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881.
This study investigated the possible effects of a commonly used foliar herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) formulation on medulla spinalis of lebistes. Fish were exposed to 2,4-D (15, 30, 45 mg L−1), behavioral changes were monitored. Fish were fixed, histopathological examination was carried out on sections taken from the upper parts of the fish body. Histopathology showed increase in neuronal loss, swelling indicating formation of intracellular edema, vacuolization noticed as the formation of vacuoles within or adjacent to cells, deformation in the Nissl granules, pyknosis and gliosis in medulla spinalis. Behavioral changes were decreased general activity, grouping, shortness in breath, sudden rotations and jumping, loss of equilibrium and colour. In conclusion, this commercial formulation of 2,4-D is considerably neurotoxic to lebistes. Fish constitute the last link in the chain of the feeding cycle in aquatic eco-system, number of studies investigating acute and chronic neurotoxicity of various herbicides in fish should be increased.  相似文献   
882.
Na He  Peijun Li  Yuncheng Zhou  Shuxiu Fan  Wanxia Ren   《Chemosphere》2009,76(11):1491-1497
The reductive dechlorination and biodegradation of 2,24,5,5-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,24,5,5-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2,4,5,5-pentachlorobiphenyl. In laboratory batch experiments, 2,24,5,5-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2,4-trichlorobiphenyl (PCB#17), a reduction product from 2,24,5,5-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.  相似文献   
883.

Background, aim and scope

Estrogenic and non-estrogenic chemicals typically co-occur in the environment. Interference by non-estrogenic chemicals may confound the assessment of the actual estrogenic activity of complex environmental samples. The aim of the present study was to investigate whether, in which way and how seriously the estrogenic activity of single estrogens and the observed and predicted joint action of estrogenic mixtures is influenced by toxic masking and synergistic modulation caused by non-estrogenic chemical confounders.

Materials and methods

The yeast estrogen screen (YES) was adapted so that toxicity and estrogenicity could be quantified simultaneously in one experimental run. Mercury, two organic solvents (dimethyl sulfoxide (DMSO) and 2,4-dinitroaniline), a surfactant (LAS-12) and the antibiotic cycloheximide were selected as toxic but non-estrogenic test chemicals. The confounding impact of selected concentrations of these toxicants on the estrogenic activity of the hormone 17ß-estradiol was determined by co-incubation experiments. In a second step, the impact of toxic masking and synergistic modulation on the predictability of the joint action of 17ß-estradiol, estrone and estriol mixtures by concentration addition was analysed.

Results

Each of the non-estrogenic chemicals reduced the apparent estrogenicity of both single estrogens and their mixtures if applied at high, toxic concentrations. Besides this common pattern, a highly substance- and concentration-dependent impact of the non-estrogenic toxicants was observable. The activity of 17ß-estradiol was still reduced in the presence of only low or non-toxic concentrations of 2,4-dinitroaniline and cycloheximide, which was not the case for mercury and DMSO. A clear synergistic modulation, i.e. an enhanced estrogenic activity, was induced by the presence of slightly toxic concentrations of LAS-12. The joint estrogenic activity of the mixture of estrogens was affected by toxic masking and synergistic modulation in direct proportion to the single estrogens, which allowed for an adequate adaptation of concentration addition and thus unaffected predictability of the joint estrogenicity in the presence of non-estrogenic confounders.

Discussion

The modified YES proved to be a reliable system for the simultaneous quantification of yeast toxicity and estrogen receptor activation. Experimental results substantiate the available evidence for toxic masking as a relevant phenomenon in estrogenicity assessment of complex environmental samples. Synergistic modulation of estrogenic activity by non-estrogenic confounders might be of lower importance. The concept of concentration addition is discussed as a valuable tool for estrogenicity assessment of complex mixtures, with deviations of the measured joint estrogenicity from predictions indicating the need for refined analyses.

Conclusions

Two major challenges are to be considered simultaneously for a reliable analysis of the estrogenic activity of complex mixtures: the identification of known and suspected estrogenic compounds in the sample as well as the substance- and effect-level-dependent confounding impact of non-estrogenic toxicants.

Recommendations and perspectives

The application of screening assays such as the YES to complex mixtures should be accompanied by measures that safeguard against false negative results which may be caused by non-estrogenic but toxic confounders. Simultaneous assessments of estrogenicity and toxicity are generally advisable.  相似文献   
884.
Background, aim, and scope  The enzyme-linked receptor assay (ELRA) detects estrogenic and anti-estrogenic effects at the molecular level of receptor binding and is a useful tool for the integrative assessment of ecotoxicological potentials caused by hormonally active agents (HAA) and endocrine disrupting compounds (EDC). The main advantage of the ELRA is its high sample throughput and its robustness against cytotoxicity and microbial contamination. After a methodological adaptation to salinity of the ELRA, according to the first part of this study, which increased its salinity tolerance and sensitivity for 17-β-estradiol, the optimised ELRA was used to investigate 13 native sediments characterised by different levels of salinity and chemical contamination. The applicability of the ELRA for routine analysis in environmental assessment was evaluated. Salinity is often a critical factor for bioassays in ecotoxicological sediment assessment. Therefore, salinity of the samples was additionally adjusted to different levels to characterise its influence on elution and binding processes of receptor-binding substances. Materials and methods  The ELRA was carried out with the human estrogen receptor α (ER) in a 96-well microplate format using the experimental setup known from the competitive immunoassay based on ligand–protein interaction. It is an important improvement that a physiologically relevant receptor was used as a linking protein instead of an antibody. The microplates were coated with a 17-β-estradiol-BSA conjugate, and dilution series of estradiol and of native sediment samples were added and incubated with the ER. After a washing step, a biotinylated mouse anti-ER antibody was added to each well. Receptor binding to estradiol, agonistic and antagonistic receptor binding, were determined by a streptavidin-POD-biotin complex with subsequent measurement of the peroxidase activity at the wavelength of 450 nm using a commercial ELISA multiplate reader. The sediment elutriates and pore water samples of sediments were tested in a dilution series to evaluate at which dilution step the receptor-binding potential ends. In the elution process (see Section 2.1 to 2.2), a method was developed to adjust the salinity to the levels of the reference testings, which offers an appropriate option to adjust the salinity in both directions. Statistical evaluation was made with a combination of the Mann–Whitney U test and the pT-method. Results  This part of the study characterised the environmental factor ‘salinity’ for prospective applications of the ELRA. Using reference substances such as 17-β-estradiol, the ELRA showed sigmoid concentration-effect relations over a broad range from 0.05 μg/l to 100 μg/l under physiological conditions. After methodological optimisation, both sensitivity and tolerance of the assay against salinity could be significantly raised, and the ELRA became applicable under salinity conditions up to concentrations of 20.5‰. The mean relative inter-test error (n = 3) was around 11% with reference substances and below 5% for single sediments elutriates in three replicates each. For sediment testings, the pore water and different salinity-adjusted elutriates of 13 sediments were used. A clear differentiation of the receptor-binding potential could be reached by application of the pT-method. Thereby, pT-values from one to six could be assigned to the sediments, and the deviation caused by the different salinity conditions was one pT-value. The mean standard deviation in the salinity adaptation procedure of the elutriates was below 5%. Discussion  Although the ELRA has already been used for assessments of wastewater, sludge and soil, its applicability for samples to different salinity levels has not been investigated so far. Even if the ELRA is not as sensitive as the E-screen or the YES-assay, with regard to reference substances like 17-β-estradiol, it is a very useful tool for pre-screening, because it is able to integrate both estrogenic as well as anti-estrogenic receptor-binding effects. According to the results of sediment testing, and given the integrative power to detect different directions of effects, the ELRA shows sufficient sensitivity and salinity tolerance to discriminate receptor-binding potentials in environmental samples. Conclusions  The optimised ELRA assay is a fast, cost-effective, reliable and highly reproducible tool that can be used for high-throughput screening in a microplate format in detecting both estrogenic and anti-estrogenic effects. Additionally, the ELRA is robust against microbial contaminations, and is not susceptible towards cytotoxic interferences like the common cell-culture methods. The general applicability and sufficient sensitivity of the ELRA was shown in freshwater environments. Marine and brackish samples can be measured up to salinity levels of 20.5‰. Recommendations and perspectives  In view of the proven sensitivity, functionality and the fastness of the ELRA, it is recommendable to standardise the test method. At the moment, no adequate in vitro test procedure exists which is standardised to DIN or ISO levels. The E-screen and the yeast estrogen/androgen screens (YES/YAS) sometimes underlie strong cytotoxic effects, as reported in the first part of this study. Further development of an ELRA assay using human androgen receptors appears to be very promising to gain information about androgenic and anti-androgenic effects, too. This would offer a possibility to use the ELRA as a fast and reliable pre-screening tool for the detection of endocrine potentials, thus minimising time and cost-expensive animal experiments.  相似文献   
885.
Part V—sorption of pharmaceuticals and personal care products   总被引:5,自引:0,他引:5  
Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.  相似文献   
886.
Background, aim and scope  The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter ‘adsorbable organic halogens’ (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. Materials and methods  The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography–mass spectrometry. Results  Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. Discussion  The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. Conclusions  The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. Recommendations and perspectives  Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.  相似文献   
887.
Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L−1. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ13C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.  相似文献   
888.
Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of 1H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H2O2 concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H2O2 concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals  相似文献   
889.
The present study deals with the application of self-organizing maps (SOM) in order to model, classify and interpret seasonal and spatial variability of 210Po, 238U and 239+240Pu levels in the Vistula river basin. The data set represents concentration values for 3 alpha emitters (210Po, 238U and 239+240Pu) measured in surface water samples collected at 19 different sampling locations (8 in major Vistula stream while 11 in right or left Vistula tributaries) during four seasons (winter, spring, summer and autumn) in the framework of a one-year quality monitoring study. The advantages of an SOM algorithm, its classification and visualization ability for environmental data sets, are stressed. The neural-network based classification made it possible to reveal specific patterns related to both seasonal and spatial variability. In the middle and upper part of Vistula catchment as well as in the right-shore tributaries, concentrations of 210Po and 238U during summer and winter are the lowest. Concentrations of 210Po and 238U increase significantly during spring and autumn in the Vistula river catchment, especially in the delta of Vistula river. High concentration of anthropogenic originated 239+240Pu indicates “site-specific” character of pollution in two large left-shore tributaries located in the middle part of the Vistula drainage area. Efficient classification of sampling locations could lead to an optimization of river radiochemical sampling networks and to a better tracing of natural and anthropogenic changes along Vistula river stream.  相似文献   
890.
At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of kmax = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d− 1. The stable isotope-based biodegradation rate constant of 0.0027 d− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d− 1. With MM-kinetics a maximum degradation rate of kmax = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor εfield of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.  相似文献   
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