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

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

Meta-analysis of environmental contamination by alkylphenols

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.     

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

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

Endocrine disrupting chemicals in indoor and outdoor air

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 effects is currently underway, so questions remain as to the health impacts of these exposures.     

Movement and fate of detergents in groundwater: a field study

The major cations, anions, and detergents in a plume of contaminated groundwater at Otis Air Base on Cape Cod (Mass., U.S.A.) have moved approximately 3.5 km down gradient from the disposal beds. We hypothesize that the detergents form two distinct plumes, which consist of alkyl benzene sulfonates (ABS) detergents and linear alkyl sulfonates (LAS) and sodium dodecyl sulfate (NaLS) detergents. The ABS detergents were deposited from approximately 1940 through 1965, when ABS detergents were banned. From 1965 to the present, LAS and NaLS detergents were in the sewage. The ABS detergents appear to be transported in the aquifer at the same rate as the specific conductance (major cations and anions) and boron, which are currently used as conservative tracers of the plume of contaminated groundwater. There appears to be little or no biological degradation of the ABS detergents in the aquifer, based on their concentration in the plume. On the other hand, the LAS and NaLS detergents have degraded rapidly and have been detected only 0.6 km down gradient. The roleof the detergents in the transport of other organic compounds in the plume is nuclear. There is a separation of the ABS detergent plume and the volatile organic compound plume; however, the time of entry of the detergents and the volatile organic compounds is unknown. Therefore, it is not possible to conclude on the interaction of these two classes of compounds.     

Probabilistic risk assessment for zinc in some commercial dishwashing detergents: the anaerobic digestion processes in US POTWs

A US patent was issued to a commercial dishwashing detergent composition in which soluble zinc serves as an anti-corrosion agent. Since the detergents are used in a down-the-drain fashion, some of the detergents are discharged as wastewater and treated in publicly owned treatment works (POTWs). A risk assessment was previously conducted which focused on the nitrification processes in US POTWs. As a conservative pollutant, zinc removed from wastewater during treatment is transferred to sludges and at sufficiently high concentrations may inhibit the sludge treatment processes. In the present assessment, a probabilistic risk assessment was conducted to quantitatively determine the risk of zinc in the detergents to the anaerobic digestion processes in US POTWs. The procedure for POTW local limit development designed by the US Environmental Protection Agency (EPA) was used as a reference when conducting the risk assessment. The assessment took into account the background zinc concentrations in POTW influents and was conducted at different market penetration rates (MPRs) for the US market of detergents based on the patented formula. Several factors were present that contributed to the conservativeness of the assessment. Results indicate that zinc in detergents does not present a significant risk to the anaerobic digestion processes in POTWs at a MPR up to 10%, with a probability of anaerobic digestion inhibition of below 1%.     

Diversity shift in bacterial phenol hydroxylases driven by alkyl-phenols in oil refinery wastewaters

Environmental Science and Pollution Research - Phenol hydroxylases (PHs) play a primary role in the bacterial degradation of phenol and alkylphenols. They are divided into two main classes,...     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.     

家用洗衣粉中磷对斜生栅藻生长的影响

以洗衣粉中的有机磷为磷源,通过室内模拟的方法研究在不同磷浓度的水体条件下斜生栅藻的生长情况,以及磷对斜生栅藻的生长是否有毒害作用.通过显微计数测定藻细胞数目来探讨洗衣粉中磷对斜生栅藻生长的影响;同时分析了洗衣粉中磷对斜生栅藻96 h生长期中光合色素的影响.结果表明,洗衣粉中的磷除了促进藻生长外,其浓度过低或过高都会抑制藻的生长.由实验结果可得,磷对藻生长的富营养化作用和毒性作用取决于磷浓度的高低.     

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

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.     

Determinations and residual characteristics of triclosan in household food detergents of Taiwan

Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) is a widely used antibacterial agent. However, it was concerned recently that triclosan might act as an antibiotic and will cause resistant bacterial strains. Furthermore, possible formation of toxic chloroform was also reported when the triclosan contained in household dishwashing soaps reacted with the chlorinated water. To assess the associate risks from possible exposures, concentrations of triclosan in household food detergents of Taiwan were determined in this study. High performance liquid chromatography (HPLC) with UV detector at 280 nm was used to analyze the triclosan in samples. Factors that might affect the residual characteristics of triclosan from detergents on dishware and fruits, including the concentrations of detergents used, the temperature and immersion time for water before the cleaning processes, the temperatures of water used for the cleaning processes, and the materials of dishware made of, were evaluated under the orthogonal experiment design by the Taguchi method. By the analysis of variance, the orders of importance of different parameters were determined. The concentrations of triclosan detected in household food detergents were found to be 1.7 x 10(-2) -5.6 x 10(-1) (triclosan/detergent, mg g(-1)). For residual characteristics, the concentration of detergents used as well as the materials of dishware were found to be the significant factors that will affect the triclosan left on the dishware. On the other hand, the concentration of triclosan in the detergents was found to be the only factor that will affect the triclosan left on fruits. The maximum dose of triclosan exposures from the use of household food detergents in Taiwan was also estimated in the study.     

Probabilistic risk assessment for zinc in some commercial dishwashing detergents: the nitrification processes in US POTWs

A US patent was issued to a commercial dishwashing detergent composition in which soluble zinc is used to protect glassware from corrosion. Some of the consumed detergents are discharged as wastewater and treated in publicly owned treatment works (POTWs). A probabilistic risk assessment was conducted to quantitatively determine the risk of zinc in the detergents to the nitrification processes in US POTWs. The procedure for POTW local limit development designed by the US Environmental Protection Agency (EPA) was used as a reference when conducting the risk assessment. The assessment took into account the background zinc concentrations in POTW influents and potential shock loading patterns, and was conducted at different market penetration rates (MPRs) for the US market of detergents based on the patented formula. The assessment involved several conservative factors including conservative determination of primary treatment efficiency, bioavailability, inhibition concentration, configuration of the nitrification process, as well as background zinc concentration in wastewater. With the conservative factors in the assessment, it was found that zinc in detergents does not present a significant risk to the nitrification processes in POTWs at a MPR up to 10%. It was noted that additional analyses would be required when the MPR is higher than 10% to adequately account for the effects of the conservative factors on the result of the assessment.     

Modelling of the fate of selected endocrine disruptors in a municipal wastewater treatment plant in South East Queensland, Australia

The aim of this study was to develop a fugacity-based analysis of the fate of selected industrial compounds (alkylphenols and phthalates) with endocrine disrupting properties in a conventional activated sludge wastewater treatment plant (WWTP A) in South East Queensland, Australia. Using mass balance principles, a fugacity model was developed for correlating and predicting the steady-state-phase concentrations, the process stream fluxes, and the fate of four phthalates and four alkylphenols in WWTP A. Input data are the compound's physicochemical properties, measured concentrations and the plant's operating design and parameters. The relative amounts of chemicals that are likely to be volatilized, sorbed to sludge, biotransformed, and discharge in the effluent water was determined. Since it was difficult to predict biotransformation, measured concentrations were used to calibrate the model in terms of biotransformation rate constant. Results obtained by applying the model for the eight compounds showed <40% differences between most of the estimated and measured data from WWTP A. All eight compounds that were modelled in this study had high removal efficacy from WWTP A. Apart from benzyl butyl phthalate and bisphenol A, the majority is removed via biotransformation followed by a lesser proportion removed with the primary sludge. Fugacity analysis provides useful insight into compound fate in a WWTP and with further calibration and validation the model should be useful for correlative and predictive purposes.     

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

Background, aim and scope

Groundwaters and source waters are exposed to environmental pollution due to agricultural and industrial activities that can enhance the leaching of organic contaminants. Pesticides are among the most widely studied compounds in groundwater, but little information is available on the presence of phthalates, alkylphenols and bisphenol A. These compounds are used in pesticide formulations and represent an emerging family of contaminants due to their widespread environmental presence and endocrine-disrupting properties. Knowledge on the occurrence of contaminants in source waters intended for bottling is important for sanitary and regulatory purposes. So the aim of the present study was to evaluate the presence of phthalates, alkylphenols, triazines, chloroacetamides and bisphenol A throughout 131 Spanish water sources intended for bottling. Waters studied were spring waters and boreholes which have a protection diameter to minimize environmental contamination.

Materials and methods

Waters were solid-phase extracted (SPE) and analysed by gas chromatography coupled to mass spectrometry (GC-MS). Quality control analysis comprising recovery studies, blank analysis and limits of detection were performed.

Results and discussion

Using SPE and GC-MS, the 21 target compounds were satisfactorily recovered (77?C124?%) and limits of quantification were between 0.0004 and 0.029???g/L for pesticides, while for alkylphenols, bisphenol A and phthalates the limits of quantification were from 0.0018???g/L for octylphenol to 0.970???g/L for bis(2-ethylhexyl) phthalate. Among the 21 compounds analysed, only 9 were detected at levels between 0.002 and 1.115???g/L. Compounds identified were triazine herbicides, alkylphenols, bisphenol A and two phthalates. Spring waters or shallow boreholes were the sites more vulnerable to contaminants. Eighty-five percent of the samples did not contain any of the target compounds.

Conclusions

Target compounds were detected in a very low concentration and only in very few samples. This indicates the good quality of source waters intended for bottling and the effectiveness of the protection measures adopted in Spain. None of the samples analysed exceeded the maximum legislated levels for drinking water both in Spain and in the European Union.     

Toxicity and detoxification of Swedish detergents and softener products

Detergents and softeners are used in large quantities and some of their ingredients are highly toxic to aquatic organisms. In the present study the acute toxicity to Daphnia magna was determined for 26 detergents and five softener Swedish products. Only one of the detergents had a 48-h EC50 > 100 mg/l. The 48-h EC50 for the other 25 detergents ranged from 4 to 85 mg/l. The 48-h EC50 for the five softeners ranged from 15 to 166 mg/l. Detoxification tests, with and without inoculum of sewage organisms, showed that all tested products were detoxified to some extent after 16 days and that the rate of detoxification was considerably higher with addition of sewage organisms. Toxicity to D. magna of the detergents and softeners, and the biotic detoxification rate was correlated with the concentration of surfactants used in formulating the products (more surfactants increased toxicity and a slower rate of detoxification). These results emphasize the importance of biological purification of domestic wastewater containing detergents and a suggested development of less toxic and more easily degradable surfactants.     

Chemical and biochemical tools to assess pollution exposure in cultured fish

There is little information regarding pollutant levels in farmed fish, and the risks associated to consumption. This study was designed to assess levels of exposure to metals, organochlorinated compounds, polycyclic aromatic hydrocarbons (PAHs) and alkylphenols (APEs) in farmed sea bass Dicentrarchus labrax from five aquacultures located in Southern Europe. Additionally, several biochemical responses (metallothionein, 7-ethoxyresorufin O-deethylase, vitellogenin) were determined as complementary tools. The obtained data indicate that pollutants exposure in farmed fish is similar to the levels reported in wild specimens from the area. Nonetheless, some biochemical responses were observed in the studied organisms, viz. metallothionein induction in Cu exposed organisms, and 7-ethoxyresorufin O-deethylase (EROD) and vitellogenin induction in PAHs and APEs exposed ones. The study further supports the usefulness of the biomarker approach as a first screening method to discriminate between basal and high levels of exposure in cultured fish.     

不同类型清洗剂对含聚油泥清洗效果及界面性质的影响

为解决聚驱采出液中产生的大量含聚油泥造成石油资源浪费和环境污染问题,选用化学清洗法对含聚油泥进行处理。不同类型化学清洗剂对含聚油泥清洗效果的规律是:无机型和非离子型清洗剂对含聚油泥清洗效果最好,阴离子型清洗剂次之,阳离子型清洗剂最差。优化了无机清洗剂Na2SiO3和非离子型清洗剂EL100的脱油条件,脱油率分别达到91.12%和85.59%。不同类型清洗剂清洗含聚油泥的脱油率与油水界面性质具有明显的关联性,即脱油率越高,水相电导率越小,油滴Zeta电位绝对值越小,油滴中值粒径越大,油水界面张力越小。     

Management options and effects on a marine ecosystem: assessing the future of the Baltic

We are using the coupled models in a decision support system, Nest, to evaluate the response of the marine ecosystem to changes in external loads through various management options. The models address all the seven major marine basins and the entire drainage basin of the Baltic Sea. A series of future scenarios have been developed, in close collaboration with the Helsinki Commission, to see the possible effects of improved wastewater treatment and manure handling, phosphorus-free detergents, and less intensive land use and live stocks. Improved wastewater treatment and the use of phosphorus-free detergents in the entire region would drastically decrease phosphorus loads and improve the marine environment, particularly the occurrence of cyanobacterial blooms. However, the Baltic Sea will remain eutrophic, and to reduce other effects, a substantial reduction of nitrogen emissions must be implemented. This can only be obtained in these scenarios by drastically changing land use. In a final scenario, we have turned 50% of all agricultural lands into grasslands, together with efficient wastewater treatments and a ban of phosphorus in detergents. This scenario will substantially reduce primary production and the extension of hypoxic bottoms, increase water transparency in the most eutrophied basins, and virtually eliminate extensive cyanobacterial blooms.     

巢湖合肥地区洗衣粉排磷占入湖磷贡献率的研究

合肥地区人均洗衣粉用量为3．12kg/a,洗衣粉总用量为8345t/a,洗衣粉带入水体的总磷量为256．08t/a,占入湖总磷负荷量的13．62％。因此,实行“禁磷”措施后,可削减该地区入湖总磷负荷量的13．62％,对改善巢湖水质将会起到一定的积极作用。     

Volatile compounds in flavor-tainted fish from the Upper Wisconsin River

Fillets from Walleye pike (Stizostedion vitreum) and Northern pike (Esox lucius) captured from the Upper Wisconsin River were analyzed for volatile components using simultaneous steam distillation-extraction and GC-MS techniques. Based on comparative odor assessments of eluting GC fractions and GC-MS analysis between control and tainted fish, trace amounts (ppb) of alkylphenols (2-isopropyl-, 4-isopropyl-, 2,4-diisopropyl-, 2,5-diisopropyl-, 2,6-diisopropyl-, 3,5-diisopropyl-, 5-methyl-2-isopropyl-, and 2-methyl-5-isopropyl-) and thiophenol were identified as the principal contributors to flavor-tainting found in fish during the spring of the year. Geosmin and 2-methylisoborneol were major contributors to mustiness flavor-tainting occurring in fish captured in the late summer and were more abundant in downstream fish than in upstream control fish.