A pesticide emission model (PEM) Part I: model development

The application of pesticides to cultivated soil and crops is a major source of pesticides that are found in the atmosphere and which are transported and deposited to land and water surfaces over distances that range from local to global scales. In this first part of a two-part paper, a pesticide emission model (PEM) is proposed for estimating the exchange with the atmosphere of pesticides applied to soils and crops. The basis of PEM is a one-dimensional numerical solution of the dynamic equations describing the advection and diffusion of heat, moisture and pesticide within the soil column and exchange with the atmosphere through heat transfer, evapotranspiration and volatilization. The soil model is coupled with an atmospheric surface layer and a simple canopy model that includes: the interception of sprayed pesticide by the crop foliage; the partitioning of pesticide within a wet or dry canopy; and, the volatilization of pesticide to the atmosphere or the wash-off to the soil by precipitation. The finite-element technique used for solving the model equations is mass conservative and multi-year periods of simulation are possible while maintaining a proper mass balance of pesticide in the soil. The model is solved using 1200 s time-steps and 49 variably spaced levels in the soil to a depth of 2 m, with the highest vertical resolution (0.002 m spacing) near the soil surface. Similarity theory is used to parameterize the fluxes of heat, moisture and pesticide through the atmospheric surface layer with hourly meteorology being provided by either climate station observations or a meteorological model. In the second part to this paper, the results of an evaluation of PEM are reported.     

Development of a regional hydrologic soil model and application to the Beerze--Reusel drainage basin

The soil compartment is an important interface between the atmosphere and the subsurface hydrosphere. In this paper a conceptual approach for regional hydrologic soil modelling (RHSM) is presented, which provides two important qualities for modelling. First, the soil compartment is directly coupled to the atmosphere via the land surface and to the aquifers. Second, extremely fine (5cm vertical) resolutions of the soil system can be realized at regional scales (several hundreds of km(2)). This high-resolution modelling could be achieved by parallel computation techniques. The RHSM approach is applied to the Beerze-Reusel drainage basin, which belongs to the Meuse River basin. Moisture transport in the soil system was calculated with extremely high vertical resolution at a regional scale based on rainfall-evaporation data for the year 2000. As a result, highly resolved regional groundwater recharge pattern addressing the heterogeneity of soil systems could be determined.     

Global circulation of atmospheric mercury: a modelling study

This paper presents a comprehensive atmospheric global and regional mercury model and its capability in describing the atmospheric cycling of mercury. This is an on-line model (integrated within the Canadian operational environmental forecasting and data assimilation system) which can be used to understand the role of meteorology in mercury cycling (atmospheric pathways), the inter-annual variability of mercury and can be evaluated against observations on global scales. This is due to the fact that the model uses a combination of actual observed and predicted meteorological state of the atmosphere at high resolution to integrate the model as opposed to the climatological approach used in existing global mercury models. The model was integrated and evaluated on global scale using only anthropogenic emissions. North to south gradients in mercury concentrations, seasonal variability, dry and wet deposition and vertical structure are well simulated by the model. The model was used to explain the observed seasonal variations in atmospheric mercury circulation. The results from this study include a global animation of surface air concentrations of total gaseous mercury for 1997.     

Modelling the fate of organic chemicals in the soil plant environment: Model study of root uptake of pesticides

The fate of organic chemicals in the soil-plant-atmosphere environment and the governing processes were studied with a coupled dynamic soil transport and plant compartment model. Scenarios with applications of pesticides on sand and loam soils with chemical uptake in barley and wheat were used in the model calculations. Root uptake and concentrations in the plant compartments stem, leave and fruit were calculated for the pesticides terbuthylazine, isoproturon and carbofuran.

The effectivity of uptake from soils with different soil sorption coefficients had been shown for sand and loam soils. The processes degradation in plant and volatilization from leaves to atmosphere are especially effective for carbofuran and terbuthylazine. Although the concentrations in corn at harvest are lower than the maximum allowed concentrations, the peak concentrations in the course of the vegetation period are significantly higher (factor ≤ 200).     

PLATIN (plant-atmosphere interaction) I: A model of plant-atmosphere interaction for estimating absorbed doses of gaseous air pollutants

A PLant-ATmosphere INteraction model (PLATIN) was developed for estimating air pollutant absorbed doses under ambient conditions. PLATIN is based on the canopy energy balance combined with a gas transport submodel. The model has three major resistance components: (1) a turbulent atmospheric resistance Rah(zm) that describes the atmospheric transport properties between a measurement height above the canopy and the conceptual height z=d+z0m which represents the sink for momentum according to the big-leaf concept; (2) a quasilaminar layer resistance R(b,A) that quantifies the way in which the transfer of sensible heat and matter (e.g. latent heat, ozone) differs from momentum transfer; (3) a canopy or surface resistance R(c,A) that describes the influences of the plant/soil system on the exchange processes. Soil water content is simulated by a Force-Restore model. By a simple interception submodel precipitation and dew are partitioned into intercepted water and water reaching the soil surface. PLATIN can be run in a prognostic or a diagnostic mode. It is also intended for on-line use in air quality monitoring networks.     

An online coupled meteorological and air quality modeling study of the effect of complex terrain on the regional transport and transformation of air pollutants over the Western United States

One of the most prominent of characteristics of the western United States that affects its meteorology is the complexity of its mountainous terrain. The meteorological Mesoscale Model, version 5 with Chemistry (MM5-Chem), an online-coupled atmospheric chemistry model, was used to investigate the effect of this terrain on a high air pollution event in the free troposphere. The simulations were evaluated by comparisons with data from the North American Regional Reanalysis (NARR). Complex terrain was shown to have an important influence on the vertical transport of air pollutants on the regional scale; emissions from ground level were vertically mixed as high as 5 km above sea surface level for the wintertime conditions simulated. The simulations showed that the vertical transport of emissions from the Earth's surface could have a more significant effect on mid and upper level chemical concentrations than chemical production. The vertical transport was caused predominately by terrain forced flow over the mountains’ ridge-line and the terrain forced flow was affected by the mountain peak height and the complexity of the terrain downwind.     

Evaluation of the Meteo-France response in ETEX release 1

During ETEX Meteo-France applied part of its emergency response system for critical events developped in the framework of the World Meteorological Organization environmental emergency response program. The atmospheric transport model used to forecast the evolution of a passive tracer is an eulerian model called MEDIA. In real time this model is driven by meteorological data from ARPEGE, the operational numerical weather prediction model available at the Meteo-France operation center. The overall evaluation of the results show that the model can reproduce the cloud displacement, but there exists a stretching in the transport direction. In the ATMES-II phase, the results are closer to the observations when meteorological data from the European Center for Medium range Weather Forecast are used. A simulation using analyzed meteorological data from ARPEGE every 6 h slightly improve the results comparing with the real-time experiment. All the simulations we performed reveal that the quality of the atmospheric transport model is strongly dependent on the quality of the driving numerical weather prediction model.     

A modeling assessment of association between East Asian summer monsoon and fate/outflow of α-HCH in Northeast Asia

Using a dynamic numerical atmospheric transport model for organochlorine pesticides (OCPs), the relationship between the East Asian summer monsoon and the fate of α-hexachlorocyclohexane (α-HCH), a banned OCP, in the atmosphere over Northeast Asia was investigated and assessed. The modeled temporal and spatial patterns and variability of α-HCH air concentrations during the summer months of 2005 revealed a strong link between this chemical in the atmosphere over Northeast Asia and the East Asian summer monsoon. At lower atmospheric levels, easterly and southeasterly winds blowing from relatively cold ocean surface convey α-HCH air concentration from southeast China to northeast China. A monsoon front extending from southeast China to Japan, characterized by a strong wind convergence, carried the air concentration to a high elevation of the atmosphere where it was delivered by southerly monsoon flow to northern China and North Pacific Ocean. This summer monsoon associated northward atmospheric transport caused a reversal of the soil/air exchange from outgassing to net deposition during spring–summer period. The modeled wet deposition fluxes of α-HCH agreed well with the changes in the typical summer monsoon rain bands, designated as Meiyu in China, Changma in Korea, and Baiu in Japan. The major wet deposition flux paralleled with the monsoon front as well as the monsoon rain bands. The temporal change in the fluxes exhibits abrupt northward advances, which is associated with a stepwise northward and northeastward advance of the East Asian summer monsoon. The modeled α-HCH outflow in the atmosphere from China occurs mostly in the summer months and through northeast China, featured strongly by the evolution of the summer month. This study suggests that the East Asian summer monsoon provides a major atmospheric pathway and summer outflows to α-HCH over East Asia.     

A screening model-based study of transport fluxes and fate of airborne mercury deposited onto catchment areas.

Dynamics of airborne mercury deposited onto catchment areas is investigated within the framework of a simulation model. Model results show that, for a particular atmospheric deposition rate, significant interannual variability in mercury transport flux in catchments is caused by climatology and corresponding differences in catchment soil loss rates; in comparison to the normal year, runoff flux increased by a factor of 2-3 for the wet year (rainfall 35% above normal) while for the dry year (rainfall 18% below normal) runoff flux decreased by factors of 5-7. The interaction of parameters describing soil type, topography and vegetation cover causes variability in both transport and emission fluxes among catchments; as soil loss rate increases by a factor of 5 due to variations in these parameters among the examined catchments, annual average transport flux increases by a factor of 3; and annual average emission flux of mercury (as Hg0) from soil to the atmosphere decreases by a factor of 2 due to the decreased levels of soil mercury associated with catchment soil loss increases. Seasonal variability of transport flux is associated with seasonal changes in precipitation and soil loss rates while seasonal changes of emission flux are primarily due to changes in soil moisture regime and temperature. Although modeled results are consistent with observational data from previous studies, they must be interpreted in a relative sense due to the screening-level character of this study.     

A diagnostic evaluation of modeled mercury wet depositions in Europe using atmospheric speciated high-resolution observations

This study is part of the Global Mercury Observation System (GMOS), a European FP7 project dedicated to the improvement and validation of mercury models to assist in establishing a global monitoring network and to support political decisions. One key question about the global mercury cycle is the efficiency of its removal out of the atmosphere into other environmental compartments. So far, the evaluation of modeled wet deposition of mercury was difficult because of a lack of long-term measurements of oxidized and elemental mercury. The oxidized mercury species gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) which are found in the atmosphere in typical concentrations of a few to a few tens pg/m³ are the relevant components for the wet deposition of mercury. In this study, the first European long-term dataset of speciated mercury taken at Waldhof/Germany was used to evaluate deposition fields modeled with the chemistry transport model (CTM) Community Multiscale Air Quality (CMAQ) and to analyze the influence of the governing parameters. The influence of the parameters precipitation and atmospheric concentration was evaluated using different input datasets for a variety of CMAQ simulations for the year 2009. It was found that on the basis of daily and weekly measurement data, the bias of modeled depositions could be explained by the bias of precipitation fields and atmospheric concentrations of GOM and PBM. A correction of the modeled wet deposition using observed daily precipitation increased the correlation, on average, from 0.17 to 0.78. An additional correction based on the daily average GOM and PBM concentration lead to a 50 % decrease of the model error for all CMAQ scenarios. Monthly deposition measurements were found to have a too low temporal resolution to adequately analyze model deficiencies in wet deposition processes due to the nonlinear nature of the scavenging process. Moreover, the general overestimation of atmospheric GOM by the CTM in combination with an underestimation of low precipitation events in the meteorological models lead to a good agreement of total annual wet deposition besides the large error in weekly deposition estimates. Moreover, it was found that the current speciation profiles for GOM emissions are the main factor for the overestimation of atmospheric GOM concentrations and might need to be revised in the future. The assumption of zero emissions of GOM lead to an improvement of the mean normalized bias for three-hourly observations of atmospheric GOM from 9.7 to 0.5, Furthermore, the diurnal correlation between model and observation increased from 0.01 to 0.64. This is a strong indicator that GOM is not directly emitted from primary sources but is mainly created by oxidation of GEM.     

Global atmospheric cycle of mercury: a model study on the impact of oxidation mechanisms

Mercury (Hg) is a global pollutant since its predominant atmospheric form, elemental Hg, reacts relatively slowly with the more abundant atmospheric oxidants. Comprehensive knowledge on the details of the atmospheric Hg cycle is still lacking, and in particular, there is some uncertainty regarding the atmospherically relevant reduction-oxidation reactions of mercury and its compounds. ECHMERIT is a global online chemical transport model, based on the ECHAM5 global circulation model, with a highly customisable chemistry mechanism designed to facilitate the investigation of both aqueous- and gas-phase atmospheric mercury chemistry. An improved version of the model which includes a new oceanic emission routine has been developed. Results of multiyear model simulations with full atmospheric chemistry have been used to examine the how changes to chemical mechanisms influence the model’s ability to reproduce measured Hg concentrations and deposition flux patterns. The results have also been compared to simple fixed-lifetime tracer simulations to constrain the possible range of atmospheric mercury redox rates. The model provides a new and unique picture of the global cycle of mercury, in that it is online and includes a full atmospheric chemistry module.     

Determination of the potential for release of mercury from combustion product amended soils: Part 1--Simulations of beneficial use

This paper describes a project that assessed the potential for mercury (Hg) release to air and water from soil amended with combustion products to simulate beneficial use. Combustion products (ash) derived from wood, sewage sludge, subbituminous coal, and a subbituminous coal-petroleum coke mixture were added to soil as agricultural supplements, soil stabilizers, and to develop low-permeability surfaces. Hg release was measured from the latter when intact and after it was broken up and mixed into the soil. Air-substrate Hg exchange was measured for all materials six times over 24 hr, providing data that reflected winter, spring, summer, and fall meteorological conditions. Dry deposition of atmospheric Hg and emission of Hg to the atmosphere were both found to be important fluxes. Measured differences in seasonal and diel (24 hr) fluxes demonstrated that to establish an annual estimate of air-substrate flux from these materials data on both of these time steps should be collected. Air-substrate exchange was highly correlated with soil and air temperature, as well as incident light. Hg releases to the atmosphere from coal and wood combustion product-amended soils to simulate an agricultural application were similar to that measured for the unamended soil, whereas releases to the air for the sludge-amended materials were higher. Hg released to soil solutions during the Synthetic Precipitation Leaching Procedure for ash-amended materials was higher than that released from soil alone. On the basis of estimates of annual releases of Hg to the air from the materials used, emissions from coal and wood ash-amended soil to simulate an agricultural application could simply be re-emission of Hg deposited by wet processes from the atmosphere; however, releases from sludge-amended materials and those generated to simulate soil stabilization and disturbed low-permeability pads include Hg indigenous to the material.     

Internal boundary layer structure under sea-breeze conditions in Hong Kong

A three-dimensional atmospheric model is used for modelling the airflow pattern and internal boundary layer (IBL) development over the Hong Kong region that comprises hilly terrain and complex coastline. Observations used to verify the model are drawn from 32 meteorological stations and a ground-based lidar system. It is found that the modelled results are in good agreement with the observed airflow field and IBL development. Due to the interaction of complex terrain and sea-breeze circulations, several confluence zones of wind fields are found in different locations, depending on the background wind velocity and the differential-heating rate between land and sea. Subsequently, these kinds of wind field patterns give rise to a three-dimensional dome-shaped IBL distribution that forms an impediment to air-pollutant dispersion outside of the layer.     

Modeling transport and deposition of contaminants to ecosystems of concern: a case study for the Laurentian Great Lakes

Transfer efficiency (TE) is introduced as a model output that can be used to characterize the relative ability of chemicals to be transported in the environment and deposited to specific target ecosystems. We illustrate this concept by applying the Berkeley-Trent North American contaminant fate model (BETR North America) to identify organic chemicals with properties that result in efficient atmospheric transport and deposition to the Laurentian Great Lakes. By systematically applying the model to hypothetical organic chemicals that span a wide range of environmental partitioning properties, we identify combinations of properties that favor efficient transport and deposition to the Lakes. Five classes of chemicals are identified based on dominant transport and deposition pathways, and specific examples of chemicals in each class are identified and discussed. The role of vegetation in scavenging chemicals from the atmosphere is assessed, and found to have a negligible influence on transfer efficiency to the Great Lakes. Results indicate chemicals with octanol-water (K(ow)) and air-water (K(aw)) partition coefficients in the range of 10(5)-10(7) and 10(-4)-10(-1) combine efficient transport and deposition to the Great Lakes with potential for biaccumulation in the aquatic food web once they are deposited. A method of estimating the time scale for atmospheric transport and deposition process is suggested, and the effects of degrading reactions in the atmosphere and meteorological conditions on transport efficiency of different classes of chemicals are discussed. In total, this approach provides a method of identifying chemicals that are subject to long-range transport and deposition to specific target ecosystems as a result of their partitioning and persistence characteristics. Supported by an appropriate contaminant fate model, the approach can be applied to any target ecosystem of concern.     

Experimental verification for real-time environmental emergency response system: WSPEEDI by European tracer experiment

Japan Atomic Energy Research Institute has developed an emergency response system WSPEEDI to forecast long-range atmospheric dispersions of radionuclides discharged into the atmosphere. The latest version of WSPEEDI consists of an atmospheric dynamic model MM5 for calculating meteorological fields and a particle random-walk model for atmospheric dispersion. The performance of WSPEEDI was evaluated by data obtained from a field tracer experiment over Europe (ETEX) in this paper. The model validation was done with respect to the following points: (1) the dependence of model accuracy on the temporal and spatial resolutions of the meteorological fields and (2) the superiority of an atmospheric dynamic model over a mass-consistent wind model. Regarding (1), it was shown that the calculation accuracy of the new version with high temporal resolution was improved, especially at the edge of the plume. Moreover, although the increase in horizontal spatial resolution of the old version had no substantial effect on the model performance, increase in horizontal resolution of the new version contributed to the significant improvement of the calculation accuracy. These results showed that the dynamically calculated meteorological field with the spatial resolution of the meso-β–γ scale greatly improved calculation accuracy.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Modelling the behaviour of PAHs during atmospheric transport from the UK to the Arctic

Persistent organic pollutants (POPs) such as PAHs are subject to long-range atmospheric transport, which can result in the contamination of remote areas such as the Arctic. A simple model was developed to describe the removal processes of four PAHs; fluorene (FLU), phenanthrene (PHEN), fluoranthene (FLA) and benzo[a]pyrene (B[a]P) transported over a 5 day period from a source area over the UK to the Russian Arctic. The purpose of this model was to study processes affecting the PAHs within the atmosphere, rather than their interaction with the earth's surface. The components to the model included gas/particle partitioning, reaction with OH radicals and dry and wet deposition (both rain and snow). Atmospheric/meteorological parameters for the geographical region of interest were generated from three-dimensional atmospheric models. Air concentrations were prescribed in the source area with no additional PAH inputs along the transect, both winter and summer scenarios were modelled. Reaction with OH was a major removal mechanism for gas-phase FLU, PHEN and FLA, most notably in the temperate atmosphere. Wet deposition in the form of snow accounted for the majority of PAH loss in the winter, although the gas and particle scavenging ratios used in this model ranged over several orders of magnitude. Using a 5 day transport scenario in a `1-hop’ event, the model predicted that a primary emission of FLA and B[a]P to the atmosphere of the southern UK, would not reach the Russian Arctic at a distance of ∼3500 km, assuming a constant windspeed of 10 m s⁻¹. However, both FLU and PHEN with calculated half-lives of >60 h during the winter could be transported to this area under this scenario.     

Modelling the dynamic air-water-sediment coupled fluxes and occurrence of polychlorinated biphenyls in a high altitude lake

The BIODEP model in terms of atmosphere-lake interactions was developed. The model was applied to an oligotrophic, dimictic high altitude lake (Lake Redo, Pyrenees) for a range of polychlorinated biphenyl (PCB) congeners. High altitude lakes, which receive their contaminant inputs uniquely from the atmosphere through long-range atmospheric transport, provide ideal controlled environments for the study of the interactions between atmospheric depositional and water column biogeochemical processes. The BIODEP model was able to predict dissolved water concentrations and PCB accumulation in the lake sediment within a factor of 2. This shows that the BIODEP model captures the essential processes driving the sink of POPs in high altitude lakes and that POP occurrence in the lake is driven by direct atmospheric inputs with limited influence from the watershed. An important seasonal variability in water column concentrations is predicted which should have important implications in sampling strategies. Furthermore, it is shown that diffusive air-water exchange dominated the PCB dynamics in the lake, especially for the less chlorinated biphenyls.     

Validation of modeling approach to evaluate congener-specific concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans in air and soil near a solid waste incinerator.

A concise modeling approach using long-term averaged meteorological data was developed to estimate site-specific concentrations of congeners of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) near a solid waste incinerator. This approach consists of calculation of atmospheric dispersion, dry and wet deposition of gaseous and particle-bound congeners, and non-steady-state concentrations in soil. The predictability of this approach was evaluated by comparison of calculated concentrations of congeners in soil with those measured at eight locations near a municipal solid waste incinerator (MSWI). The variation of these concentrations due to variability of meteorological parameters is small. A considerable number of mean values show good agreement with measured concentrations within a factor of three. The reasonable agreement between calculated and measured concentrations indicates that algorithms for the calculation of vapor-phase deposition and non-steady-state concentrations in soil must be included in the modeling approach for an accurate estimation of the concentrations of congeners of PCDD/Fs emitted from MSWIs to the atmosphere. For a detailed estimation of site-specific concentrations, it is important to specify the bulk density of soil in the evaluated area, together with meteorological parameters.     

Use of CALPUFF for exposure assessment in a near-field,complex terrain setting

CALPUFF is an atmospheric source-receptor model recommended by the U.S. Environmental Protection Agency for use on a case-by-case basis in complex terrain and wind conditions. The ability of the model to provide useful information for exposure assessments in areas with those topographical and meteorological conditions has received little attention. This is an important knowledge gap for use of CALPUFF outside of regulatory applications, such as exposure analyses conducted in support of risk assessments and health studies. We compared deposition of cadmium (Cd), lead (Pb), and zinc (Zn) calculated with CALPUFF as a result of emissions from a zinc smelter with corresponding concentrations of the metals measured in attic dust and soil samples obtained from the surrounding area. On a point-by-point analysis, predictions from CALPUFF explained 11% (lead) to 53% (zinc) of the variability in concentrations measured in attic dust. Levels of heavy metals in soil interpolated to 100 residential addresses from the distribution of concentrations measured in soil samples also agreed well with deposition predicted with CALPUFF: R² of 0.46, 0.76, and 079 for Pb, Cd, and Zn, respectively. Community-average concentrations of Cd, Pb, and Zn measured in soil were significantly (p < 0.0001) and strongly correlated (R² ranged from 0.77 to 0.98) with predicted deposition rates. These findings demonstrate that CALPUFF can provide reasonably accurate predictions of the patterns of long-term air pollutant deposition in the near-field associated with emissions from a discrete source in complex terrain. Because deposition estimates are calculated as a linear function of air concentrations, CALPUFF is expected to be reliable model for prediction of long-term average, near-field ambient air concentrations in complex terrain as well.