Elimination of endocrine disrupting chemicals nonylphenol and bisphenol A and personal care product ingredient triclosan using enzyme preparation from the white rot fungus Coriolopsis polyzona

The biocatalytic elimination of the endocrine disrupting chemicals (EDC) nonylphenol (NP) and bisphenol A (BPA) and the personal care product ingredient triclosan (TCS) by the enzyme preparation from the white rot fungus Coriolopsis polyzona was investigated. Analysis of variance methodology showed that the pH and the temperature are statistically significant factors in the removal of NP, BPA and TCS. The elimination of NP and TCS was best at a temperature of 50 degrees C and the disappearance of BPA at 40 degrees C, whereas the most suitable pH for all three micropollutants was 5. After a 4-h treatment of the three target compounds at concentrations of 5 mg l(-1) all of the NP and BPA were eliminated. In the case of TCS, 65% was removed after either a 4 or an 8-h treatment. The utilisation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) in the laccase/mediator system significantly increased the efficiency of the enzymatic treatment. The elimination of NP and BPA was directly associated with the disappearance of the estrogenic activity. Mass spectrometry analysis showed that the enzymatic treatment produced high molecular weight metabolites through a radical polymerization mechanism of NP, BPA and TCS. These oligomers were produced through the formation of C-C or C-O bonds. The polymerization of NP produced dimers, trimers, tetramers and pentamers which had molecular weights of 438, 656, 874 and 1092 amu respectively. The polymerization of BPA produced dimers, trimers and tetramers which had molecular weights of 454, 680 and 906 amu. Finally, the polymerization of TCS produced dimers, trimers and tetramers which had molecular weights of 574, 859 and 1146 amu.     

Population-level toxicity of the insecticide, spinosad and the nonylphenol polyethoxylate, R-11, to the cladoceran species Ceriodaphnia dubia Richard

The effects of the natural insecticide, spinosad, and the agricultural adjuvant, R-11, were evaluated on populations of the water flea, Ceriodaphnia dubia after chronic 8-day exposures. The number of individuals used to start the chronic exposure studies (founders) and the number of offspring/surviving female were significantly reduced after exposure to spinosad concentrations ≥ 2.5 μg/L. The final number of individuals was significantly reduced after exposure to spinosad concentrations ≥ 1.0 μg/L. Population growth rate was significantly reduced after exposure to spinosad concentrations ≥ 1 μg/L. Extinction occurred (defined as negative population growth rate) after exposure to spinosad concentrations of 10 μg/L. Therefore, negative effects were observed in C. dubia after exposure to spinosad at a concentration near the chronic expected environmental concentration (EEC) of 2.3 μg/L. R-11 was much less toxic to C. dubia than spinosad. The number of founders was not significantly reduced until C. dubia were exposed to 12,000 μg/L. The number of offspring/surviving female, final number of individuals, and population growth rate were significantly reduced after exposure to R-11 concentrations ≥ 5,000 μg/L. Extinction occurred after exposure to R-11 concentrations of 12,000 μg/L which was above the EEC of 790 μg/L. These results indicate that spinosad and R-11 both have lethal and sublethal effects on C. dubia. However, spinosad appears to affect C. dubia at or near the EEC while R-11 does not negatively affect this species until concentrations are much higher than the EEC.     

Interaction of chemical cues from fish tissues and organophosphorous pesticides on Ceriodaphnia dubia survival

Cladocera are frequently used as test organisms for assessing chemical and effluent toxicity and have been shown to respond to stimuli and cues from potential predators. In this study, the interactive effects of visual and chemical cues of fish and two organophosphorous pesticides on survival of Ceriodaphnia dubia were examined. A significant chemical cue (homogenized Pimephales promelas) and malathion interaction was observed on C. dubia survival (P = 0.006). Chemical cue and 2.82 microg/L malathion resulted in a 76.0% reduction in survival compared to malathion alone (P < 0.01). Furthermore, potentiation of malathion toxicity varied based on the source of chemical cues (i.e., epithelial or whole body). It is unclear in this study whether these chemical cues elicited a predation-related stress in C. dubia. Future research should examine the mechanism of this interaction and determine what role, if any, stress responses by C. dubia might play in the interaction.     

Reduction in labile copper in the 7-day Ceriodaphnia dubia toxicity test due to the interaction with zooplankton food

Due to the increased popularity of zooplankton toxicity tests, it is important to investigate potential confounding factors. Though zooplankton food has been studied extensively to meet the nutritional needs of the zooplankton, less research has been done on whether food addition reduces the toxicity of metals in the tested sample. This investigation combines toxicity tests and metal speciation analysis to determine whether the EPA recommended food of YCT (yeast, cerophyll, and trout chow) and Pseudokirchneriella subcapitata (formerly Selenastrum capricornutum) reduces copper toxicity by decreasing the concentration of labile copper. Toxicity tests were performed with Ceriodaphnia dubia on culture water spiked with 0, 787, and 1574 nM copper with five different food levels. A Chelex-100 cation exchange resin and a graphite furnace-atomic absorption spectrophotometer were used in conjunction with the toxicity tests to measure the amount of labile copper in the culture water. At the EPA recommended food dosage, the C. dubia food has a chelating capacity of approximately 500 nM Cu. For both concentrations of spiked culture water, the toxicity to C. dubia was reduced with increasing food level, which seemed to be both from a decrease in labile copper concentration and an increase in the nutritional condition of the zooplankton.     

Feasibility of constructed wetlands for removing chlorothalonil and chlorpyrifos from aqueous mixtures

Chlorpyrifos (an insecticide) and chlorothalonil (a fungicide) are transported in stormwater runoff and can be lethal to receiving aquatic system biota. This study determined removal rates of chlorpyrifos and chlorothalonil in simulated stormwater runoff treated in constructed wetland mesocosms. Using sentinel species, Ceriodaphnia dubia and Pimephales promelas, observed declines in toxicity of the simulated runoff after treatment were 98 and 100%, respectively. First order removal rates were 0.039/h for chlorpyrifos and 0.295/h for chlorothalonil in these experiments. Constructed wetland mesocosms were effective for decreasing concentrations of chlorpyrifos and chlorothalonil in simulated stormwater runoff, and decreasing P. promelas and C. dubia mortality resulting from these exposures. The results from this study indicate that constructed wetlands could be part of an efficient mitigation strategy for stormwater runoff containing these pesticides.     

Surface metal adsorption on zooplankton carapaces: implications for exposure and effects in consumer organisms

The current study aimed to determine the potential of two important aquatic invertebrate crustacean species, Daphnia magna and Ceriodaphnia dubia, to adsorb cadmium on to their carapaces from aqueous solution. Using the Langmuir equation to model data outputs, it was shown that cadmium readily became associated with the carapace surfaces of both species, with uptake being dependent on exposure time and concentration. Maximum carapace-adsorption potential was found to be directly related to surface area, so that at predicted carapace saturation, D. magna neonates bound approximately five times more cadmium than the smaller C. dubia neonates. However, adsorption per unit surface area was found to be similar under the same exposure conditions. Results of surface metal adsorption studies in C. dubia suggested that short term exposures to high concentrations of aqueous cadmium would lead to similar levels of adsorption as obtained with long-term exposures to low concentrations. The study illustrates that contaminants adsorbed to prey surfaces may be an important mechanism of exposure to predators, and highlights some potential problems of feeding organisms during long-term toxicity tests.     

Irrigation runoff insecticide pollution of rivers in the Imperial Valley, California (USA)

The Alamo and New Rivers located in the Imperial Valley, California receive large volumes of irrigation runoff and discharge into the ecologically sensitive Salton Sea. Between 1993 and 2002 we conducted a series of studies to assess water quality using three aquatic species: a cladoceran (Ceriodaphnia dubia), a mysid (Neomysis mercedis), and a larval fish (Pimephales promelas). Although no mortality was observed with the P. promelas, high-level toxicity to the invertebrate species was documented in samples from both rivers during many months of each year. Toxicity identifications and chemical analyses identified the organophosphorus insecticides (OP), chlorpyrifos and diazinon, as the cause of C. dubia toxicity. The extent of the C. dubia mortality was highly correlated with quantities of these OPs applied in the river watersheds. C. dubia mortality occurred during more months of our 2001/2002 study than in the 1990s investigations. During 2001/2002, the extensive C. dubia mortality observed in New River samples was caused by OP insecticide pollution that originated from Mexico. Mortality to N. mercedis in New River samples was likely caused by contaminants other than OP insecticides. Our studies document OP insecticide-caused pollution of the Alamo River over a 10-year period and provide the necessary information for remediation efforts.     

Toxicity of prednisolone, dexamethasone and their photochemical derivatives on aquatic organisms

Light exposure of aqueous suspensions of prednisolone and dexamethasone causes their partial phototransformation. The photoproducts, isolated by chromatographic techniques, have been identified by spectroscopic means. Prednisolone, dexamethasone and their photoproducts have been tested to evaluate their acute and chronic toxic effects on some freshwater chain organisms. The rotifer Brachionus calyciflorus and the crustaceans Thamnocephalus platyurus and Daphnia magna were chosen to perform acute toxicity tests, while the alga Pseudokircheneriella subcapitata (formerly known as Selenastrum capricornutum) and the crustacean Ceriodaphnia dubia to perform chronic tests. The photochemical derivatives are more toxic than the parent compounds. Generally low acute toxicity was found. Chronic exposure to this class of pharmaceuticals caused inhibition of growth population on the freshwater crustacean C. dubia while the alga P. subcapitata seems to be less affected by the presence of these drugs.     

Chloroperoxidase-mediated transformation of highly halogenated monoaromatic compounds

Peroxidase transformations of widely distributed pollutants, tetra- and penta-chlorinated phenols and anilines, were studied using different peroxidases. Chloroperoxidase from Caldariomyces fumago was able to transform tetra- and penta-chlorinated phenols and anilines, while horseradish peroxidase, lignin peroxidase from Phanerochaete chrysosporium and versatile peroxidase from Bjerkandera adusta were able only to transform the halogenated phenols. Chloroperoxidase showed a specific activity on pentachlorophenol two orders of magnitude higher than lignin peroxidase and horseradish peroxidase, and one order of magnitude higher than versatile peroxidase. The main product from peroxidase oxidation in all cases was a polymeric and insoluble material. The insolubilization of halogenated phenols and anilines permits their removal, reduces their bioavailability, and thus reduces their environmental impact. The other minor products from the enzymatic transformation of highly chlorinated compounds were determined by mass spectrometry. Tetrachloroquinone, dimers and trimers of halogenated compounds were also identified. Chloroperoxidase was able to halogenate tetrachloroaniline to form pentachloroaniline.     

Aquatic toxicity of glyphosate-based formulations: comparison between different organisms and the effects of environmental factors

Glyphosate-based herbicides (e.g. Roundup) are extensively used in the aquatic environment, but there is a paucity of data on the toxicity of the formulated products and the influences by environmental factors. In this study, the acute toxicity of technical-grade glyphosate acid, isopropylamine (IPA) salt of glyphosate, Roundup and its surfactant polyoxyethylene amine (POEA) to Microtox bacterium (Vibrio fischeri), microalgae (Selenastrum capricornutum and Skeletonema costatum), protozoa (Tetrahymena pyriformis and Euplotes vannus) and crustaceans (Ceriodaphnia dubia and Acartia tonsa) was examined and the relative toxicity contributions of POEA to Roundup were calculated. The effects of four environmental factors (temperature, pH, suspended sediment and algal food concentrations) on the acute toxicity of Roundup to C. dubia were also examined. Generally, the toxicity order of the chemicals was: POEA>Roundup>glyphosate acid>IPA salt of glyphosate, while the toxicity of glyphosate acid was mainly due to its high acidity. Microtox bacterium and protozoa had similar sensitivities towards Roundup toxicity (i.e. IC50 from 23.5 to 29.5 mg AE/l). In contrast, microalgae and crustaceans were 4-5 folds more sensitive to Roundup toxicity than bacteria and protozoa. Except photosynthetic microalgae, POEA accounted for more than 86% of Roundup toxicity and the toxicity contribution of POEA was shown to be species-dependent. Increase in pH (6-9) and increase of suspended sediment concentration (0-200 mg/l) significantly increased the toxicity of Roundup to C. dubia, but there were no significant effects due to temperature change and food addition.     

Phototransformation products of tamoxifen by sunlight in water. Toxicity of the drug and its derivatives on aquatic organisms

Transformation of tamoxifen has been observed in water by prolonged sunlight irradiation. The main photoproducts, isolated by chromatographic techniques, have been identified by spectroscopic means. Photoisomerization, photocyclization and, to a lesser extent, photooxygenation appear to be involved in the degradation of the drug. The acute and chronic toxicity of the parent drug and its photoproducts were tested on non-target aquatic organisms (Brachionus calyciflorus, Thamnocephalus platyurus, Daphnia magna and Ceriodaphnia dubia). Exposure to all the compounds induced mainly chronic effects without significant differences among the parental and derivative compounds.     

Response of Ceriodaphnia dubia to ionic silver: discrepancies among model predictions, measured concentrations and mortality

Silver thiosulfate, often a waste product of photoprocessing, is less bioavailable or toxic to aquatic organisms than is ionic silver. We conducted duplicate 48-h Ceriodaphnia dubia tests in reconstituted laboratory water using treatments of 92.7 nM Ag+ with various concentrations of thiosulfate. Expected Ag+ concentrations were generated for thiosulfate treatment levels using MINEQL + chemical equilibrium modeling. Ag+ concentrations in treatments were determined using a novel silicon-based sensor. Based on predicted Ag+ and published 48-h LC50 values for C. dubia, we did not expect to observe adverse effects. Yet, 100% mortality was observed at low thiosulfate treatments, whereas > 85% and > 95% survival was observed at higher thiosulfate treatment levels, respectively. Our results indicate that biotic responses match the sensor-based Ag+ concentrations. However, there is a discrepancy between these empirical results and responses expected to occur with Ag+ concentrations as predicted by MINEQL + chemical modeling. By correlating silicon sensor data with toxicity results obtained from our laboratory, our work clearly relates a specific chemical form (Ag+) to toxicity results.     

Acute toxicity of triphenyltin hydroxide to three cladoceran species

The toxicity of an organotin pesticide, triphenyltin hydroxide, was assessed with several freshwater cladoceran species. Daphnia pulex, Daphnia magna, and Ceriodaphnia dubia were exposed for 48 h to triphenyltin hydroxide in static acute toxicity tests. Values of the 48-h trimmed Spearman-Karber EC(50)s for the three species were found to be 14.5, 16.5, and 11.3 microg litre(-1), respectively. Analysis of variance performed on EC(50) values of replicates revealed no significant differences between the three species. Methods were employed which decrease animal handling stress and increase the accuracy and precision of the concentrations.     

Waterborne and sediment toxicity of fluoxetine to select organisms

Ecological risk assessments of pharmaceuticals are currently difficult because little-to-no aquatic hazard and exposure information exists in the peer-reviewed literature for most therapeutics. Recently several studies have identified fluoxetine, a widely prescribed antidepressant, in municipal effluents. To evaluate the potential aquatic toxicity of fluoxetine, single species laboratory toxicity tests were performed to assess hazard to aquatic biota. Average LC(50) values for Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas were 0.756 (234 microg/l), 2.65 (820 microg/l), and 2.28 microM (705 microg/l), respectively. Pseudokirchneriella subcapitata growth and C. dubia fecundity were decreased by 0.044 (14 microg/l) and 0.72 microM (223 microg/l) fluoxetine treatments, respectively. Oryias latipes survival was not affected by fluoxteine exposure up to a concentration of 28.9 microM (8.9 mg/l). An LC(50) of 15.2 mg/kg was estimated for Chironomus tentans. Hyalella azteca survival was not affected up to 43 mg/kg fluoxetine sediment exposure. Growth lowest observed effect concentrations for C. tentans and H. azteca were 1.3 and 5.6 mg/kg, respectively. Our findings indicate that lowest measured fluoxetine effect levels are an order of magnitude higher than highest reported municipal effluent concentrations.     

Tolerance and acclimation to zinc of Ceriodaphnia dubia

Zinc is an essential metal for all living organisms. However, so far, little or no attention has been paid to the consequences of zinc deficiency or acclimation to this metal during culturing and testing on toxicity test results. In this study, the cladoceran Ceriodaphnia dubia was acclimated for 10 generations to four zinc concentrations ranging from 0 to 100 microg Zn/l and changes in zinc tolerance were monitored using acute (48 h) and chronic (9 days) assays. C. dubia deprived of zinc and acclimated to 13 microg Zn/l had a lower fitness in comparison with organisms acclimated to 50 and 100 microg Zn/l. In the two lowest versus the two highest acclimation concentrations the 9dEC50 values (on immobility) were 358-387 microg Zn/l versus 486-489 microg Zn/l; the mean number of young per female was 11-18 versus 25-32; and the time to first brood was 4.7-5.0 days versus 4.0-4.3 days. Moreover, the coefficient of variation of all parameters tested was highest in the two lowest acclimation concentrations. The results indicate that culturing test animals in media lacking trace metals such as zinc could give rise to animals that are unnaturally sensitive to those same metals daring toxicity tests.     

Inter- and intra-species variation in acute zinc tolerance of field-collected cladoceran populations

Acute zinc toxicity was assessed for 10 freshwater cladoceran species collected in six different ecosystems across Europe and for two standard laboratory-reared species (Daphnia magna and Ceriodaphnia dubia). The collected organisms belonged to five different genera: Daphnia (subgenus Daphnia and Ctenodaphnia), Ceriodaphnia, Simocephalus, Acroperus and Chydorus. The 48-h EC50 of the field-collected organisms tested in standard laboratory water ranged from 375+/-141 to 4314+/-1513 microg Znl(-1). The laboratory clone of D. magna was less sensitive than the majority of the field-collected species, while our laboratory Ceriodaphnia dubia was the second most sensitive. Considerable inter-species variation was found within the genus of Ceriodaphnia (factor 6) and within the genus Daphnia (factor 8). Among the different (sub)genera tested, Chydorus and Ctenodaphnia were significantly more tolerant than the others (up to a factor 3 difference). A significant positive relationship (r2=0.67, p<0.05) between the mean cladoceran 48-h EC50 and the ambient zinc concentration of the different aquatic systems was demonstrated, suggesting a role of acclimation and/or adaptation. No significant correlation between the acute zinc tolerance and the length of the organisms was found.     

The effects of elevated metals on benthic community metabolism in a Rocky Mountain stream

The effects of elevated metals (dissolved Zn, Mn and/or Fe) in a Rocky Mountain stream were assessed using measures of primary productivity, community respiration and water-column toxicity. Primary productivity was measured as rates of O2 evolution from natural substrates incubated in situ in closed chambers. Oxygen depletion within these chambers, when incubated in the dark, provided estimates of periphyton community respiration. Sediment community respiration on fine-grained sediments, collected and composited along each stream study reach, was measured on-site by incubating these sediments in closed chambers and measuring O2 depletion. Toxicity was measured as percent mortality of Ceriodaphnia dubia during 48 h acute tests. Gross (GPP) and net primary productivity (NPP) decreased significantly with increasing metal concentrations, from 10.88 +/- 1.46 g O2 m(-2) day(-1) to 0.83 +/- 0.20 g O2 m(-2) day(-1) and 9.85 +/- 1.43 g O2 m(-2) day(-1) to 0.81 +/- 0.20 g O2 m(-2) day(-1), respectively for the reference and most impacted site. Community respiration (CR) declined from 0.65 +/- 0.08 g O2 m(-2) day(-1) to 0.02 +/- 0.01 g O2 m(-2) day(-1) with increasing metal concentrations. Sediment community respiration (SCR) decreased from 0.26 +/- 0.02 g O2 m(-2) day(-1) to 0.01 +/- 0.01 g O2 m(-2) day(-1) at these same sites. Ceriodaphnia dubia mortality increased from 0% at the reference site to 95 +/- 5% at the most impacted sites. Net daily metabolism, quantum yield and assimilation ratio all decreased with increasing metal concentrations, suggesting that both autotrophic and heterotrophic components of the periphyton community were impaired. Overall, functional measures were able to discern sites receiving greater metal impacts from less-impacted sites, with combinations of dissolved metals explaining between 25 and 92% of the variance in the regression models. Using these regression models we were able to calculate lethal and inhibition concentrations of dissolved Zn in the Eagle River. The lethal concentration (LC50) of Zn for Ceriodaphnia dubia is 123 mg liter(-1). The concentrations of Zn which inhibited respiration (IC50) were 177 mg liter(-1) for CR and 199 mg liter(-1) for SCR. These results indicate functional measures may be as sensitive to metal concentrations as acute toxicity tests.     

Health risk assessment of occupational exposure to styrene in Neyshabur electronic industries

Environmental Science and Pollution Research - Styrene is one of the essential components in making thousands of everyday products. Occupational exposure to styrene causes pulmonary, neurological,...     

Synergistic toxic effect of nano-Al2O3 and As(V) on Ceriodaphnia dubia

Engineered nanomaterials (ENMs) alone could negatively impact the environment and human health. However, their role in the presence of other toxic substances is not well understood. The toxicity of nano-Al(2)O(3), inorganic As(V), and a combination of both was examined with C. dubia as the model organisms. Bare nano-Al(2)O(3) particles exhibited partial mortality at concentrations of greater than 200mg/L. When As(V) was also present, a significant amount of As(V) was accumulated on the nano-Al(2)O(3) surface, and the calculated LC(50) of As(V) in the presence of nano-Al(2)O(3) was lower than that it was without the nano-Al(2)O(3). The adsorption of As(V) on the nano-Al(2)O(3) surface and the uptake of nano-Al(2)O(3) by C. dubia were both verified. Therefore, the uptake of As(V)-loaded nano-Al(2)O(3) was a major reason for the enhanced toxic effect.     

Integrated assessment of the impacts of agricultural drainwater in the Salinas River (California,USA)

The Salinas River is the largest of the three rivers that drain into the Monterey Bay National Marine Sanctuary in central California. Large areas of this watershed are cultivated year-round in row crops and previous laboratory studies have demonstrated that acute toxicity of agricultural drainwater to Ceriodaphnia dubia is caused by the organophosphate (OP) pesticides chlorpyrifos and diazinon. In the current study, we used a combination of ecotoxicologic tools to investigate incidence of chemical contamination and toxicity in waters and sediments in the river downstream of a previously uncharacterized agricultural drainage creek system. Water column toxicity was investigated using a cladoceran C. dubia while sediment toxicity was investigated using an amphipod Hyalella azteca. Ecological impacts of drainwater were investigated using bioassessments of macroinvertebrate community structure. The results indicated that Salinas River water downstream of the agricultural drain is acutely toxic to Ceriodaphnia, and toxicity to this species was highly correlated with combined toxic units (TUs) of chlorpyrifos and diazinon. Laboratory tests were used to demonstrate that sediments in this system were acutely toxic to H. azteca, which is a resident genus. Macroinvertebrate community structure was moderately impacted downstream of the agricultural drain input. While the lowest macroinvertebrate abundances were measured at the station demonstrating the greatest water column and sediment toxicity and the highest concentrations of pesticides, macroinvertebrate metrics were more significantly correlated with bank vegetation cover than any other variable. Results of this study suggest that pesticide pollution is the likely cause of laboratory-measured toxicity in the Salinas River samples and that this factor may interact with other factors to impact the macroinvertebrate community in the system.