OBOMod - Integrated modelling framework for residents' exposure to pesticides.

BACKGROUND: Pesticides can be transported from the site of application to homes via different routes and lead to exposure of residents, raising concerns regarding health effects. We built a deterministic model framework (OBOmod) to assess exposure of residents living near fields where pesticides are applied. METHODS: OBOmod connects five independent models operating on an hourly timescale and high spatial resolution (meters). Models include descriptions of spray drift, volatilization, atmospheric transport and dispersion, exchange between outdoor and indoor air and exchange between indoor air and dust. Fourteen bulb field applications under different weather conditions and comprising 12 pesticides were simulated. Each simulation included the first seven days after the application. The concentrations computed with OBOmod were compared with those measured in outdoor and indoor air and the amounts measured in indoor dust samples. RESULTS: Model evaluation indicated suitability of the developed framework to estimate outdoor and indoor air concentrations. For most pesticides, model accuracy was good. The framework explained about 30% to 95% of the temporal and spatial variability of air concentrations. For 20% of the simulations, the framework explained more than 35% of spatial variability of concentrations in dust. In general, OBOmod estimates remained within one order of magnitude from measured levels. Calculations showed that in addition to spray drift during application, volatilization from the field after spraying and pesticides in house dust are important routes for residents' exposure to pesticides. CONCLUSIONS: Our framework covers many processes needed to calculate exposure of residents to pesticides. The evaluation phase shows that, with the exception of the dust model, the framework can be used in support of health and epidemiological studies, and can serve as a tool to support development of regulations and policy making regarding pesticide use.

Modelling pesticides volatilisation in greenhouses: Sensitivity analysis of a modified PEARL model.

BACKGROUND: The application of the existing PEARL model was extended to include estimations of the concentration of crop protection products in greenhouse (indoor) air due to volatilisation from the plant surface. The model was modified to include the processes of ventilation of the greenhouse air to the outside atmosphere and transformation in the air. RESULTS: A sensitivity analysis of the model was performed by varying selected input parameters on a one-by-one basis and comparing the model outputs with the outputs of the reference scenarios. CONCLUSION: The sensitivity analysis indicates that - in addition to vapour pressure - the model had the highest ratio of variation for the rate ventilation rate and thickness of the boundary layer on the day of application. On the days after application, competing processes, degradation and uptake in the plant, becomes more important.

Implementation of the effects of physicochemical properties on the foliar penetration of pesticides and its potential for estimating pesticide volatilization from plants.

Volatilization from plant foliage is known to have a great contribution to pesticide emission to the atmosphere. However, its estimation is still difficult because of our poor understanding of processes occurring at the leaf surface. A compartmental approach for dissipation processes of pesticides applied on the leaf surface was developed on the base of experimental study performed under controlled conditions using laboratory volatilization chamber. This approach was combined with physicochemical properties of pesticides and was implemented in SURFATM-Pesticides model in order to predict pesticide volatilization from plants in a more mechanistic way. The new version of SURFATM-Pesticide model takes into account the effect of formulation on volatilization and leaf penetration. The model was evaluated in terms of 3 pesticides applied on plants at the field scale (chlorothalonil, fenpropidin and parathion) which display a wide range of volatilization rates. The comparison of modeled volatilization fluxes with measured ones shows an overall good agreement for the three tested compounds. Furthermore the model confirms the considerable effect of the formulation on the rate of the decline in volatilization fluxes especially for systemic products. However, due to the lack of published information on the substances in the formulations, factors accounting for the effect of formulation are described empirically. A sensitivity analysis shows that in addition to vapor pressure, the octanol-water partition coefficient represents important physicochemical properties of pesticides affecting pesticide volatilization from plants. Finally the new version of SURFATM-Pesticides is a prospecting tool for key processes involved in the description of pesticide volatilization from plants.

Volatilisation of pesticides under field conditions: inverse modelling and pesticide fate models.

BACKGROUND: A substantial fraction of the applied crop protection products on crops is lost to the atmosphere. Models describing the prediction of volatility and potential fate of these substances in the environment have become an important tool in the pesticide authorisation procedure at the EU level. The main topic of this research is to assess the rate and extent of volatilisation of ten pesticides after application on field crops. RESULTS: For eight of the ten pesticides, the volatilisation rates modelled with PEARL (Pesticide Emission Assessment at Regional and Local scales) corresponded well to the calculated rates modelled with ADMS (Atmospheric Dispersion Modelling System). For the other pesticides, large differences were found between the models. Formulation might affect the volatilisation potential of pesticides. Increased leaf wetness increased the volatilisation of propyzamide and trifloxystrobin at the end of the field trial. The reliability of pesticide input parameters, in particular the vapour pressure, is discussed. CONCLUSION: Volatilisation of propyzamide, pyrimethanil, chlorothalonil, diflufenican, tolylfluanid, cyprodinil and E- and Z-dimethomorph from crops under realistic environmental conditions can be modelled with the PEARL model, as corroborated against field observations. Suggested improvements to the volatilisation component in PEARL should include formulation attributes and leaf wetness at the time of pesticide application. © 2015 Society of Chemical Industry.

Volatilisation of pesticides after application in vegetable greenhouses.

BACKGROUND: Volatilisation of pesticides after application to the soil or the crop is an important source of emission into the atmosphere. As a result, workers, residents and bystanders are potentially at risk when exposed to these volatilised substances. Nonetheless, data on measured concentrations are quite scarce, especially in greenhouses. The objective of this work is to present the results of volatilisation experiments performed in greenhouses. RESULTS: The results indicate that the concentrations are highest in the hours after application and rapidly decline during the days following application. CONCLUSION: Greenhouse temperature, ventilation rate, the substance vapour pressure and the rate of competing processes were identified as important factors influencing volatilisation in greenhouses. The results from this study contribute to a better understanding of volatilisation in greenhouses and may help to improve the recent PEARL model for volatilisation in greenhouses.

Volatilisation and competing processes computed for a pesticide applied to plants in a wind tunnel system.

BACKGROUND: Volatilisation of pesticides from crop canopies can be an important emission pathway. In addition to pesticide properties, competing processes in the canopy and environmental conditions play a part. A computation model is being developed to simulate the processes, but only some of the input data can be obtained directly from the literature. RESULTS: Three well-defined experiments on the volatilisation of radiolabelled parathion-methyl (as example compound) from plants in a wind tunnel system were simulated with the computation model. Missing parameter values were estimated by calibration against the experimental results. The resulting thickness of the air boundary layer, rate of plant penetation and rate of phototransformation were compared with a diversity of literature data. The sequence of importance of the canopy processes was: volatilisation > plant penetration > phototransformation. CONCLUSION: Computer simulation of wind tunnel experiments, with radiolabelled pesticide sprayed on plants, yields values for the rate coefficients of processes at the plant surface. As some input data for simulations are not required in the framework of registration procedures, attempts to estimate missing parameter values on the basis of divergent experimental results have to be continued.

Volatilization of parathion and chlorothalonil from a potato crop simulated by the PEARL model.

The volatilization of pesticides from crop canopies in the field should be modeled within the context of evaluating environmental exposure. A model concept based on diffusion through a laminar air-boundary layer was incorporated into the PEARL model (pesticide emission assessment at regional and local scales) and used to simulate volatilization of the pesticides parathion and chlorothalonil from a potato crop in a field experiment. Rate coefficients for the competing processes of plant penetration, wash off, and phototransformation in the canopy had to be derived from a diversity of literature data. Cumulative volatilization of the moderately volatile parathion (31% of the dosage in 7.6 days) could be simulated after calibrating two input data derived for the related compound parathion-methyl. The less volatile and more slowly transformed chlorothalonil showed 5% volatilization in 7.6 days, which could be explained by the simulation. Simulated behavior of the pesticides in the crop canopy roughly corresponded to published data.

Volatilization of the pesticides chlorpyrifos and fenpropimorph from a potato crop.

Volatilization of pesticides from crops in the field can be an important emission pathway. In a field experiment with characterization of meteorological conditions, the pesticides chlorpyrifos and fenpropimorph were sprayed onto a potato crop, after which concentrations in the air and on/in the plants were measured. Rates of volatilization were estimated with the aerodynamic profile (ADP), energy balance (EB), relaxed eddy accumulation (REA), and plume dispersion (PD) methods. The volatilization rates obtained with the ADP and EB methods were similar, while some rates obtained with the REA and PD methods in the initial period were lower. Cumulative volatilization of chlorpyrifos during daylight hours (ADP and EB methods) was estimated to be about 65% of the dosage. By far the majority of this volatilization occurred in the first few days. Competing processes at the plant surface had a considerable effect on the dissipation of fenpropimorph, so cumulative volatilization during daylight hours was estimated to be only 7% of the dosage. Plant surface residues were higher than would correspond with the volatilization rate, indicating that penetration into the leaves had occurred.

Measured and computed volatilisation of the fungicide fenpropimorph from a sugar beet crop.

Depending on their vapour pressure, volatilisation can be one of the main pathways of emission of pesticides into the environment. The volatilisation of fenpropimorph was studied in a field experiment in which the fungicide was sprayed onto a sugar beet crop. Volatilisation rates were calculated by measuring the concentration gradient in air, using the Aerodynamic and Bowen Ratio methods. A simplified computation model was used to simulate pesticide volatilisation, together with the concurrent processes of penetration into the plant leaves and phototransformation. Input data for the model had already been obtained by carrying out a wind-tunnel study with fenpropimorph, whereby field conditions were imitated. The computations yielded a reasonable description of the level and rate of decline of fenpropimorph volatilisation in the first 4 h after spraying. The continued volatilisation 2 and 3 days after spraying could be described by assuming that a fraction of the deposit was poorly exposed with comparatively low rates of the decline processes. In the first 3 days, penetration of fenpropimorph into the plant leaves was computed to be the main route for the pesticide (52% of the dosage), with substantial contributions from volatilisation (12%) and phototransformation (11%). The computation model can be developed further as a tool for extrapolating results on volatilisation from small-scale experiments to field conditions, but this requires more information on the effect of environmental conditions on the model parameters.