) during 2003-04 to describe the physical, chemical, and biological characteristics of the lake. Riparian and shoreline areas surrounding Sturgeon Lake consist primarily of deciduous tree and shrub cover with minimal amounts of commercial or residential land use. Woody debris and aquatic vegetation are the major types of physical habitat suitable for fish and invertebrates. Among 10 bottom-sediment sampling sites, 24 organic wastewater compounds, 1 organochlorine pesticide metabolite (p,p’DDE), and total polychlorinated biphenyls (PCBs) were detected in the bottom sediments of Sturgeon Lake. The most prevalent class of compounds detected were polyaromatic hydrocarbons. Other classes of compounds detected include sterols, disinfectants, plastic components, alkylphenols, and fragrances. Three compounds detected (bisphenol A, benzo[a]pyrene, and triclosan) are considered endocrine disrupting compounds. Twenty-one and 49 invertebrate taxa were identified from 10 bottom-sediment and 6 woody-debris/vegetation samples, respectively. Most of the taxa were Diptera in the family Chironomidae. The most common invertebrate in terms of density in bottom-sediment samples was the burrowing mayfly (Hexagenia sp.). Trichoptera in the families Hydropsychidae or Polycentropodidae were common in most of the woody-debris samples. The presence of the Hexagenia larvae in samples indicates that the bottom sediments are stable and that dissolved oxygen concentrations in the lake do not drop to acute or sub-lethal anoxic conditions. Backwater lakes such as Sturgeon Lake are important areas of habitat for aquatic organisms along the Mississippi River, and this report provides baseline physical, chemical, and biological information that resource managers can

  12. Potential hazards of environmental contaminants to avifauna residing in the Chesapeake Bay Estuary

    USGS Publications Warehouse

    Rattner, B.A.; McGowan, P.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, pertluorinated 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 moderate-sized 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.

  13. Surface-Active Agents for Isolation of the Core Component of Avian Myeloblastosis Virus 1

    PubMed Central

    Stromberg, Kurt

    1972-01-01

    Sixty-one surface-active agents were evaluated in a procedure designed to assess their ability to remove the envelope from the core component of avian myeloblastosis virus (AMV). The procedure consisted of centrifugation of intact AMV through a series of sucrose gradients each containing an upper layer of agent at one of eight concentrations between 0.01 and 10%. The effectiveness of an agent in producing AMV cores was indicated by (i) the appearance of light-scattering bands in the region of core buoyant density in gradient tubes; (ii) the range of surfactant concentration over which these bands appeared; and (iii) an electron microscopy assessment by the negative-staining technique of the relative proportion of core to non-core material in each of these bands. Six nonionic surfactants were selected by this screening method for comparison in regard to recovery of core protein and endogenous ribonucleic acid (RNA)-dependent deoxyribonucleic acid (DNA) polymerase activity, as well as further morphologic evaluation by electron microscopy. The nonionic surfactants of the polyoxyethylene alcohol class (particularly, Sterox SL) were most effective. Nonionic surfactants of the polyoxyethylene alkylphenol class (particularly, Nonidet P-40) were also effective. Sterox SL and Nonidet P-40 each gave a more than fivefold increase in specific activity of endogenous RNA-dependent DNA polymerase, and each gave a low recovery of core protein. Sterox SL did not interfere to the extent that Nonidet P-40 did in procedures which involved spectrophotometric assay at 260 nm. The use of Sterox SL resulted in the least envelope contamination of core preparations by electron microscopy examination, the most recovery of protein and endogenous RNA-dependent DNA polymerase activity, and a core buoyant density in sucrose of 1.27 g/ml. Images PMID:4112071

  14. Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

    NASA Technical Reports Server (NTRS)

    McCollom, T. M.; Simoneit, B. R.

    1999-01-01

    The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

  15. 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

    removes a significant amount of the surface water. In this presentation, we report the results of measurements of the molecular packing and rates of kinetic exchange of the trisiloxane surfactants at the air/water interface in order to confirm our picture of trisiloxane packing, and provide additional insight into the superspreading process. We used the pendant bubble technique as a Langmuir trough to measure the trisiloxane equation of state which relates the tension to the surface concentration. From these measurements we obtain accurate values for the maximum packing density. We find that trisiloxanes with 4 and 8 ethoxylate groups have the same maximum packing concentration, indicating that the maximum packing is controlled by the cross section of the head group. For trisiloxanes with larger than eight ethoxylates, the maximum packing increases with ethoxylate number, indicating that the disposition of the ethoxylate chain (i.e., its effective size) is controlling. This supports our picture of superspreading: The superspreading ability of trisiloxanes decreases considerably for trisiloxanes with larger than eight ethoxylates; the packing measurements indicate that for the higher ethoxylate number trisiloxanes, the compact nonpolar head groups are pushed apart by the ethoxylate chain. They leave spaces of surface water on adsorption and do not lower the solid tension as much as their lower chain analogues. Finally the report measurements of the dynamic tension reduction accompanying the adsorption of trisiloxanes onto an initially clean interface using the pendant bubble technique, and we obtain from these relaxations, the equation of state and a mass transfer model, the rate constants for kinetic exchange. We find that the rate constants for desorption of trisiloxanes are generally much slower than for analogous aliphatic polyethoxylate surfactants with identical ethoxylate chain lengths. When an aqueous drop of a superspreader solution is placed on a hydrophobic

  16. Endocrine active chemicals, pharmaceuticals, and other chemicals of concern in surface water, wastewater-treatment plant effluent, and bed sediment, and biological characteristics in selected streams, Minnesota-design, methods, and data, 2009

    USGS Publications Warehouse

    Lee, Kathy E.; Langer, Susan K.; Barber, Larry B.; Writer, Jeff H.; Ferrey, Mark L.; Schoenfuss, Heiko L.; Furlong, Edward T.; Foreman, William T.; Gray, James L.; ReVello, Rhiannon C.; Martinovic, Dalma; Woodruff, Olivia R.; Keefe, Steffanie H.; Brown, Greg K.; Taylor, Howard E.; Ferrer, Imma; Thurman, E. Michael

    2011-01-01

    This report presents the study design, environmental data, and quality-assurance data for an integrated chemical and biological study of selected streams or lakes that receive wastewater-treatment plant effluent in Minnesota. This study was a cooperative effort of the U.S. Geological Survey, the Minnesota Pollution Control Agency, St. Cloud State University, the University of St. Thomas, and the University of Colorado. The objective of the study was to identify distribution patterns of endocrine active chemicals, pharmaceuticals, and other organic and inorganic chemicals of concern indicative of wastewater effluent, and to identify biological characteristics of estrogenicity and fish responses in the same streams. The U.S. Geological Survey collected and analyzed water, bed-sediment, and quality-assurance samples, and measured or recorded streamflow once at each sampling location from September through November 2009. Sampling locations included surface water and wastewater-treatment plant effluent. Twenty-five wastewater-treatment plants were selected to include continuous flow and periodic release facilities with differing processing steps (activated sludge or trickling filters) and plant design flows ranging from 0.002 to 10.9 cubic meters per second (0.04 to 251 million gallons per day) throughout Minnesota in varying land-use settings. Water samples were collected from the treated effluent of the 25 wastewater-treatment plants and at one point upstream from and one point downstream from wastewater-treatment plant effluent discharges. Bed-sediment samples also were collected at each of the stream or lake locations. Water samples were analyzed for major ions, nutrients, trace elements, pharmaceuticals, phytoestrogens and pharmaceuticals, alkylphenols and other neutral organic chemicals, carboxylic acids, and steroidal hormones. A subset (25 samples) of the bed-sediment samples were analyzed for carbon, wastewater-indicator chemicals, and steroidal hormones; the

  17. Occurrence of POPs and other persistent organic contaminants in the European eel (Anguilla anguilla) from the Loire estuary, France.

    PubMed

    Couderc, M; Poirier, L; Zalouk-Vergnoux, A; Kamari, A; Blanchet-Letrouvé, I; Marchand, P; Vénisseau, A; Veyrand, B; Mouneyrac, C; Le Bizec, B

    2015-02-01

    The chemical contamination of the Loire estuary by three classes of persistent organic pollutants (POPs): the polychlorinated biphenyls (PCBs), the polybrominated diphenyl ethers (PBDEs) and the perfluorinated and polyfluorinated alkyl substances (PFAS), and three families of organic contaminants, the alkylphenols (APs), the polycyclic aromatic hydrocarbon metabolites (OH-PAHs) and the bisphenol A (BPA) were investigated in the muscles and bile of European eel (Anguilla anguilla). Yellow eels (n=30) were caught in three different points along the estuary to highlight variations between sites and sources of contaminations. Silver eels (n=15) were also studied to compare contaminant impregnation between different life stages of the species. Average concentrations in the muscles of the eel ranged between: 857 and 4358 ng/gLW for the PCBs, 26 and 46 ng/gLW for the PBDEs, 130 and 1293 ng/gLW for the PFAS; and in bile: 31 and 286 μg/g protein for the APs, 9 and 26 μg/g protein for the OH-PAHs and ND-1213 μg/g protein for the BPA. Among PCBs, PCB 153 (40% contribution to the sum of PCBs) was predominant in all eel muscles. PBDE 47 (60%) was the most predominant PBDE congeners, while perfluorooctanesulfonic acid (85%) was the most widely detected PFAS. For APs, 4p-nonylphenol (91%) was the most abundant and for the OH-PAHs, it was 1OH-Pyrene (63%). All the eels exceeded the environmental quality standards (EQS) for biota for the PBDEs and about 75% were higher than the EQS specific to PFOS. Finally, 20% of the analyzed eels presented TEQ concentrations above the maximum limits for lipid-rich species. These results supplied new data on the occurrence, levels, and patterns of 53 organic chemicals in the eels from the Loire estuary and they highlighted the need of further investigations focused notably on the potential effects of these chemicals on this species and their analysis in the water and sediments of the estuary. PMID:25461022

  18. Interaction of xenobiotics with estrogen receptors α and β and a putative plasma sex hormone-binding globulin from channel catfish (Ictalurus punctatus)

    USGS Publications Warehouse

    Gale, William L.; Patino, Reynaldo; Maule, Alec G.

    2004-01-01

    Estrogens are important regulators of physiological functions. Although environmental contaminants (xenoestrogens) which interfere with estrogen signaling are of increasing concern, there is only limited information about their ability to interact with estrogen-binding proteins (SHBG) or receptors (ER). Recombinant ER?? and ?? were obtained after transient transfection of COS-7 cells with channel catfish ER cDNA. Plasma from adult female channel catfish was the source of SHBG. Tritiated estradiol ( 3H-E2) was used in standard radioligand-binding assays to characterize the binding properties of channel catfish SHBG (ccfSHBG) and to estimate the inhibition constants for various estrogenic compounds. Binding of 3H-E2 to ccfSHBG was saturable and of high affinity with a Kd (??SE) of 1.9??0.14nM and a Bmax of 14.3??2.4pmol/mg protein (n=3 assays). Additionally, ccfSHBG displayed binding s