Evaluating the environmental fate of lindane in France

Lindane, a highly persistent and lipophilic pesticide, is still used in large quantities. This chemical can be found with appreciable concentrations in biota, atmosphere, and in other environmental compartments in the adsorbed form. This information provided a basis for assessing the simulation performances of CHEMFRANCE, a regional level III fugacity model allowing to generate environmental behavior profile of organic chemicals in France. The comparison between the estimated environmental fate and field and laboratory observations suggests that this fugacity model can be used to determine the processes that control the environmental fate of lindane in France. CHEMFRANCE also provides accurate estimates of environmental compartment contaminations.     

Atrazine degradation in a containerized rhizosphere system

The effect of atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) on rhizosphere microorganisms and its fate in a containerized rhizosphere system was studied. The rhizosphere system consisted of corn grown in pot containing a defined potting mix of sand and bark with atrazine. Sterilized potting mix and a container without plants served as controls. Atrazine was extracted and analyzed via HPLC. Fluorescent pseudomonad populations increased 100-fold in the rhizposphere during a 60-day incubation period as compared to the nonvegetated control. Atrazine degradation was higher in the rhizosphere system (half-life of 7 days) compared to the nonvegetated control (half-life of greater than 45 days). The major degradation product detected in the rhizosphere system was deisopropylatrazine; other products detected included deethylatrazine, deethylhydroxyatrazine, deisopropylatrazine and hydroxyatrazine. Hydroxyatrazine was detected in the nonvegetated and sterile controls. The containerized rhizosphere system provides an experimental system to study the fate of pesticidal chemicals as well as the effects on microbial populations.     

Biodegradability of Atrazine,Cyanazine and Dicamba under methanogenic condition in three soils of China

Persistence and degradation of the herbicides Atrazine, Cyanazine and Dicamba were measured in laboratory microcosms incubated under methanogenic condition using three soils of China. Results showed that Atrazine was more resistant to degradation than Cyanazine and Dicamba for the 300 days of incubation. Between 30% and 40% of the initially introduced chemicals were found to be not recoverable through solvent extraction of the incubated soils. Our results also indicated that the half-life of these herbicides in the three soils generally followed: Atrazine>Cyanazine>Dicamba. Biodegradation of Cyanazine and Dicamba was further substantiated by establishing enrichment cultures in which the degradation of the respective herbicides could be accelerated by the microorganisms. Our results suggest that biodegradation of xenobiotics can be established through enrichment culture transfer technique and non-extractability of chemicals should be taken into account in evaluation of chemicals' fate and risk.     

Atrazine degradation in a containerized rhizosphere system

Abstract

The effect of atrazine (2‐chloro‐4‐ethylamino‐6‐isopropylamino‐s‐triazine) on rhizosphere microorganisms and its fate in a containerized rhizosphere system was studied. The rhizosphere system consisted of corn grown in pot containing a defined potting mix of sand and bark with atrazine. Sterilized potting mix and a container without plants served as controls. Atrazine was extracted and analyzed via HPLC. Fluorescent pseudomonad populations increased 100‐fold in the rhizposphere during a 60‐day incubation period as compared to the nonvegetated control. Atrazine degradation was higher in the rhizosphere system (half‐life of 7 days) compared to the nonvegetated control (half‐life of greater than 45 days). The major degradation product detected in the rhizosphere system was deisopropylatrazine; other products detected included deethylatrazine, deethylhydroxyatrazine, deisopropylatrazine and hydroxyatrazine. Hydroxyatrazine was detected in the nonvegetated and sterile controls. The containerized rhizosphere system provides an experimental system to study the fate of pesticidal chemicals as well as the effects on microbial populations.     

Meta-analysis and experimental validation identified atrazine as a toxicant in the male reproductive system

Environmental Science and Pollution Research - Atrazine (ATZ), as a widely used triazine herbicide, is an environmental endocrine disruptor (EDC) that can cause many health problems. Therefore, we...     

Influence of Lead on Atrazine Uptake by Rice (Oryza sativa L.) Seedlings from Nutrient Solution (7 pp)

Background Atrazine is a widely used herbicide, and its persistence in soil and water causes environmental concerns. In the past, plat uptake processes are mainly investigated for single contaminants. However, in many cases, contaminants co-exist in environmental matrix, such as soil, and plant uptake of one contaminant may be influenced by its co-existing ones.Methods The uptake of atrazine by rice seedlings (Oryza sativa L.) from nutrient solution through the roots was investigated in a solution culture, over an exposure period of 4 weeks. Atrazine accumulation in plant tissues was determined by gas chromatography, and lead was determined using atomic absorption spectrometry.Results and Discussion With different ratios of atrazine and Pb2+ concentrations in solution, the observed atrazine concentrations in shoots and roots varied significantly. In atrazine-Pb2+ mixture systems, the added Pb2+ either increased or decreased the concentrations or BCFs of atrazine in seedlings (relative to those without Pb2+), depending on the atrazine-Pb2+ ratio in nutrient solution. The enhanced atrazine uptake results presumably from atrazine-Pb2+ complex formation. The reduced atrazine uptake, which occurred mainly at high atrazine concentrations, is attributed to atrazine toxicity that inhibited seedling growth and transpiration. Conclusion The formation of atrazine-Pb2+ complex both in the solution and within plant tissues may affect the accumulation of both contaminants by rice plants.     

Using biochar for remediation of soils contaminated with heavy metals and organic pollutants

Soil contamination with heavy metals and organic pollutants has increasingly become a serious global environmental issue in recent years. Considerable efforts have been made to remediate contaminated soils. Biochar has a large surface area, and high capacity to adsorb heavy metals and organic pollutants. Biochar can potentially be used to reduce the bioavailability and leachability of heavy metals and organic pollutants in soils through adsorption and other physicochemical reactions. Biochar is typically an alkaline material which can increase soil pH and contribute to stabilization of heavy metals. Application of biochar for remediation of contaminated soils may provide a new solution to the soil pollution problem. This paper provides an overview on the impact of biochar on the environmental fate and mobility of heavy metals and organic pollutants in contaminated soils and its implication for remediation of contaminated soils. Further research directions are identified to ensure a safe and sustainable use of biochar as a soil amendment for remediation of contaminated soils.     

Fugacity superposition: a new approach to dynamic multimedia fate modeling

The fugacities, concentrations, or inventories of pollutants in environmental compartments as determined by multimedia environmental fate models of the Mackay type can be superimposed on each other. This is true for both steady-state (level III) and dynamic (level IV) models. Any problem in multimedia fate models with linear, time-invariant transfer and transformation coefficients can be solved through a superposition of a set of n independent solutions to a set of coupled, homogeneous first-order differential equations, where n is the number of compartments in the model. For initial condition problems in dynamic models, the initial inventories can be separated, e.g. by a compartment. The solution is obtained by adding the single-compartment solutions. For time-varying emissions, a convolution integral is used to superimpose solutions. The advantage of this approach is that the differential equations have to be solved only once. No numeric integration is required. Alternatively, the dynamic model can be simplified to algebraic equations using the Laplace transform. For time-varying emissions, the Laplace transform of the model equations is simply multiplied with the Laplace transform of the emission profile. It is also shown that the time-integrated inventories of the initial conditions problems are the same as the inventories in the steady-state problem. This implies that important properties of pollutants such as potential dose, persistence, and characteristic travel distance can be derived from the steady state.     

Prediction of overall persistence and long-range transport potential with multimedia fate models: robustness and sensitivity of results

The hazard indicators persistence (P) and long-range transport potential (LRTP) are used in chemicals assessment to characterize chemicals with regard to the temporal and spatial extent of their environmental exposure. They are often calculated based on the results of multimedia fate models. The environmental and substance-specific input parameters of such models are subject to a range of methodological uncertainties and also influenced by natural variability. We employed probabilistic uncertainty analysis to quantify variance in P and LRTP predictions for chemicals with different partitioning and transport behavior. Variance found in the results is so large that it prevents a clear distinction between chemicals. Additionally, only small improvements are observed when evaluating the results relative to a benchmark chemical. This can be explained by the dominance of substance-specific parameters and the only small direct influence of environmental parameters on P and LRTP as model outcomes. The findings underline the importance of learning how environmental conditions cause variability in substance behavior for improved substance ranking and classification.     

Spatial variability in compartmental fate modelling

A new approach is presented which is designed to address the spatial heterogeneity of the environment in compartmental mass balance models of chemical fate in the environment. It rests on the assumption of chemical equilibration within one phase despite prevailing environmental heterogeneity. Composite D- and Z-values are derived from sub-unit specific environmental parameters and are used to solve mass balance equations which can be adopted essentially unchanged from existing compartmental fugacity models. With the resulting common fugacity value for each compartment, sub-unit specific concentrations and process rates can be calculated. The approach is illustrated using the QWASI lake model to calculate the fate of hexachlorobenzene in a hypothetical lake sub-divided in four distinct sub-units. The approach allows the subdivision of each compartment in a large number of sub-units with distinct environmental characteristics without substantially increasing model complexity. This is a necessary condition for linking fugacity models to geographical information systems.     

Including degradation products of persistent organic pollutants in a global multi-media box model

GOAL, SCOPE AND BACKGROUND: Global multi-media box models are used to calculate the fate of persistent organic chemicals in a global environment and assess long-range transport or arctic contamination. Currently, such models assume substances to degrade in one single step. In reality, however, intermediate degradation products are formed. If those degradation products have a high persistence, bioaccumulation potential and / or toxicity, they should be included in environmental fate models. The goal of this project was to gain an overview of the general importance of degradation products for environmental fate models, and to expand existing, exposure-based hazard indicators to take degradation products into account. METHODS: The environmental fate model CliMoChem was modified to simultaneously calculate a parent compound and several degradation products. The three established hazard indicators of persistence, spatial range and arctic contamination potential were extended to include degradation products. Five well-known pesticides were selected as example chemicals. For those substances, degradation pathways were calculated with CATABOL, and partition coefficients and half-lives were compiled from literature. RESULTS: Including degradation products yields a joint persistence value that is significantly higher than the persistence of the parent compound alone: in the case of heptachlor an increase of the persistence by a factor of 58 can be observed. For other substances, the increase is much smaller (4% for alpha-HCH). The spatial range and the arctic contamination potential (ACP) can increase significantly, too: for 2,4-D and heptachlor, an increase by a factor of 2.4 and 3.5 is seen for the spatial range. However, an important increase of the persistence does not always lead to a corresponding increase in the spatial range: the spatial range of aldrin increases by less than 50%, although the persistence increases by a factor of 20 if the degradation products are included in the assessment. Finally, the arctic contamination potential can increase by a factor of more than 100 in some cases. DISCUSSION: Influences of parent compounds and degradation products on persistence, spatial range and ACP are discussed. Joint persistence and joint ACP reflect similar characteristics of the total environmental exposure of a substance family (i.e., parent compound and all its degradation products). CONCLUSIONS: The present work emphasizes the importance of degradation products for exposure-based hazard indicators. It shows that the hazard of some substances is underestimated if the degradation products of these substances are not included in the assessment. The selected hazard indicators are useful to assess the importance of degradation products. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that degradation products be included in hazard assessments to gain a more accurate insight into the environmental hazard of chemicals. The findings of this project could also be combined with information on the toxicity of degradation products. This would provide further insight into the importance of degradation products for environmental risk assessments.     

Fate of atrazine in switchgrass–soil column system

Atrazine, a broad-leaf herbicide, has been used widely to control weeds in corn and other crops for several decades and its extensive used has led to widespread contamination of soils and water bodies. Phytoremediation with switchgrass and other native prairie grasses is one strategy that has been suggested to lessen the impact of atrazine in the environment. The goal of this study is to characterize: (1) the uptake of atrazine into above-ground switchgrass biomass; and (2) the degradation and transformation of atrazine over time. A fate study was performed using mature switchgrass columns treated with an artificially-created agricultural runoff containing 16 ppm atrazine. Soil samples and above-ground biomass samples were taken from each column and analyzed for the presence of atrazine and its chlorinated metabolites. Levels of atrazine in both soil and plant material were detectable through the first 2 weeks of the experiment but were below the limit of detection by Day 21. Levels of deethylatrazine (DEA) and didealkylatrazine (DDA) were detected in soil and plant tissue intermittently over the course of the study, deisopropylatrazine (DIA) was not detected at any time point. A radiolabel study using [¹⁴C]atrazine was undertaken to observe uptake and degradation of atrazine with more sensitivity. Switchgrass columns were treated with a 4 ppm atrazine solution, and above-ground biomass samples were collected and analyzed using HPLC and liquid scintillation counting. Atrazine, DEA, and DIA were detected as soon as 1 d following treatment. Two other metabolites, DDA and cyanuric acid, were detected at later time points, while hydroxyatrazine was not detected at all. The percentage of atrazine was observed to decrease over the course of the study while the percentages of the metabolites increased. Switchgrass plants appeared to exhibit a threshold in regard to the amount of atrazine taken up by the plants; levels of atrazine in leaf material peaked between Days 3 and 4 in both studies.     

Comparison of two methods for estimation of soil sorption for imidacloprid and carbofuran

Predicting the fate and transport of pesticides in soil environment is an important issue especially in understanding and modelling of the environmental behaviour of pesticides. Classical batch sorption method often has been identified as insufficient to derive the actual extent of sorption. In this study, the batch equilibrium method was compared to the centrifugation method, which can permit measurement of sorption under more natural conditions. The results of the comparison of the batch with the centrifugation method for imidacloprid and carbofuran pesticides indicate that the batch method overestimates sorption in comparison to the centrifugation method. These results are in agreement with others, which use high soil:solution ratios with batch and those that used the centrifugation method.     

Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

The fate of the three environmentally relevant β-blockers atenolol, metoprolol and propranolol has been studied in batch experiments involving aquifer material and nitrate reducing conditions. Results from the about 90 d long tests indicate that abiotic processes, most likely sorption, jointly with biotransformation to atenololic acid were responsible for the 65% overall removal observed for atenolol. Zero order kinetics, typical of enzyme-limited reactions, controlled the transformation of this beta blocker to its corresponding carboxylic acid. The mass balance evidences that no mineralization of atenolol occurs in the biotic experiment and that atenololic acid is more stable than its parent compound under the studied conditions. This finding stresses the importance of considering atenololic acid as target compound in the environmental studies on the fate of atenolol. For metoprolol and propranolol the results from the experiment suggest a slower sorption to be the dominant removal process, which led to final decreases in concentrations of 25–30% and 40–45%, respectively. Overall, the removals observed in the experiments suggest that subsurface processes potentially constitute an alternative water treatment for the target beta-blockers, when compared to the removals reported for conventional wastewater treatment plants.     

Fate of β-blockers in aquifer material under nitrate reducing conditions: Batch experiments

The fate of the three environmentally relevant β-blockers atenolol, metoprolol and propranolol has been studied in batch experiments involving aquifer material and nitrate reducing conditions. Results from the about 90 d long tests indicate that abiotic processes, most likely sorption, jointly with biotransformation to atenololic acid were responsible for the 65% overall removal observed for atenolol. Zero order kinetics, typical of enzyme-limited reactions, controlled the transformation of this beta blocker to its corresponding carboxylic acid. The mass balance evidences that no mineralization of atenolol occurs in the biotic experiment and that atenololic acid is more stable than its parent compound under the studied conditions. This finding stresses the importance of considering atenololic acid as target compound in the environmental studies on the fate of atenolol. For metoprolol and propranolol the results from the experiment suggest a slower sorption to be the dominant removal process, which led to final decreases in concentrations of 25-30% and 40-45%, respectively. Overall, the removals observed in the experiments suggest that subsurface processes potentially constitute an alternative water treatment for the target beta-blockers, when compared to the removals reported for conventional wastewater treatment plants.     

The biodegradability and microbial toxicity testing of lubricants--some recommendations

In recent years there has been a growing demand for information on the biodegradability (fate) and microbial toxicity (effects) of lubricants. This has been driven by the need to comply with environmental legislation and to meet the requirements of ecolabelling schemes, standards and customer specifications for 'environmentally acceptable' lubricants. This paper describes suitable approaches for generating this information under a variety of environmental conditions (e.g. aerobic, anaerobic, freshwater, marine), gives examples of the results obtained and discusses their interpretation. Recommendations on the use of each test are made.     

Constructed wetlands for mitigation of atrazine-associated agricultural runoff

Atrazine was amended into constructed wetlands (59-73x14x0.3 m) for the purpose of monitoring transport and fate of the pesticide to obtain information necessary to provide future design parameters for constructed wetlands mitigation of agricultural runoff. Following pesticide amendment, a simulated storm and runoff event equal to three volume additions was imposed on each wetland. Targeted atrazine concentrations were 0 microg/l (unamended control), 73 microg/l, and 147 microg/l. Water, sediment, and plant samples were collected weekly for 35 days from transects longitudinally distributed throughout each wetland and were analyzed for atrazine using gas chromatography. Between 17 and 42% of measured atrazine mass was within the first 30-36 m of wetlands. Atrazine was below detection limits (0.05 microg/kg) in all sediment and plant samples collected throughout the duration of this study. Aqueous half lives ranged from 16 to 48 days. According to these data, conservative buffer travel distances of 100-280 m would be necessary for effective runoff mitigation.     

Enantioselectivity in environmental risk assessment of modern chiral pesticides

Chiral pesticides comprise a new and important class of environmental pollutants nowadays. With the development of industry, more and more chiral pesticides will be introduced into the market. But their enantioselective ecotoxicology is not clear. Currently used synthetic pyrethroids, organophosphates, acylanilides, phenoxypropanoic acids and imidazolinones often behave enantioselectively in agriculture use and they always pose unpredictable enantioselective ecological risks on non-target organisms or human. It is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in environmental risk assessment. The enantioselective toxicology and the fate of these currently widely used pesticides have been discussed in this review article.