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Surfactants such as alkylphenol polyethoxylates (APEOs) and nonylphenol ethoxylates (NPEOs) are commonly used worldwide, but the majority of these compounds, together with their metabolites, have been reported to induce severe biological toxicity. Here, we evaluated for the first time the cytotoxicity, genotoxicity and mitochondrial damage in Chinese hamster ovary (CHO-K1) cells caused by a novel non-ionic surfactant, vanillin ethoxylates (VAEOs), an alternative to APEOs. In parallel, the same in vitro bioassays were conducted on NPEOs along with their metabolic byproducts 4-nonylphenol (4-NP) and vanillin. The results showed that the cytotoxic potency order was NPEOs > 4-NP > VAEOs > vanillin using CCK-8 assays. Also, 4-NP showed potential direct DNA damage in SOS/umu tests, whereas NPEOs, VAEOs and vanillin showed no positive result with and without S9 addition. In addition, none of the test compounds showed obvious genotoxic effects with low olive tail moment value using comet assays. However, all test compounds were shown to cause mitochondrial impairment by increasing mitochondrial mass and decreasing mitochondrial membrane potential in a concentration-dependent manner. And further analysis of reactive oxygen species (ROS) and mitochondrial superoxide (MNSOD) measurement showed that mitochondrial impairment was induced by oxidative stress with intracellular ROS and MNSOD overproduction. It's worth noting that VAEOs and vanillin cause relative lower cytotoxic, genotoxic and mitochondrial damage effects than NPEOs and 4-NP, indicating that VAEOs have the potential to substitute NPEOs as suitable surfactants. Take together, this study elucidates the toxicity profiles of VAEOs and NPEOs relatively comprehensively, and further toxicity analyses are suggested in the population, community and ecosystem. Unlabelled Image [ABSTRACT FROM AUTHOR]

Abstract In this study, different generation of poly(amidoamine) (PAMAM) coated magnetic iron oxide nanoparticles were successfully synthesized via divergent growth approach of dendrimer for the removal of nonylphenol (NP) from water. The characterization of synthesized nanoparticles was performed by XRD, FTIR, TEM, FE-SEM, EPX, and VSM. The results suggested that there is a direct correlation between the number of dendrimer generation and its adsorption capacity; however, the rising generation >10 could not enhance NP removal efficiency, significantly. The 10th generation of PAMAM-MNP was modified by 4-aminophenol (MNP-G10-pAP) to enhance its adsorption capacity. The kinetic studies were performed after the determination of optimal adsorption conditions (pH, 7; Detention time, 60 min). It was found that Dubinin–Radushkevich (D–R) isotherm and pseudo-second order model are perfectly stimulated the adsorption behavior and kinetic rate of NP uptake. Furthermore, the NP removal efficiencies of 70, 67, 63 and 65% were observed for distilled water, drinking water, well water and treated wastewater, respectively. Finally, it was revealed that the synthesized product had acceptable reusability in eight times and NP removal efficiency decreased by just 15%. Highlights • Different generation of PAMAM dendrimer-coated iron oxide nanoparticles was synthesized. • The removal of NP from water by prepared nanoparticles was good. • Modification of MNP-G10 by 4-aminophenol enhanced its adsorption ‎capacity, significantly. • D-R isotherm model was perfectly stimulated the adsorption behavior of NP uptake by the sorbent. [ABSTRACT FROM AUTHOR]

4‐nonylphenol is a persistent organic pollutant with endocrine‐disrupting properties. A nonpolar product of microbial degradation derived from the surfactant nonylphenol polyethoxylate, 4‐nonylphenol is capable of long‐range transport attached to particulates. Bioactive concentrations of 4‐nonylphenol have been found in the surface water, soils, snow, and particulate matter of the Eastern Sierra Nevada Mountains (USA) hundreds of miles from their origins. As a result of particulate deposition, seasonal and glacial snow pack concentrations measured 20 to 100 times higher than in surface waters. Batch desorption assays were run on particulate matter dosed with 4‐nonylphenol. Desorption was measured in 63 to 500 μm particles under 2 different temperature conditions with varying fractions of organic carbon in turbulent or undisturbed states. Lower temperatures (4 °C) decreased the mean percentage of 4‐nonylphenol released from particulates in disturbed and undisturbed conditions, whereas the mean percentage of 4‐nonylphenol released at 20 °C was reduced by agitation. The effect of agitation at 4 °C was not practically or statistically significant. Particulates with a higher percentage of organic carbon (75%) released very little of the bound 4‐nonylphenol (0.53%) compared with particulates containing 4 to 5% of organic carbon that released up to 13%. Larger particles released the least amount of 4‐nonylphenol, whereas smaller particles released the most amount. Water and sediment samples taken from below the Palisades Glacier in the Sierra Nevada Mountains showed the greatest 4‐nonylphenol concentrations directly below the glacier, implying that glacial particulates will release adsorbed 4‐nonylphenol. Environ Toxicol Chem 2019;38:350–360. © 2018 SETAC [ABSTRACT FROM AUTHOR]

Abstract BPA and NP are both typical endocrine disruptors, the exposed populations are widespread, and the health risks mustn't be ignored. However, the interactions between them on spermatogenesis are rarely mentioned. And the underlying mechanism is unclear yet. In the present study, prepubertal SD rats were exposed to different low doses of BPA and NP separately or jointly for 4 weeks. The results indicate that the joint exposure induced excessive apoptosis and autophagy in the testes, as proved by a series of characteristics such as chromatin condensation and autophagosomes formation. Besides, endocrine disorders and oxidative stress were also caused by the exposure. Apoptosis was mediated by the mitochondrial apoptosis pathway, since the Bax and Caspase-3 gene expressions significantly increased with a prominent decrease of Bcl-2. While autophagy was caused by the inhibition of the Akt/mTOR pathway, as the expressions of the downstream genes Beclin-1, Atg5, Atg12 and the split of LC3 protein increased altogether. Worse yet, autophagy and apoptosis might reinforce each other and make the situation more severe in the joint group. What's more, remarkable histopathological changes such as spermatogenic epithelium atrophy, germ cell loss, and various ultrastructural modifications were strongly related to the apoptosis and autophagy. In aggregate, this study shows the enormous risk on male reproductive system brought by the interactions between BPA and NP. The findings provide a broader vision to understand the roles of apoptosis and autophagy induced by the joint exposure in the aggravation of spermatogenesis impairment, which could be a reference for the situation of complex EDCs exposure-induced male reproductive toxicity, and possibly inspire us to find new ideas for preventive and therapeutic treatments. Graphical abstract Image 1 Highlights • Joint exposure of BPA and NP induced apoptosis and autophagy in testes of prepuberty SD rats. • Joint exposure of BPA and NP disturbed the Akt/mTOR pathway and mitochondrial apoptosis pathway. • Autophagy and apoptosis reinforce each other and make the situation even worse in the joint groups. • Other apoptosis pathways might also be involved in the process. Joint exposure of BPA and NP harms spermatogenesis. [ABSTRACT FROM AUTHOR]

Abstract Nonylphenol (NP) is a commercially produced nonionic surfactant that has become a global environmental pollutant due to poor biodegradability. Many studies have confirmed that NP has detrimental effects on the central nervous system. However, the damaging roles of NP on the cerebellum and the underlying mechanisms remain unclear. Therefore, we investigated the effects of perinatal exposure to NP on cerebellar Purkinje cell (PC) dendrites and explored the potential mechanism involved. The animal model of perinatal exposure to NP was established by orally administering dams with either corn oil or NP (10, 50, or 100 mg/kg) during pregnancy and lactation. Offspring subjected to NP exposure during pregnancy and lactation had shorter and fewer cerebellar PC dendritic branches in childhood (postnatal day (PND)21) and adulthood (PND80). Contrary to expectations, perinatal NP treatment increased phosphorylation of protein kinase C gamma on PND21, but not on PND80. However, perinatal exposure to NP decreased phosphorylation of stathmin and tropomyosin-related kinase B (TrkB), as well as the expression of brain derived neurotrophic factor (BDNF) in cerebellar PCs on PND21 and PND80. These results indicate that perinatal exposure to NP irreversibly inhibited dendritic growth of PCs in the cerebella of offspring. Furthermore, the irreversible damage to PC dendrites in the cerebella of offspring subjected to perinatal NP exposure may be due to increased stathmin activity mediated by BDNF-TrkB signaling. Highlights • Perinatal exposure to nonylphenol impairs dendritic outgrowth of Purkinje cell. • The impairment of dendritic outgrowth persists into adulthood. • BDNF/TrkB signaling may be involved in the irreversible impairment. [ABSTRACT FROM AUTHOR]

Abstract Nonylphenol (NP) and/or bisphenol A (BPA) may have reproductive effects. Although the mechanisms of action remain unclear, steroid hormones biosynthesis, hypothalamus pituitary adrenal axis activity, oxidative stress, and crosstalk interaction of NP and BPA mixture and its pathways may play a contributory role. This cross-sectional study examined whether the interactive effects of NP/BPA and oxidative stress biomarkers played a role in reproductive indices (penis length and anogenital distance (AGD)) in 244 mother-fetus pairs. Four biomarkers of oxidative stress, (8-hydroxy-2′-deoxyguanosine (8-OHdG), 8-nitroguanine (8-NO 2 Gua), 8-iso-prostaglandin F 2α (8-isoPF 2α), and 4-hydroxy-2-nonenal-mercapturic acid (HNE-MA)) were simultaneously analyzed using the high-performance liquid chromatography-electrospray ionization tandem mass spectrometry method. No significant associations were found between reproductive indices and NP/BPA or oxidative stress biomarkers. Maternal exposure to a mixture of NP and BPA may enhance 8-OHdG. Interactive effects were found in the high 8-isoPF 2α group, and prenatal NP exposure was inversely associated with penis length (β = −3.68 mm; p = 0.01). Similar results were noted among boys who were born to mothers in the high 8-isoPF 2α group, in which BPA was inversely associated with penis length (β = −4.43 mm; p = 0.005). Our findings suggest important implications for prenatal exposure to oxidative stress, as evidenced by the 8-isoPF2α level. Thus, NP and BPA may interact to shape fetal reproductive tract development, particularly in boys. The interactive effects of NP/BPA, oxidative stress, and reproductive indices should be considered. Highlights • Maternal NP exposure may induce 8-OHdG and 8-NO 2 Gua. • Prenatal BPA may induce 8-isoPF 2α. • Concurrent exposure to NP and BPA may enhance 8-OHdG. • In the high 8-isoPF 2α group, NP/BPA is inversely related with the fetal penis length. • The interactions of NP/BPA, oxidative stress and penis length should be considered. [ABSTRACT FROM AUTHOR]

The distribution and fate of organic pollutants determines pollution control strategies and definition of environmental standards. So far, few models predict accurately the fate of organic pollutants. Therefore, here we tested the Markov chains model to simulate the distribution and fate of nonylphenol and naphthalene in the aquatic environment. Results show that the removal of nonylphenol and naphthalene from the water/sediment system is higher in the wet season and lower in the dry season. Due to its hydrophilic hydroxyl group, nonylphenol remains in water, whereas naphthalene, being more hydrophobic, accumulates in the sediment. Results of Markov chains modeling perfectly matched results from microcosm experiments. [ABSTRACT FROM AUTHOR]

The urbanization and industrialization of cities around the coastal region of the Bohai Sea have produced large amounts of sewage sludge from sewage treatment plants. Research on the biodegradation of nonylphenol (NP) and the influencing factors of such biodegradation during sewage sludge composting is important to control pollution caused by land application of sewage sludge. The present study investigated the effect of aeration on NP biodegradation and the microbe community during aerobic composting under two intermittent aeration treatments in a full-scale plant of sewage sludge, sawdust, and returned compost at a ratio of 6:3:1. The results showed that 65% of NP was biodegraded and that Bacillus was the dominant bacterial species in the mesophilic phase. The amount of NP biodegraded in the mesophilic phase was 68.3%, which accounted for 64.6% of the total amount of biodegraded NP. The amount of NP biodegraded under high-volume aeration was 19.6% higher than that under low-volume aeration. Bacillus was dominant for 60.9% of the composting period under high-volume aeration, compared to 22.7% dominance under low-volume aeration. In the thermophilic phase, high-volume aeration promoted the biodegradation of NP and Bacillus remained the dominant bacterial species. In the cooling and stable phases, the contents of NP underwent insignificant change while different dominant bacteria were observed in the two treatments. NP was mostly biodegraded by Bacillus , and the rate of biodegradation was significantly correlated with the abundance of Bacillus ( r  = 0.63, p  < 0.05). Under aeration, Bacillus remained the dominant bacteria, especially in the thermal phase; this phenomenon possibly increased the biodegradation efficiency of NP. High-volume aeration accelerated the activity and prolonged the survival of Bacillus . The risk of organic pollution could be decreased prior to sewage sludge reuse in soil by adjusting the ventilation strategies of aerobic compost measurements. [ABSTRACT FROM AUTHOR]

Cell-based bioanalytical tools are considered one alternative to overcome limitations of sensitivities of instrumental, analytical chemistry for monitoring estrogenic chemicals in the environment. Because these tools also reflect non-additive interactions of chemicals in mixtures, their outcomes often deviate from outcomes of chemical analytical approaches that assume additivity, e.g. the concentration addition (CA) model. Often this is because CA is unable to adequately represent effects of partial agonists, i.e. estrogens with lesser efficacies compared to 17β-estradiol. A generalized concentration addition (GCA) model has been proposed to address this shortcoming. In the present study, we investigated effects of mixtures of isomers of nonylphenol as partial model agonists in a cell-based estrogenicity assay. Whether the GCA model was able to more accurately predict the outcomes of these and previously published mixture experiments was evaluated, as well as the potency of a set of comprehensively characterized sewage effluent samples, compared to CA. If samples contained partial agonists, the GCA model consistently predicted potencies of mixtures and extracts of environmental samples more accurately than did the CA model. These findings enable more accurate estimations of potencies of estrogenicity explained by concentrations of agonists and partial agonists, thus significantly improving the ability to identify causative chemicals. [ABSTRACT FROM AUTHOR]

Many of the world's large coastal cities discharge partially treated wastewater effluents containing various endocrine disrupting chemicals (EDCs) to coastal environments. Nonylphenols (NP) and bisphenol A (BPA) were found to be the most abundant EDCs in sewage effluents in Hong Kong. The environmental fate and ecological risk of these two EDCs remains largely unknown, particular for coastal systems with complex hydrodynamic flows. Based on a validated three-dimensional (3D) multiple-scale hydrodynamic model, a field-based study was conducted to track the two EDCs from potential sources to the only marine reserve in Hong Kong. The two compounds were detected in all seawater, suspended particle, and sediment samples, with higher aqueous concentrations in wet season than in dry season. High concentrations in sediments suggest sediment is a sink, posing an ecological risk to the benthos. The fate and transport of the two EDCs was predicted using a 3D near-field Lagrangian jet model seamlessly coupled with a 3D shallow water circulation model. The results suggested the NP and BPA in the marine reserve cannot be solely attributed to the nearby submarine sewage outfall, but likely concurrently contributed by other sources. This study calls for more effective measures of reducing the use and release of these EDCs, and research to investigate their impacts on the marine benthos. [ABSTRACT FROM AUTHOR]

Alkylphenols (APs) are ultimate breakdown products of alkylphenol polyethoxylate (APEs) that are used in cleaning and industrial processes. The most commonly used APEs in the market are the nonylphenol ethoxylates (NPEs) and octylphenol ethoxylates (OPEs). As a result of their widespread use and their lipophilic nature, these compounds are ubiquitous in the environment and are currently of concern because of their toxicity, oestrogenic properties and widespread contamination. This review summarizes the concentrations of NPE and NP in different environmental media. The sources of NPE in the environment and toxicity are reviewed. Their distribution patterns in the environment as well as exposure pathways are discussed with a view to provide better understanding of these emerging environmental contaminants. It is envisaged that this review will heighten the importance of identifying emerging issues and data gaps, and generate a future research agenda on APEs. [ABSTRACT FROM AUTHOR]

The objective of the present work was to evaluate the toxic effect of nonylphenol (NP) on the antioxidant response and antitumor activity of Gracilaria lemaneiformis. An obvious oxidative damage was observed in this study. The thallus exposed to NP showed 1.2-2.0-fold increase in lipid peroxide and displayed a maximum level of 16.58 μmol g Fw on 0.6 mg L for 15-day exposure. The activities of antioxidant enzymes such as superoxide dismutase (SOD) and catalase (CAT) enhanced significantly by 1.1-3.2-fold and subsequently diminished at the high concentrations and prolonged exposure. The results of DNA damage in comet assay also supported that NP was obviously toxic on G. lemaneiformis with increasing the percentage of tail DNA in a dose-dependent manner. Furthermore, the ethanol extract of G. lemaneiformis (EEGL) did exhibit antitumor potential against HepG-2 cells. While decreased in cell inhibition, ROS generation, apoptosis, and caspase-3 in HepG-2 cells treated with the EEGL were observed when G. lemaneiformis was exposed to NP for 15 days, and which were related to exposure concentration of NP. These suggested that NP has strongly toxic effect on the antitumor activity of G. lemaneiformis. The results revealed in this study imply that macroalgae can be useful biomarkers to evaluate marine pollutions. [ABSTRACT FROM AUTHOR]

Nonylphenol (NP) and octylphenol (OP) are priority environmental contaminants that have a potential role as endocrine disruptors. They can be biomagnified in the food chain and pose an estrogenic health risk to human health. A 28-day oral toxicity study was performed to observe the impact of single and combined exposure to NP and OP on 5-HT transporter (SERT) as well as 5-HT receptor. Results showed that the 5-HT levels in rat plasma increased with exposure to middle-dose and high-dose NP, to high-dose OP, and to low, middle, and high doses of combined NP and OP ( P < 0.05), while the 5-HT levels in rat platelets increased when exposed to NP/OP or combined NP and OP of middle or high dose ( P < 0.05). The expression levels of SERT in rat platelets decreased when exposed to high-dose NP/OP or high dose of combined NP and OP ( P < 0.05). Meanwhile, the expression levels of 5-HT in rat platelets decreased when exposed to high-dose NP/OP as well as combined NP and OP ( P < 0.05). These findings suggested that exposure to NP and OP could influence the metabolic network of 5-hydroxytryptamine via transportation and receptor binding pathways. [ABSTRACT FROM AUTHOR]

Nonylphenol is considered an endocrine disruptor and has been reported to affect male reproductive functions. In our in vitro study, we evaluated the effects of 4-nonylphenol (4-NP) on cholesterol levels, hormone formation and viability in cultured Leydig cells from adult ICR male mice. We also determined the potential impact of 4-NP on generation of reactive oxygen species (ROS) after 44 h of cultivation. The cells were cultured with addition of 0.04; 0.2; 1.0; 2.5 and 5.0 μg/mL of 4-NP in the present of 1 IU/mL human chorionic gonadotropin (hCG) and compared to the control. The quantity of cholesterol was determined from culture medium using photometry. Determination of hormone production was performed by enzyme-linked immunosorbent assay. Metabolic activity assay was used for quantification of cell viability. The chemiluminescence technique, which uses a luminometer to measure reactive oxygen species, was employed. Applied doses of 4-NP (0.04–5.0 μg/mL) slight increase cholesterol levels and decrease production of dehydroepiandrosterone after 44 h of cultivation, but not significantly. Incubation of 4-NP treated cells with hCG significantly (P < 0.001) inhibited androstenedione, but not testosterone, formation at the highest concentration (5.0 μg/mL). The viability was significantly (P < 0.05); (P < 0.001) increased at 1.0; 2.5 and 5.0 μg/mL of 4-NP after 44 h treatment. Furthermore, 44 h treatment of 4-NP (0.04–5.0 μg/mL) caused significant (P < 0.001) intracellular accumulation of ROS in exposed cells. Taken together, the results of our in vitro study reported herein is consistent with the conclusion that 4-nonylphenol is able to influence hormonal profile, cell viability and generate ROS. [ABSTRACT FROM AUTHOR]

A flocculation method was used for the removal of trace nonylphenol (NP) from synthetic surface water containing natural organic matters (humic acid, HA) and suspended inorganic particles (kaolin). A polymeric flocculant (CMCND), with enhanced cationic property and unique switchable hydrophobic/hydrophilic characteristic, was specially designed for this application. CMCND showed a high efficiency for trace NP removal, turbidity and UV 254 abatements: under optimized conditions (pH: 4; T: 35 °C; dosage: 40 mg/L), the removal of NP reached up to 79%. By using dosage-pH flocculation diagrams and correlation analyses as tools, kaolin and HA were found to exert synergistic effects on NP removal, with the aid of CMCND; the synergistic effect of HA is higher due to π-π stacking. Zeta potential-dosage profiles clearly demonstrated charge neutralization predominated at pH 4, due to the strong cationic groups in the flocculant. Floc size monitoring displayed that the delayed phase transformation process (from hydrophilicity to hydrophobicity) of CMCND at 35 °C enhanced NP removal. In addition, spectral analyses clarified the interactions among CMCND, NP, kaolin and HA: charge attraction and hydrophobic interaction between CMCND and NP played the key roles. The findings are of significance for removing endocrine-disrupting chemicals in environmental remediation. [ABSTRACT FROM AUTHOR]

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 604 ng g − 1 dw was calculated and nonylphenol was the main contributor in almost all sampling points. [ABSTRACT FROM AUTHOR]

Environmental risk assessment (ERA) is often considered as the most transparent, objective and reliable decision-making tool for informing the risk management of chemicals and nanomaterials. ERAs are based on the assumption that it is possible to provide accurate estimates of hazard and exposure and, subsequently, to quantify risk. In this paper we argue that since the quantification of risk is dominated by uncertainties, ERAs do not provide a transparent or an objective foundation for decision-making and they should therefore not be considered as a “holy grail” for informing risk management. We build this thesis on the analysis of two case studies (of nonylphenol and nanomaterials) as well as a historical analysis in which we address the scientific foundation for ERAs. The analyses show that ERAs do not properly address all aspects of actual risk, such as the mixture effect and the environmentally realistic risk from nanomaterials. Uncertainties have been recognised for decades, and assessment factors are used to compensate for the lack of realism in ERAs. The assessment factors' values were pragmatically determined, thus lowering the scientific accuracy of the ERAs. Furthermore, the default choice of standard assay for assessing a hazard might not always be the most biologically relevant, so we therefore argue that an ERA should be viewed as a pragmatic decision-making tool among several, and it should not have a special status for informing risk management. In relation to other relevant decision-making tools we discuss the use of chemical alternative assessments (CAAs) and the precautionary principle. [ABSTRACT FROM AUTHOR]

Contaminant exposure in aqueous systems typically involves complex chemical mixtures. Given the large number of compounds present in the environment, it is critical to identify hazardous chemical interactions rapidly. The present study utilized a prototype for a novel high-throughput assay to quantify behavioral changes over time to identify chemical interactions that affect toxicity. The independent and combined effects of 2 chemicals, diazinon (an insecticide) and 4-nonylphenol (a detergent metabolite), on the swimming behavior of the freshwater crustacean Daphnia pulex were examined. Cumulative distance and change in direction were measured repeatedly via optical tracking over 90 min. Exposure to low concentrations of diazinon (0.125-2 µM) or 4-nonylphenol (0.25-4 µM) elicited significant concentration- and time-dependent effects on swimming behavior. Exposure to 0.5 µM 4-nonylphenol alone did not significantly alter mean cumulative distance but did elicit a small, significant increase in mean angle, the measure of change in direction. When 0.5 µM 4-nonylphenol was used in combination with diazinon (0.125-0.5 µM), it augmented the adverse impact of diazinon on the swimming behavior of Daphnia. Additionally, enhanced sensitivity to diazinon was observed in animals exposed to treated wastewater effluent for 24 h prior to a diazinon challenge. The present experiments demonstrate that exposure to 4-nonylphenol and complex chemical mixtures (e.g., treated wastewater) can enhance the toxicity of exposure to the insecticide diazinon. Environ Toxicol Chem 2015;34:1145-1153. © 2015 SETAC [ABSTRACT FROM AUTHOR]

Endocrine-disrupting chemicals (EDC) are defined as environmental compounds that produce adverse health manifestations in mammals by disrupting the endocrine system. Benzophenone-1 (2,4-dihydroxybenzophenone, BP1) and nonylphenol (NP), which are discharged from numerous industrial products, are known EDC. The aim of this study was to examine the effects of BP1 and NP on proliferation and metastasis of MCF-7 human breast cancer cells expressing estrogen receptors (ER). Treatment with BP1 (10−5-10−7M) and NP (10−6-10−7M) promoted proliferation of MCF-7 cells similar to the positive control 17 -beta-estradiol (E2). When ICI 182,780, an ER antagonist, was co-incubated with E2, BP1, or NP, proliferation of MCF-7 cells returned to the level of a control. Addition of BP1 or NP markedly induced migration of MCF-7 cells similar to E2. To elucidate the underlying molecular mechanisms produced by these EDC, alterations in transcriptional and translational levels of proliferation and metastasis-related markers, including cyclin D1, p21, and cathepsin D, were determined. Data showed increase in expression of cyclin D1 and cathepsin D and decrease in p21 at both transcriptional and translational levels. However, BP1- or NP-induced alterations of these genes were blocked by ICI 182,780, suggesting that changes in expression of these genes may be regulated by an ERα-dependent pathway. In conclusion, BP1 and NP may accelerate growth of MCF-7 breast cancer cells by regulating cell cycle-related genes and promote cancer metastasis through amplification of cathepsin D. [ABSTRACT FROM PUBLISHER]

The article offers information on the Significant New Use Rule (SNUR) proposed by the U.S. Environmental Protection Agency (EPA) under the Toxic Substances Control Act (TSCA) on October 1, 2014 related to chemical substances commonly known as nonylphenols (NP) and nonylphenol ethoxylates (NPE). Topics discussed include concerns of EPA regarding the potential impacts of NP and NPE chemicals on aquatic environment, implementation of action plan of agency and Inventory Update Rule (IUR).

Dust and particulate distribution patterns are shifting as global climate change brings about longer drought periods. Particulates act as vehicles for long range transport of organic pollutants, depositing at locations far from their source. Nonylphenol, a biodegradation product of nonylphenol polyethoxylate, is a known endocrine disruptor. Nonylphenol polyethoxylate enters the environment as an inert ingredient in pesticide sprays, potentially traveling great distances from its application site. This is of concern when a highly agricultural region, California's Central Valley, lies adjacent to sensitive areas like the Eastern Sierra Nevada Mountains. The distribution and transport mechanisms for 4-nonylphenol were investigated in Eastern Sierra Nevada canyons. Regions close to canyon headwalls showed trace amounts of 4-nonylphenol in surface water, snow, and atmospheric deposition. Exposed areas had yearly average concentrations as high as 9 μg/L. Distribution patterns are consistent with particulate-bound transport. This suggests with increasing drought periods, higher levels of persistent organic pollutants are likely. [ABSTRACT FROM AUTHOR]

As the predominant environmental biodegradation product of nonylphenol (NP) ethoxylates and with proven estrogenic effects, NP is formed during the alkylation process of phenols. The purposes of this study were (1) to examine maternal and prenatal exposure to NP in Taiwan, (2) to determine the level of placental protection against NP exposure as well as the level of NP in breast milk, and (3) to assess the potential risk for breastfed newborns exposed to NP through the milk. Thirty pairs of maternal and fetal blood samples, placenta, and breast milk during the 1st and the 3rd months of lactation were collected. External NP exposures of these specimens were then analyzed by using high-performance liquid chromatography coupling with fluorescence detection. Next, the socio-demographics, lifestyle, delivery method, dietary and work history were collected using a questionnaire. In addition, the daily intake of NP from consuming breast milk in the 1st and 3rd months for newborns was studied through deterministic and probabilistic risk assessment methods. The geometric means and geometric standard deviation of NP levels in maternal blood, fetal cord blood, placenta, and breast milk in the 1st and 3rd months were 14.6 (1.7) ng/ml, 18.8 (1.8) ng/ml, 19.8 (1.9) ng/g, 23.5 (3.2) ng/ml, and 57.3 (1.4) ng/ml, respectively. The probabilistic percentiles (50th, 75th, and 95th) of daily intake NP in breast milk were 4.33, 7.79, and 18.39 μg/kg-bw/day in the 1st month, respectively, and were 8.11, 10.78, 16.08 μg/kg-bw/day in the 3rd month, respectively. The probabilistic distributions (5th, 25th, and 50th) of risk for infants aged 1 month old were 0.27, 0.64, and 1.15, respectively, and that for infants aged 3 month old were 0.31, 0.46, and 0.62, respectively. Through repeated exposure from the dietary intake of expectant mothers, fetuses could encounter a high NP exposure level due to transplacental absorption, partitioning between the maternal and fetal compartments. Daily NP intake via breast milk in three month-old babies exceeded the tolerable daily intake (TDI) of 5 µg/kg bw/day indicated a potential risk for Taiwan infants. [ABSTRACT FROM AUTHOR]

Highlights: [•] We studied Nonylphenol (NP) effects on HPA axis of Podarcis sicula lizard. [•] We showed a time-dependent stimulation of the whole HPA axis. [•] We have also demonstrated that NP disrupted the negative feedback of HPA axis. [•] The persistence of NP might pose a potential threat to human health. [•] Our data may help to predict the NP biological alterations upon adrenal function. [Copyright &y& Elsevier]

Highlights: [•] The SSD model can be used for the derivation of PNEC for nonylphenol. [•] We established the PNEC value of nonylphenol in both freshwater and seawater. [•] Nonylphenol occurs ubiquitously in coastal waters of China with RQ values up to 70. [Copyright &y& Elsevier]

Abstract: In this work, we have proposed a sensitive and selective detection technique for 2-nonylphenol (2-NP) based on the differential pulse voltammetry at a molecularly imprinted film on a glassy carbon electrode (GCE). The imprinted film was immobilised on the GCE by electrodeposition of a molecularly imprinted polymer (MIP) sol–gel consisting of a multiwalled carbon nanotube (MWNT)–Nafion (NF) composite. The modification procedure was characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscope (SEM). The recognition between MIP sol–gel film and target molecule was observed by measuring the change in DPV response of the oxidation-reduction probe, K3Fe(CN)6 on GCE. Under optimized operational conditions, a linear response was obtained covering the concentration range from 0.2 to 360μmolL −1 with a detection limit of 0.06μmolL −1. The proposed sensor was applied to 2-NP determination in water and soil samples with the recoveries from 95.4 to 98.1%, showing a promising potential application in environment samples. Additionally, The imprinted sensor demonstrated higher affinity for target 2-NP than that of non-imprinted polymer (NIP) sensor. [Copyright &y& Elsevier]

Fate of nonylphenol (NP) in soils and the effects of nitrogen fertilizers are unclear. Using 14C-tracer, we studied the aerobic and anaerobic degradation of 4-NP111 in a paddy red soil amended without and with ammonium chloride. Under oxic conditions, 4-NP111 had a half-life of 16.1 ± 1.6 days and minor mineralization (3.84 ± 0.02%), forming no extractable metabolite but abundant bound residues (60.9 ± 1.7%, mostly bound to humin) after 49 days of incubation. The ammonium amendment (8 mmol/kg soil) significantly inhibited the degradation (half-life of 68.0 ± 7.7 days), mineralization (2.0 ± 1.1%), and bound-residue formation (23.7 ± 0.2%). Under anoxic conditions, 4-NP111 did not degrade during 49 days of incubation and the ammonium amendment (40 mmol/kg soil) did not affect its persistence. Our results demonstrate that bound-residue formation was a major mechanism for NP dissipation in the red soil under oxic conditions and that chemical nitrogen fertilizer at average field application rate may already considerably increase NP recalcitrance in agricultural soils. [Copyright &y& Elsevier]

Abstract: Nonylphenol (NP) is an endocrine disruptor with harmful effects including feminization and carcinogenesis on various organisms. This substance is a degradation product of nonylphenol ethoxylates (NPEO) that is used in several industrial and agricultural processes. In this paper, we examined the assessment of NP exposure on chick embryo development, using a concentration consistent with the environmental concentrations of NP. With this aim, NP (between 0.1 and 50μg/egg) was injected into the yolk of egg through a small needle hole in the shell. We report the effect of NP on chick reproductive system development although the effect we observed is lower than those observed by exposition to other endocrine disruptors. However, histological analysis highlighted a decrease of intraluminal seminiferous surface area in 64.12% of case (P=0.0086) and an heterogeneous organization of the renal tubules when 10μg/egg were injected. Moreover, an impairment of liver development with an abnormal bile spillage was observed when higher concentration of NP was injected (50μg/egg). [Copyright &y& Elsevier]

Abstract: We examined the distribution and removal efficiencies of phenolic endocrine disruptors (EDs), namely nonylphenol diethoxylates (NP2EO), nonylphenol monoethoxylates (NP1EO), nonylphenol (NP), and octylphenol (OP), in wastewater treated by estuarine and freshwater constructed wetland systems in Dapeng Bay National Scenic Area (DBNSA) and along the Dahan River in Taiwan. Water samples were taken bimonthly at 30 sites in three estuarine constructed wetlands (Datan, Pengcun and Linbian right bank (A and B)) in DBNSA, for eight sampling campaigns. The average removal efficiencies were in the range of 3.13–97.3% for wetlands in DBNSA. The highest average removal occurred in the east inlet to the outlet of the Tatan wetland. The most frequently detected compound was OP (57.7%), whose concentration was up to 1458.7ng/L in DBNSA. NP was seen in only 20.5% of the samples. The temporal variation of EDs showed a decrease across seasons, where summer>spring>winter>autumn in these constructed wetlands. The removal efficiencies of EDs by estuarine wetlands, in decreasing order, were Datan>Pengcun>Linbian right bank in DBNSA. Water samples collected at 18 sites in three freshwater constructed wetlands (Daniaopi, Hsin-Hai I, and Hsin-Hai II) along the riparian area of Dahan River. NP2EO was the most abundant compound, with a concentration of up to 11200ng/L. Removal efficiencies ranged from 55% to 91% for NP1EO, NP2EO, and NP in Hsin-Hai I. The average removal potential of EDs in freshwater constructed wetlands, in decreasing order, was Hsin-Hai II>Daniaopi>Hsin-Hai I constructed wetlands. The lowest concentrations of the selected compounds were observed in the winter. The highest removal efficiency of the selected phenolic endocrine disruptors was achieved by Hsin-Hai I wetland. The calculated risk quotients used to evaluate the ecological risk were up to 30 times higher in the freshwater wetlands along Dahan River than in the estuarine (DBNSA) constructed wetlands, indicating that existing concentrations of these EDs in wetland systems pose a high ecological risk to aquatic organisms. The decreasing risk quotient from influent to effluent indicates that phenolic endocrine disruptors can be treated in these constructed wetlands. Our results of this research can serve as a preliminary understanding on the ED removal efficiencies in different types of constructed wetlands. [Copyright &y& Elsevier]

A response surface optimization based on ionic liquid dispersive liquid phase microextraction was developed for analysis of the endocrine disrupting compounds bisphenol A and 4-nonylphenol in water samples. The volume of the extraction solvent, volume of dispersive solvent, and pH were found to have significant effects on the response. Analysis of variance indicated that the model was significant at a high level. The reproducibility was investigated in six replicate experiments under optimum conditions. Taken together, these results indicated that the developed method would be a useful green method for rapid determination of bisphenol A and 4-nonylphenol at trace levels in tap and surface waters. [ABSTRACT FROM AUTHOR]

The seasonal variations and spatial distributions of 4-tert-octylphenol (OP), 4-nonylphenol (NP) and bisphenol A (BPA) in surface waters, suspended solids and surface sediments in the Huangpu River and its tributaries (Suzhou River and Yunzao Brook) were firstly investigated. The mean concentrations of OP, NP and BPA in the three rivers were 10.59, 120.96 and 22.93 ng L in surface waters, 199.87, 2,300.87 and 84.11 ng g in suspended solids and 9.49, 119.44 and 7.13 ng g dry weight in surface sediments, respectively. The concentrations of NP and OP were higher in summer than in winter in the suspended solids and surface sediments, while the reverse was true in surface waters. Similarly, the levels of BPA were lower in summer than in winter in surface sediments, while the opposite was true in surface waters and suspended solids. These seasonal variations might be attributed to temperature and stream flows. High levels of OP, NP and BPA were found in surrounding river intersections, residential and industrial areas. Their concentrations decreased gradually with increasing distance from those areas, while the lowest levels were measured in near less urbanized and agricultural areas. These phenomena might indicate that the stream current and pollutant source were the major factors that affect the spatial distributions of OP, NP and BPA in the three rivers. Ecological risk assessment indicated that NP was the only one of the three pollutants with the potential to influence local aquatic organisms. The results of this study provide scientific support for control of these pollutants. [ABSTRACT FROM AUTHOR]

Abstract: 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. [Copyright &y& Elsevier]

Abstract: Atrazine (ATZ) and nonylphenol (NP) are commonly identified contaminants in aquatic habitats; however, few studies have considered the impact of these endocrine disrupters on immune function and resistance to disease. This study examined the immunotoxicological effects of ATZ and NP at multiple levels of biological organization. Juvenile rainbow trout (Oncorhynchus mykiss) were exposed to a solvent control (0.00625%, v/v anhydrous ethanol), or sub-lethal concentrations of ATZ (59μg/L and 555μg/L) or NP (2.3μg/L or 18μg/L) for 4d. At the end of exposure, fish were assessed for a number of physiological endpoints, including a host resistance challenge, and liver gene expression was assessed using a salmonid microarray (cGRASP, 32K version 1). While the low ATZ and low NP treatments had no measurable effects on the physiological endpoints measured, fish exposed to the high ATZ concentration (555μg/L) exhibited significantly elevated plasma cortisol, a decrease in SSI, and decreased lymphocytes and increased monocytes in peripheral blood, with suppression of early immune system processes apparent at the molecular level. In contrast, fish exposed to the high NP concentration (18μg/L) showed physiological (e.g. significantly elevated LSI) and gene expression changes (e.g. induction of vitellogenin) consistent with estrogenic effects, as well as decreased lymphocytes in the peripheral blood and more limited alterations in immune system related pathways in the liver transcriptome. Fish exposed to high ATZ or NP concentrations incurred higher mortality than control fish following a disease challenge with Listonella anguillarum, while fish exposed to the lower concentrations were unaffected. Microarray analysis of the liver transcriptome revealed a total of 211 unique, annotated differentially regulated genes (DRGs) following high ATZ exposure and 299 DRGs following high NP exposure. Functional (enrichment) analysis revealed effects on immune system function, metabolism, oxygen homeostasis, cell cycle, DNA damage, and other processes affected by ATZ or NP exposure. Overall, this study provides evidence at multiple levels of biological organization that both ATZ and NP are immunotoxic at sub-lethal concentrations and highlights the potential risk posed by these chemicals to wild fish populations. [Copyright &y& Elsevier]

Low molecular-mass nonylphenol ethoxylates (NPEOs) and 4-nonylphenol (NP) are biodegradation products of higher molecular mass NPEOs used as surface active agents, and they are endocrine-disrupting contaminants. In this study, surface soil (0-20 cm) samples and different vegetable samples were collected from 27 representative vegetable farms located in Shenzhen, Dongguan, and Huizhou within the Pearl River Delta region, South China, and NP and nonylphenol monoethoxylate (NPEO) were analyzed using high-performance liquid chromatography with ultraviolet detection. The results show that NP and NPEO were detected in soil and vegetable samples. The concentrations of NP and NPEO in soil samples ranged from nondetectable (ND) to 7.22 μg kg dry weight (dw) and from ND to 8.24 μg kg dw, respectively. The average concentrations of both NP and NPEO in soil samples decreased in the following order: Dongguan > Huizhou > Shenzhen. The levels of NP and NPEO in vegetable samples varied from 1.11 to 4.73 μg kg dw and from 1.32 to 5.33 μg kg dw, respectively. The greatest levels of both NP and NPEO were observed in water spinach, and the lowest levels of NP and NPEO were recorded in cowpea. The bioconcentration factors (the ratio of contaminant concentration in plant tissue to soil concentration) of NP and NPEO were <1.0 (mean 0.535 and 0.550, respectively). The occurrences of NP and NPEO in this study are compared with other studies, and their potential sources are discussed. [ABSTRACT FROM AUTHOR]

Abstract: One of the chemical breakdown products of nonylphenol ethoxylates, 4-nonylphenol (4-NP), accumulates in organisms and is of concern as an environmental pollutant due to its endocrine disrupting effects. We measured 4-NP levels in the seawater, sediment, and twelve organisms within the California estuary, Morro Bay, and examined biomagnification of 4-NP using stable isotope abundances (δ 15N and δ 13C) to quantify trophic position. 4-NP concentrations in organisms from Morro Bay included 25000±8600ngg−1 lw in liver of California sea lion, 14000±5600ngg−1 lw in liver of harbor porpoise, 138000±55000ngg−1 lw in liver of sea otters, 15700±3600ngg−1 lw in liver of seabirds, 36100±6100ngg−1 lw in arrow goby fish, 62800±28400ngg−1 lw in oysters, and 12700±1300ngg−1 lw in mussels. 4-NP levels generally showed a pattern of trophic dilution among organisms in Morro Bay, with exceptions of biomagnification observed between three trophic links: mussel to sea otter (BMF 10.9), oyster to sea otter (BMF 2.2), and arrow goby to staghorn sculpin (BMF 2.7). Our examination of other west coast estuaries of USA and Canada revealed that mean 4-NP concentrations in gobies and mussels from Morro Bay were significantly higher than those from a more urbanized estuary, San Francisco Bay (goby: 11100±3800ngg−1 lw) and from a remote estuary, Bamfield Inlet, Canada (goby: 9000±900ngg−1 lw, mussel: 6100±700ngg−1 lw). Relative to other estuaries worldwide, 4-NP levels in seawater (0.42±0.16μgL−1) and sediment (53±14ngg−1 dw) of Morro Bay are low, but gobies and oysters have higher 4-NP levels than comparable fauna. [Copyright &y& Elsevier]

Abstract: The fate and behaviour of two groups of endocrine disrupting chemicals, steroid estrogens and nonylphenol ethoxylates, have been evaluated during the anaerobic digestion of primary and mixed sewage sludge under mesophilic and thermophilic conditions. Digestion occurred over six retention times, in laboratory scale reactors, treating sludges collected from a sewage treatment works in the United Kingdom. It has been established that sludge concentrations of both groups of compounds demonstrated temporal variations and that concentrations in mixed sludge were influenced by the presence of waste activated sludge as a result of transformations during aerobic treatment. The biodegradation of total steroid estrogens was >50% during primary sludge digestion with lower removals observed for mixed sludge, which reflected bulk organic solids removal efficiencies. The removal of nonylphenol ethoxylates was greater in mixed sludge digestion (>58%) compared with primary sludge digestion and did not reflect bulk organic removal efficiencies. It is apparent that anaerobic digestion reduces the concentrations of these compounds, and would therefore be expected to confer a degree of protection against exposure and transfer of both groups of compounds to the receiving/re-use environment. [Copyright &y& Elsevier]

Abstract: The sorption behavior of nonylphenol (NP, a toxic endocrine disruptor) on marine sediments was studied in detail through a series of kinetic and thermodynamic sorption experiments. The results showed that the sorption reaction of NP on marine sediments reached equilibrium in 1.5h and that it accorded well with the non-linear Ho-McKay pseudo-second-order model. The sorption isotherms of NP on H2O-treated sediments could be well described by the Linear isotherm model, while the sorption isotherm on H2O2-treated sediments could be well fitted with the Freundlich isotherm model. A positive correlation was found between the distribution coefficient (Kd ) and the sediment organic carbon contents. The medium salinity showed a positive relation with the Kd and a negative relation with the dissolved organic carbon (DOC). Hexadecyl trimethyl ammonium bromide (CTAB) enhanced the sorption amount of NP the most, while sodium dodecylbenzenesulfonate (SDBS) enhanced it the least. The sorption reaction of NP on marine sediments was a spontaneous, physical, exothermic and entropy-decreasing process. [Copyright &y& Elsevier]

Using 14C- and 13C-ring-labeling, degradation of five p-nonylphenol (4-NP) isomers including four branched (4-NP38, 4-NP65, 4-NP111, and 4-NP112) and one linear (4-NP1) isomers in a rice paddy soil was studied under oxic conditions. Degradation followed an availability-adjusted first-order kinetics with the decreasing order of half-life 4-NP111 (10.3 days) > 4-NP112 (8.4 days) > 4-NP65 (5.8 days) > 4-NP38 (2.1 days) > 4-NP1 (1.4 days), which is in agreement with the order of their reported estrogenicities. One metabolite of 4-NP111 with less polarity than the parent compound occurred rapidly and remained stable in the soil. At the end of incubation (58 days), bound residues of 4-NP111 amounted to 54% of the initially applied radioactivity and resided almost exclusively in the humin fraction of soil organic matter, in which chemically humin-bound residues increased over incubation. Our results indicate an increase of specific estrogenicity of the remaining 4-NPs in soil as a result of the isomer-specific degradation and therefore underline the importance of understanding the individual fate (including degradation, metabolism, and bound-residue formation) of isomers for risk assessment of 4-NPs in soil. 4-NP1 should not be used as a representative of 4-NPs for studies on their environmental behavior. [ABSTRACT FROM AUTHOR]

To assess the toxicity of nonylphenol towards aquatic crustaceans, Neocaridina denticulata were exposed short-term to sublethal concentration (0.001-0.5 mg/L). Following treatment, differentially expressed genes were identified using suppression subtractive hybridization on samples prepared from whole specimens. There were 20 differentially expressed sequence tags that corresponded to known genes and could be divided into six functional classes: defence, translation, metabolism, ribosomal gene expression, respiration, and genes involved in the stress response. Using semi-quantitative RT-PCR, we found that 14 of the differentially expressed sequence tags significantly responded to nonylphenol, including six at a nominal concentration of 0.01 mg/L; among them, 12 genes were down-regulated. These results suggest that under non-lethal concentrations of nonylphenol, the polluted aquatic environment may still present a potential risk to N. denticulata. [ABSTRACT FROM AUTHOR]

Endocrine Disruptor Chemicals (EDCs) with estrogen-like properties i.e nonylphenol (NP) induce vitellogenin (VTG) synthesis in males of aquatic and semi-aquatic specie. In the oviparous species VTG is a female-specific oestrogen dependent protein. Males are unable to synthesize VTG except after E2 treatment. This study aimed to verify if NP, administered via food and water, is able to induce the expression of VTG even in males of vertebrates with a terrestrial habitat such as the lizard Podarcis. By means of ICC, ISH, W/B and ELISA we demonstrated that NP induces the presence of VTG in the plasma and its expression in the liver. VTG, undetectable in untreated males, reaches the value of 4.34 μg/μl in the experimental ones. Expression analysis and ISH in the liver showed that an NP-polluted diet also elicits the expression of ERα in the liver which is known to be related to VTG synthesis in Podarcis. [Copyright &y& Elsevier]

A computer-aided docking study was conducted to explore in detail the binding interactions between the structurally unlikely environmental oestrogen 4-nonylphenol (4NP) and three of its metabolites with the human oestrogen receptor alpha (hERα). Docking was done within the Schrodinger Suite 2008 using both a conventional rigid receptor with flexible ligand and the induced-fit docking protocol. Induced-fit docking allows side-chain and backbone movement in the receptor to accommodate the ligand. This study has revealed unconventional interactions between the ligands and the hERα binding pocket that could explain the observed oestrogen-like behaviour of 4NP and suggests some of the metabolites of 4NP may also be oestrogenic. [ABSTRACT FROM AUTHOR]

Technical mixtures of nonylphenol (NP) contain over 20 p-substituted isomers. Mono- and di-chlorinated derivatives are generated during the chlorination process in water treatment. Four NP isomers (i.e. 4n-, p353-, p33-, p363-NP) and their mono- (MCl) and di-chlorinated (DCl) derivatives were tested for their estrogenic and androgenic potency using yeast estrogenic and androgenic assay. The p353-NP and 4n-MClNP isomers showed the highest and the lowest estrogenic potency, respectively. The p363-MClNP exhibits estrogenic potency comparable to the parent isomer, whereas all p-DClNP compounds displayed a decrease in the estrogenic potency. In the anti-androgenic screen, all substances exhibited a positive response; the mono- and di-chlorinated derivatives exhibit lower potency than the parent isomers. The isomer p363-NP and its corresponding mono- and di-chlorinated derivatives were almost inactive. Furthermore, all compounds were tested for anti-estrogenic and androgenic assays, but none of them showed a positive response. These results indicate that for assessing the xeno-hormone potency of chlorinated derivatives of NP, the use of pure compounds is essential because the mixtures are not representative. In fact the concentrations of NP isomers differ in technical mixtures according to the producers; after chlorination different technical mixtures can generate dissimilar ratios of chlorinated derivatives. Finally, the chlorinated derivatives of NP didn't show an increase in xeno-hormone potency compared to the parent isomers, and for this reason the many oxidized by-products generated during chlorination process mask the xeno-hormone potency of the pure chlorinated isomers of NP. [ABSTRACT FROM AUTHOR]

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

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 (NP1-3EC) 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, and polysaccharides. Secondary effluents from this study are characterized by low bulk organic concentrations and comparatively high micropollutant concentrations. Based on the biodegradation mechanism proposed in this study, application of high rate tertiary biological treatment processes to secondary effluents characterized by low bulk organic concentrations and comparatively high APEO concentrations is predicted to provide a sustainable solution to micropollutant removal. [ABSTRACT FROM AUTHOR]

Two membrane bioreactors (MBRs) were operated at high sludge retention time (SRT) (between 30 and 75 d) in parallel to a conventional activated sludge plant (CASP) conducted at SRT = 10 d. The fate of linear alkylbenzene sulfonate (LAS), nonylphenol ethoxylates (NPnEO, n = 1-15), nonylphenoxy carboxylates (NPnEC, n = 1-2), and nonylphenol (NP) in these systems was investigated. All systems were very efficient in the removal of LAS (around 99%). The analysis of variance showed that the difference in the removal efficiency of LAS in the CASP and the MBR operated at SRT = 65-75 d (respectively 99.0 ± 0.43 and 99.8 ± 0.11) were significant (p < 0.05), confirming the importance of SRT in the removal of LAS. Comparison between the CASP and the MBRs in the removal efficiency of nonylphenolic compounds were conducted considering NP3-15EO, the sum of NP1-15EO, NP1-2EC, and nonylphenol (NP). In all cases MBRs were more efficient than the CASP. In the case of NP the removal was about 76 ± 7.5% for the CASP and 90% ± 12.1 and 82 ± 8.7% for the MBRs. Better performance of MBRs in the removal of nonylphenolic compounds can be attributed to a better degradation. For example, if the sum of NP1-15EO and NP1-2EC is considered, estimated biodegradation was about 48% for the CASP and 72% for MBRs. [ABSTRACT FROM AUTHOR]

Abstract: Nonylphenols are very important environmentally relevant substances in the focus of the world-wide endocrine disrupter research for over 25years. Thus, they are among the 10 priority hazardous substances of the new European Union Water Framework Directive. They consist of a very complex mixture of isomers representing therefore a multi-component problem like dioxins or PCBs. As estrogenic effect and degradation behavior in the environment of individual 4-nonylphenols are heavily dependent on the structure and bulkiness of the side chain, it is absolutely necessary to consider the nonylphenol problem from an isomer-specific viewpoint. Therefore a range of 28 differently branched nonylphenol isomers were synthesized for biological and environmental studies. Nonylphenols with a quaternary α-carbon, like 4-(1,1,3,4-tetramethylpentyl)phenol (4-NP 95 ) and 4-(1-ethyl-1,3,3-trimethylbutyl)phenol (4-NP 170 ), were obtained by Friedel–Crafts alkylation of anisole with tertiary nonyl bromides and demethylation with BI3. Nonylphenols with a tertiary α-carbon, such as 4-(1,2-dimethylheptyl)phenol (4-NP 10 ) and 4-(1,2,4-trimethylhexyl)phenol (4-NP 41 ), were accessible via coupling of p-methoxyphenylmagnesium bromide with ketones. Nonylphenols bearing a quaternary β-carbon, like 4-(2,2-dimethylheptyl)phenol (4-NP 15 ) and 4-(1,2,2-trimethylhexyl)phenol (4-NP 39 ), were synthesized starting from 4′-methoxyisobutyrophenone. The compounds were characterized by GC–MS and NMR-spectroscopy. The individual isomers were designated according to the Juelich Nomenclature. [ABSTRACT FROM AUTHOR]

The Deepwater Horizon oil spill has led to the use of >1 M gallons of oil spill dispersants, which are mixtures of surfactants and solvents. Because of this large scale use there is a critical need to understand the potential for toxicity of the currently used dispersant and potential alternatives, especially given the limited toxicity testing information that is available. In particular, some dispersants contain nonylphenol ethoxylates (NPEs), which can degrade to nonylphenol (NP), a known endocrine disruptor. Given the urgent need to generate toxicity data, we carried out a series of in vitro high-throughput assays on eight commercial dispersants. These assays focused on the estrogen and androgen receptors (ER and AR), but also included a larger battery of assays probing other biological pathways. Cytotoxicity in mammalian cells was also quantified. No activity was seen in any AR assay. Two dispersants showed a weak ER signal in one assay (EC50 of 16 ppm for Nokomis 3-F4 and 25 ppm for ZI-400). NPs and NPEs also had a weak signal in this same ER assay. Note that Corexit 9500, the currently used product, does not contain NPEs and did not show any ER activity. Cytotoxicity values for six of the dispersants were statistically indistinguishable, with median LC50 values ∼100 ppm. Two dispersants, JD 2000 and SAF-RON GOLD, were significantly less cytotoxic than the others with LC50 values approaching or exceeding 1000 ppm. [ABSTRACT FROM AUTHOR]

Biochemically, nonylphenol ethoxylates (NPnEOs) and its breakdown products nonylphenol (NP), NP monoethoxylate (NP1EO), and NP diethoxylate (NP2EO) are considered endocrine disrupting compounds. These NPnEOs have been detected in aquatic environments and are of concern. NP, NP1EO, and NP2EO were detected in water samples collected from the main watercourse and polluted tributaries of Kaoping River, Taiwan. Concentrations were below the detection limit (1EO, and from 2EO. It was found that concentrations of the three compounds in a low flow period were significantly greater than in the high flow period due to the low dilution effect. The risk to aquatic organisms by NP, NP1EO, and NP2EO was expressed as hazard quotient and hazard index and simulated with the Monte Carlo method. Results from this study suggested an inadequately treated domestic wastewater caused high concentrations of NP, NP1EO, and NP2EO and a high risk to aquatic organisms. [ABSTRACT FROM AUTHOR]

Municipal sewage and WWTP effluents are considered to be a major source of pollution, regarding the occurrence of endocrine disrupting compounds (EDCs) in the environment. Although removal potential of many EDCs by conventional WWTPs is recognised, literature data are not easily comparable. Besides, in order to reach very low concentrations, a further treatment might be sometimes required. Positive results can be achieved by tertiary chemical oxidation; nevertheless, technical-economic suitability is still to be fully demonstrated. In this work, two estrogen-like susbstances were considered: nonylphenol (NP) (and its parent compounds) and bisphenol A (BPA). The experimental work was conducted at Verona (Northern Italy) WWTP (370,000 p.e.): after a 15 days sampling campaign, which was carried out in order to calculate mass balance of target compounds, chemical oxidation tests were performed on effluent by means of UV/H2O2 process and ozonation. Technical-economic feasibility of these solutions is discussed. [ABSTRACT FROM AUTHOR]

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 × 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 × 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. [ABSTRACT FROM AUTHOR]