Ozonation of a mixture of estrogens and progestins in aqueous solution: Interpretation of experimental results by computational methods

In this paper the results of a thorough evaluation of the environmental fate and effects of azilsartan are presented. Azilsartan medoxomil is administered as a pro-drug for the treatment of patients with essential hypertension. The pro-drug is converted by hydrolysis to the active pharmaceutical ingredient azilsartan. Laboratory tests to evaluate the environmental fate and effects of azilsartan medoxomil were conducted with azilsartan and performed in accordance with OECD test guidelines. The predicted environmental concentration (PEC) in surface water was estimated at 0.32 μg L⁻¹ (above the action limit of 0.01 μg L⁻¹), triggering a Phase II assessment. Azilsartan is not readily biodegradable. Results of the water sediment study demonstrated significant shifting of azilsartan metabolites to sediment. Based on the equilibrium partitioning method, metabolites are unlikely to pose a risk to sediment-dwelling organisms. Ratios of the predicted environmental concentrations (PECs) to the predicted-no-effect concentrations (PNECs) did not exceed the relevant triggers, and the risk to aquatic, sewage treatment plant (STP), groundwater and sediment compartments was concluded acceptable. A terrestrial assessment was not triggered. Azilsartan poses an acceptable risk to the environment.     

1,2,4-trichlorobenzene marine risk assessment with special emphasis on the Osparcom region North Sea

A risk assessment on 1,2,4-trichlorobenzene was carried out specifically for the marine environment according to the methodology laid down in the EU Risk Assessment Regulation 1488/94 and the Guidance Documents of the EU Existing Substances Regulation 793/93. The study consists of the collection and evaluation of data on effects and environmental concentrations from analytical monitoring programs in large rivers and estuaries in the North Sea area. The risk is indicated by comparing the predicted environmental concentration (PEC) with the predicted no-effect concentrations (PNEC) for the marine aquatic environment. A PNECwater) value of 0.3 microg/l and a PNECsed value of 38 microg/kgdw were derived from the results of toxicological studies in organisms representing three trophic levels, i.e. aquatic plants, invertebrates and fish. Based on monitoring data two situations are distinguished: a typical case and a worst case with a PECwater of <0.047 and 0.1 microg/l, respectively, and a PECsed of 40 and 90 microg/kgdw, respectively. The calculated PEC/PNEC ratios were 0.16 and 0.3 for water and 1 and 2.4 for sediment, respectively. It was concluded that no risks are expected for aquatic organisms. Based on the combination of worst-case assumptions risks to benthic organisms could not be fully excluded, but since all open uses of 1,2,4-trichlorobenzene will be ended following the EU risk assessment outcome of 2001 any potential risk is expected to be reduced accordingly. 1,2,4-trichlorobenzene is not considered toxic according to the EU criteria and the available data on persistence of 1,2,4-trichlorobenzene indicate a half-life in water of a few days and a significant biodegradation potential. The bioaccumulation potential is low to moderate with most BCF ratios for fish ranging from 600 to 1400 and one highest of 2020. Based on an extensive evaluation of persistence, biodegradation and bioaccumulation data it is concluded that 1,2,4-trichlorobenzene is not a PBT, since it does not fulfill any of the EU criteria. Biomagnification in the food chain is not expected due to the relatively high elimination rate constants.     

An environmental fate, exposure and risk assessment of ethylene oxide from diffuse emissions

Ethylene oxide (EO) is mainly used as a chemical intermediate and as a fumigant and sterilizing agent. Through its manufacturing and intended uses, EO may be released into the environment. Therefore, an assessment of the environmental significance of those potential emissions was conducted. Data were collected describing pertinent physical properties, degradation and other loss mechanisms that control the fate of EO in the environment. Available aquatic and terrestrial ecotoxicity data were assembled and used as the basis of calculating critical toxicity values to characterize hazard. Environmental compartment concentrations of EO were calculated using Level III fugacity-based modeling. Six scenarios were developed to account for different climatic conditions in various portions of the US. Finally, potential regional-scale risks to aquatic and terrestrial wildlife were determined. In the conceptual model that was developed in this assessment, EO diffuses into air, partitions between environmental compartments, is transported out of the different compartments via advection, and undergoes abiotic and biological degradation within each compartment. All known emissions within the continental USA were assumed to enter a modeled region roughly the size of the State of Ohio. Organisms (receptors) were assumed to dwell in both terrestrial and aquatic compartments. Receptors were assumed to include small mammals, soil invertebrates, water column (pelagic) organisms, and sediment benthos. The goal of this assessment was to characterize any potential adverse risks to terrestrial and aquatic wildlife populations. Hazard Quotients (HQ) were calculated by dividing predicted concentrations of EO in air, water, sediment, and soil by their critical toxicity values. Maximum calculated HQ values in air were 1.52x10(-7), in water were 1.17x10(-5), in sediment were 2.25x10(-4), and in soil were 1.37x10(-5). The results of this assessment suggest that EO as currently manufactured and used does not pose adverse risks to aquatic or terrestrial wildlife. In all cases, the HQ values were much less than the maximum desired HQ value of 1.0 (4,400-6,600,000 times), indicating that the potential for diffuse emissions of EO to pose adverse environmental risks is quite low.     

A multispecies study to assess the toxic and genotoxic effect of pharmaceuticals: furosemide and its photoproduct

Pharmaceutical products for humans and animals, as well as their related metabolites end up in the aquatic environment after use. Recent investigations show that concentrations of pharmaceuticals are detectable in the order of ng/l-mug/l in municipal wastewater, groundwater and also drinking water. Little is known about the effects, and the hazard of long-term exposure to low concentrations of pharmaceuticals for non-target aquatic organisms. This study was designed to assess the ecotoxicity of furosemide, a potent diuretic agent, and its photoproduct in the aquatic environment. Bioassays were performed on bacteria, algae, rotifers and microcrustaceans to assess acute and chronic toxicity, while the SOS Chromotest and the Ames test were utilized to detect the genotoxic potential of the investigated compounds. A first approach to risk characterization was to calculate the environmental impact of furosemide by measured environmental concentration and predicted no effect concentration ratio (MEC/PNEC). To do so we used occurrence data reported in the literature and our toxicity results. The results showed that acute toxicity was in the order of mg/l for the crustaceans and absent for bacteria and rotifers. Chronic exposure to these compounds caused inhibition of growth population on the consumers, while the algae did not seem to be affected. A mutagenic potential was found for the photoproduct compared to the parental compound suggesting that byproducts ought to be considered in the environmental assessment of drugs. The risk calculated for furosemide suggested its harmlessness on the aquatic compartment.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

Acute toxicity of leachates of tire wear material to Daphnia magna--variability and toxic components

Large amounts of tire rubber are deposited along the roads due to tread wear. Several compounds may leach from the rubber and cause toxicity to aquatic organisms. To investigate the toxic effects of tire wear material from different tires, rubber was abraded from the treads of twenty-five tires. Leachates were prepared by allowing the rubber to equilibrate with dilution water at 44 degrees C for 72 h. Then the rubber was filtered from the leachates, and test organisms (Daphnia magna) were added. Forty-eight hour EC50s ranged from 0.5 to >10.0 g l(-1). The toxicity identification evaluation (TIE) indicated that non-polar organic compounds caused most of the toxicity. UV exposure of the filtered tire leachates caused no significant increase in toxicity. However, when tested as unfiltered leachates (the rubber was not filtered from the leachates before addition of D. magna) photo-enhanced toxicity was considerable for some tires, which means that test procedures are important when testing tire leachates for aquatic (photo) toxicity. The acute toxicity of tire wear for Daphnia magna was found to be <40 times a predicted environmental concentration based on reports on the concentration of a tire component found in environmental samples, which emphasizes the need for a more extensive risk assessment of tire wear for the environment.     

Behavior of sartans (antihypertensive drugs) in wastewater treatment plants,their occurrence and risk for the aquatic environment

Pharmaceuticals and other anthropogenic trace contaminants reach wastewaters and are often not satisfactorily eliminated in sewage treatment plants. These contaminants and/or their degradation products may reach surface waters, thus influencing aquatic life. In this study, the behavior of five different antihypertonic pharmaceuticals from the sartan group (candesartan, eprosartan, irbesartan, olmesartan and valsartan) is investigated in lab-scale sewage plants. The elimination of the substances with related structures varied broadly from 17 % for olmesartan up to 96 % for valsartan. Monitoring data for these drugs in wastewater effluents of six different sewage treatment plants (STPs) in Bavaria, and at eight rivers, showed median concentrations for, e.g. valsartan of 1.1 and 0.13 μg L^?1, respectively. Predicted environmental concentrations (PEC) were calculated and are mostly consistent with the measured environmental concentrations (MEC). The selected sartans and the mixture of the five sartans showed no ecotoxic effects on aquatic organisms in relevant concentrations. Nevertheless, the occurrence of pharmaceuticals in the environment should be reduced to minimize the risk of their distribution in surface waters, ground waters and bank filtrates used for drinking water.     

Biodegradation and removal of 3,4-dichloroaniline by Chlorella pyrenoidosa based on liquid chromatography-electrospray ionization-mass spectrometry

3,4-Dichloroaniline (3,4-DCA), widely used in the synthesis of dyes, textile and herbicides, is toxic to living organisms. The purpose of this study was to investigate the capability of green algae in degrading and removing 3,4-DCA in water. An environmentally ubiquitous green alga Chlorella pyrenoidosa was isolated from fresh aquatic environment. Then unicellular alga was incubated with 3,4-DCA at a concentration of 4.6 μg/?mL in water. The residual concentration of 3,4-DCA in the medium and the metabolites were analyzed. A removal percentage of 78.4 % was obtained over a 7-day period. Two major metabolites with less toxicity were identified as 3,4-dichloroformanilide and 3,4-dichloroacetanilide from the liquid chromatography-electrospray ionization-mass spectrometry analysis. The application of microalga C. pyrenoidosa may have potential for removing the environmental pollutant in aquatic environment.     

Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China

This study investigated the presence and distribution of 22 antibiotics, including eight quinolones, nine sulfonamides and five macrolides, in the water, sediments, and biota samples from Baiyangdian Lake, China. A total of 132 samples were collected in 2008 and 2010, and laboratory analyses revealed that antibiotics were widely distributed in the lake. Sulfonamides were the dominant antibiotics in the water (0.86-1563 ng L⁻¹), while quinolones were prominent in sediments (65.5-1166 μg kg⁻¹) and aquatic plants (8.37-6532 μg kg⁻¹). Quinolones (17.8-167 μg kg⁻¹) and macrolides [from below detection limit (BDL) to 182 μg kg⁻¹] were often found in aquatic animals and birds. Salvinia natans exhibited the highest bioaccumulation capability for quinolones among three species of aquatic plants. Geographical differences of antibiotic concentrations were greatly due to anthropogenic activities. Sewage discharged from Baoding City was likely the main source of antibiotics in the lake. Risk assessment of antibiotics on aquatic organisms suggested that algae and aquatic plants might be at risk in surface water, while animals were likely not at risk.     

Toxic potential of the emerging contaminant nicotine to the aquatic ecosystem

Nicotine is a “life-style compound” widely consumed by human populations and, consequently, often found in surface waters. This fact presents a concern for possible effects in the aquatic ecosystems. The objective of this study was to assess the potential lethal and sublethal toxicity of nicotine in aquatic organisms from different trophic levels (Vibrio fischeri, Pseudokirchneriella subcapitata, Thamnocephalus platyurus, and Daphnia magna). The bioassays were performed by exposing the organisms to concentrations of nicotine in a range of 0.5–1000 μg/L. Results showed that nicotine, at tested concentration, was not acutely toxic to V. fischeri and T. platyurus. On the contrary, this substance exhibited toxicity to P. subcapitata and Daphnia magna. Thus, concentrations of nicotine of 100 and 200 μg/L promoted an inhibition in the growth of P. subcapitata. In addition, a concentration of 100 μg/L nicotine acted on the reproduction of the crustacean D. magna, by decreasing the number of juveniles produced by female. On the other hand, the results showed that concentrations equal to or greater than 10 μg/L induced the production of daphnids male offspring, which may indicate that nicotine is a weak juvenoid compound of the D. magna endocrine system. Furthermore, the result showed that concentrations tested of this chemical have the capacity to revert the effect of fenoxycarb, a strong juvenoid chemical insecticide. The results of the study revealed that nicotine can induce several changes in some of the most important key groups of the aquatic compartment, which can compromise, in a short time, the balance of aquatic ecosystem. Finally, a preliminary environmental risk assessment of this stimulant was performed from the highest measured concentration in surface water and the no observable effect concentration value in the most sensitive species, i.e., D. magna. This process revealed that nicotine can produce an important risk to aquatic organisms.     

Environmental risk assessment of musk ketone and musk xylene in the Netherlands in accordance with the EU-TGD

An environmental risk assessment has been carried out for musk ketone and musk xylene according to the EU Technical Guidance Document for Environmental Risk Assessment for New and Existing Substances [1]. Musk ketone and musk xylene are used in fragrances for cosmetics and household products. For the fragrance industry these are important fragrance ingredients because of their excellent substantivity as well as for their unique smell, which determines largely the odor of a product.

The initial environmental risk assessment is based on information provided by the fragrance industry as represented in the Netherlands by its association NEA, by the Research Institute for Fragrance Materials (RIFM) and data reported in the international open literature. The risk assessment includes an evaluation of the risks for aquatic organisms in surface water and sediment and for soil organisms in soil after application of sewage sludge. Secondary poisoning of fish-eating birds and mammals is considered as well. For each compartment the Predicted Environmental Concentration (PEC) is compared to the Predicted No Effect Concentration (PNEC) to obtain PEC/PNEC ratios. Since monitoring data are available in water, sediment and fish, similar ratios are obtained with measured concentrations instead of the predicted ones.

For both substances, PEC/PNEC ratios are at or below 0.1 for organisms in the aquatic environment, including sediment organisms. PEC/PNEC ratios for fish-eating predators are 0.01. Ratios based on monitoring data are below 0.01 for all of these organisms. For soil organisms the PEC/PNEC ratio is 0.5 for musk ketone and 1.3 for musk xylene. Although in the Netherlands (as well as in some other European countries), sewage sludge presently finds no application as fertilizer on agricultural soil, the aim of environmental policy is to upgrade the sludge quality to enable future applications on agricultural and grassland. The reliability of the predicted soil concentrations can be greatly improved by obtaining experimental data on fate and behaviour of musk ketone and musk xylene in digested sludge and soil.

The risk assessment provides reassurance for the aquatic compartment while pointing the way for obtaining aditional data for the soil compartment.     

Haloacetic acids in the aquatic environment. Part II: ecological risk assessment

Haloacetic acids (HAAs) are environmental contaminants found in aquatic ecosystems throughout the world as a result of both anthropogenic and natural production. The ecological risk posed by these compounds to organisms in freshwater environments, with a specific focus on aquatic macrophytes, was characterized. The plants evaluated were Lemna gibba, Myriophyllum spicatum and M. sibiricum and the HAAs screened were monochloroacetic acid (MCA), dichloroacetic acid (DCA), trichloroacetic acid (TCA), trifluoroacetic acid (TFA) and chlorodifluoroacetic acid (CDFA). Laboratory toxicity data formed the basis of the risk assessment, but field studies were also utilized. The estimated risk was calculated using hazard quotients (HQ), as well as effect measure distributions (EMD) in a modified probabilistic ecological risk assessment. EMDs were used to estimate HAA thresholds of toxicity for use in HQ assessments. This threshold was found to be a more sensitive measure of low toxicity than the no observed effect concentrations (NOEC) or the effective concentration (EC10). Using both deterministic and probabilistic methods, it was found that HAAs do not pose a significant risk to freshwater macrophytes at current environmental concentrations in Canada, Europe or Africa for both single compound and mixture exposures. Still, HAAs are generally found as mixtures and their potential interactions are not fully understood, rendering this phase of the assessment uncertain and justifying further effects characterization. TCA in some environments poses a slight risk to phytoplankton and future concentrations of TFA and CDFA are likely to increase due to their recalcitrant nature, warranting continued environmental surveillance of HAAs.     

Concentrations and possible sources of polychlorinated biphenyls in the surface water of the Yangtze River Delta, China

In this study, polychlorinated biphenyls (PCBs) pollution in the surface water of the Yangtze River Delta (YRD) was investigated. A total of 26 samples were collected from water bodies in three cities within the YRD during the dry season from October to November of 2009. The total PCBs (dissolved plus particulate) ranged from 1.23 to 16.6 ng L(-1) and were dominated by tri-, tetra-, and penta-chlorinated biphenyls. The mean PCBs in the Beijing-Hangzhou Grand Canal and the Yangtze River were 8.84 and 3.36 ng L(-1), respectively. A t-test showed that there were no significant differences in the concentration of samples from the metropolitan area and the development zone. According to the Chinese national environmental quality standards for surface water (GB 3838-2002), the concentrations of PCBs observed in this study do not pose a hazard to aquatic or human health. Overall, this study described the PCB concentration and homolog distribution patterns in one of the most rapidly developing areas in China, and the results can be used as reference levels for future PCB monitoring programs.     

Health and ecotoxicological risk assessment for human and aquatic organism exposure to polycyclic aromatic hydrocarbons in the Baiyangdian Lake

Seasonal and regional distributions of 17 polycyclic aromatic hydrocarbons (PAHs) in surface waters from four different main water functional regions of the Baiyangdian Lake were analyzed through GC/MS/MS during spring and summer season. The aim was to identify their possible pollution sources and evaluate their health risk for human and ecotoxicological risk for aquatic organisms. Results showed that the range of total PAH concentration is 35.38–88.06 ng/L (average 46.57 ng/L) in spring and 25.64–301.41 ng/L (average 76.23 ng/L) in summer. PAH contamination was observed slightly lower in the summer season from the pollution characteristics of water bodies in most areas of the Baiyangdian Lake, and the levels of PAH pollution in the water body of urban residential regions and rural residential regions were relatively higher than those in tourist regions and low human disturbance regions. Source analysis based on diagnostic ratios confirmed that combustion sources and petroleum sources were two main sources for PAHs entering into the waters of the Baiyangdian Lake. Human health risk assessment showed that PAHs in surface waters from the Baiyangdian Lake will not cause a potential non-carcinogenic risk to local residents and the carcinogenic risk could mostly be accepted, but the potential lifetime carcinogenic risk for infants in rural residential regions should be concerned about. Urban residential regions and rural residential regions were subject to higher cumulative non-carcinogenic and carcinogenic risk when compared to the other functional regions. Ecotoxicological risk assessment found a moderate risk to aquatic organisms presented by individual PAH and a low risk by total PAHs, and PAHs in the water body of urban residential regions and rural residential regions also have relatively higher harm effects to aquatic organisms compared with the other two functional regions. This study revealed the pollution characteristics of PAHs and their possible sources in waters of the Baiyangdian Lake, clarified its correlation to regional anthropogenic activities, and provided corresponding risk management strategies for human and aquatic organisms.

     

Tetrabromobisphenol A: tissue distribution in fish, and seasonal variation in water and sediment of Lake Chaohu, China

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardants (BFRs). It has been detected in various environment media and has been approved to be high toxic to aquatic organisms. However, the exposure levels of TBBPA in the main watersheds in China have not been investigated sufficiently. In this study TBBPA concentrations in water, sediment and tissues of four fish species from Lake Chaohu were determined. Spatial and temporal distribution patterns of TBBPA in water and sediment, and the relationship among TBBPA concentrations in fish tissues and fish size were analyzed. The results showed that the maximum TBBPA concentration in sediment was 518 ng/g in March 2008. It is almost the highest value than those ever reported anywhere in the world. In lake water, TBBPA level reached the maximum value of 4.87???g/L in July. Tissue distributions of TBBPA in four fish species were similar, and the mean concentrations in the fish were in the range of 28.5?C39.4 ng/g, much higher than those reported in Japan, Europe, and the United States. The maximum concentrations of TBBPA were found in kidneys where TBBPA concentration was positively correlated with fish size of Cyprinus carpio. Results demonstrated a widespread distribution of TBBPA in Lake Chaohu. The source was mainly inflow rivers near the cities. The distribution coefficient among water, fish, and sediment was 1:28:117. This indicated that sediment was the main repository for TBBPA within Lake Chaohu. Furthermore, TBBPA may pose a potential ecological risk in the lake during summer.     

Effects assessment: boron compounds in the aquatic environment

In previous studies, boron compounds were considered to be of comparatively low toxicity in the aquatic environment, with predicted no effect concentration (PNEC) values ranging around 1 mg B/L (expressed as boron equivalent). In the present study, we describe an evaluation of toxicity data for boron available for the aquatic environment by different methods.For substances with rich datasets, it is often possible to perform a species sensitivity distribution (SSD). The typical outcome of an SSD is the Hazardous Concentration 5% (HC₅), the concentration at which 95% of all species are protected with a probability of 95%. The data set currently available on the toxic effects of boron compounds to aquatic organisms is comprehensive, but a careful evaluation of these data revealed that chronic data for aquatic insects and plants are missing. In the present study both the standard assessment factor approach as well as the SSD approach were applied. The standard approach led to a PNEC of 0.18 mg B/L (equivalent to 1.03 mg boric acid/L), while the SSD approach resulted in a PNEC of 0.34 mg B/L (equivalent to 1.94 mg boric acid/L). These evaluations indicate that boron compounds could be hazardous to aquatic organisms at concentrations close to the natural environmental background in some European regions. This suggests a possible high sensitivity of some ecosystems for anthropogenic input of boron compounds. Another concern is that the anthropogenic input of boron could lead to toxic effects in organisms adapted to low boron concentration.     

Methyl tertiary hexyl ether and methyl tertiary octyl ether as gasoline oxygenates: assessing risks from atmospheric dispersion and deposition

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10(-3) and 10(-2) for MtHxE and MtOcE, respectively, in Boston, and 10(-2) and 10(-1) in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.     

Population-level effects of the neem insecticide, Neemix, on Daphnia pulex

Although natural insecticides from the neem tree are generally perceived as less harmful to the environment than synthetic insecticides, new evidence indicates that these products may pose a risk to certain nontarget organisms. In this paper, acute and chronic effects of commercial neem insecticides on the aquatic invertebrate, Daphnia pulex were examined. The acute toxicity of two commercial neem insecticides, Neemix, Azatin and the experimental insecticide, RH-9999 to D. pulex was investigated using traditional 48 hr concentration-mortality estimates. Neemix and Azatin were equitoxic with LC50's of 0.68 and 0.57 ppm; RH-9999 was significantly less toxic with an LC50 of 13 ppm. A 10 d population growth study was conducted for Neemix and a Neemix formulation blank (Neemix devoid of the active ingredients) to determine whether the active ingredients of Neemix and/or components of the formulation were responsible for toxicity. D. pulex populations went to extinction after exposure to a Neemix concentration of 0.45 ppm azadirachtin (equivalent to the acute LC7). Neemix No Observable Effect Concentration (NOEC) and Lowest Observable Effect Concentration (LOEC) values for population growth were 0.045 and 0.15 ppm azadirachtin, respectively. The mean number of offspring per surviving female (Ro) declined in a concentration-dependent manner after exposure to Neemix with no offspring being produced after exposure to 0.45 ppm. Neemix NOEC and LOEC values for reproduction were 0.045 and 0.15 ppm, respectively. The formulation blank caused no mortality in the individuals used to start the population growth study but reduced reproduction and population growth accounting for 47% of the toxicity caused by Neemix at a concentration of 0.15 ppm. Thus, the formulation contributes substantially to the toxicity of Neemix but neem components are also toxic to D. pulex. Because the NOEC for population growth and reproduction were higher than the estimated environmental concentration of 0.035 ppm (a measure developed for forest pest mananagement), Neemix should pose little risk to populations of D. pulex.     

Androgenic and antiandrogenic activities in water and sediment samples from the river Lambro, Italy, detected by yeast androgen screen and chemical analyses

The river Lambro is the most polluted tributary of the river Po in North Italy and was chosen as a representative water course discharging industrialized areas. Water and sediment samples of the river Lambro were investigated regarding the presence of endocrine disrupting compounds. A combined procedure was used consisting of solid-phase extraction and HPLC based fractionation of samples, of screening for (anti)androgenic activity using the yeast androgen screen (YAS) and of chemical analysis using HPLC-MS/MS and GC-MS. Androgenic and antiandrogenic activities were found in specific fractions of the water and sediment while the total extracts showed antiandrogenic activity only. The chemical analysis of the fractions and total extracts with antiandrogenic activities revealed the presence of compounds with suspected antiandrogenic potency such as bisphenol A, iprodione, nonylphenol, p,p'-DDE and tert-octylphenol but other unknown compounds contributed mainly to the observed antiandrogenic activities. The antiandrogenic load of the river Lambro ranged between 1.34 and 17.1 microM flutamide-equivalents and may pose a risk to aquatic environments. Future screenings for EDC in the environment that have the potential to interfere with reproduction of aquatic organisms should be extended to different modes of actions including (anti)androgenic ones.     

Ecological risk of pesticide residues in the British Columbia environment: 1973–2012

An updated ecological risk assessment was conducted to re-evaluate and review the overall risk of pesticide residues to certain aquatic life. The focus was the impact on offsite non-target, freshwater organisms of pesticide operational sprays in British Columbia from 1973 until 2012. The values of risk quotients for pesticides of selected indicator organisms were determined to measure the effect. When compared with organophosphorus, carbamate, and other miscellaneous pesticides, this risk assessment analysis suggests that the historical use of persistent and highly toxic organochlorine pesticides posed, and continue to pose, a deleterious ecological risk. The risk is both short-term acute and long-term sub-acute, chronic toxicity to offsite, non-target aquatic invertebrates and juvenile salmonid fish. Data indicated that these organisms were, and remain, subjected to harmful effects of pesticide residues to varying degrees. Most vulnerable were, and also are, benthic organisms inhabiting bottom sediments. This substrate is the natural sink for persistent pesticide residues, predominantly organochlorine pesticides from historical use, as well as dioxins, furans, and polycyclic aromatic hydrocarbons from wood preservatives, and other sources. Environment Canada's main aquatic protection strategy was a 10 metre no-treatment buffer zone, augmented with an additional appropriate setback along shorelines of fishery and wildlife resource-sensitive water bodies. This study discusses why this guideline was necessary, useful and effective, but was only partially successful. The physical-chemical properties of pesticide residues, from either an individual compound or different compounds in combination, also influence the nature of biological impacts on non-target, aquatic organisms. Few studies have been conducted in British Columbia aquatic environments to investigate the significance of this aspect.