PLATIN (plant-atmosphere interaction) II: Co-occurrence of high ambient ozone concentrations and factors limiting plant absorbed dose

There is an ongoing debate as to which components of the ambient ozone (O3) exposure dynamics best explain adverse crop yield responses. A key issue is regarding the importance of peak versus mid-range hourly ambient O3 concentrations. While in this paper the importance of peak atmospheric O3 concentrations is not discounted, if they occur at a time when plants are conducive for uptake, the corresponding importance of more frequently occurring mid-range O3 concentrations is described. The probability of co-occurrence of high O3 concentrations and O3 uptake limiting factors is provided using coherent data sets of O3 concentration, air temperature, air humidity, mean horizontal wind velocity and global radiation measured at representative US and German air quality monitoring sites. Using the PLant-ATmosphere INteraction (PLATIN) model, the significance of the aforementioned meteorological parameters on ozone uptake is examined. In addition, the limitations of describing the O3 exposure for plants under ambient, chamberless conditions by SUM06, AOT40 or W126 exposure indices are discussed.     

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.     

Chemical transport models

Background, aim, and scope  Improving the parameterization of processes in the atmospheric boundary layer (ABL) and surface layer, in air quality and chemical transport models. To do so, an asymmetrical, convective, non-local scheme, with varying upward mixing rates is combined with the non-local, turbulent, kinetic energy scheme for vertical diffusion (COM). For designing it, a function depending on the dimensionless height to the power four in the ABL is suggested, which is empirically derived. Also, we suggested a new method for calculating the in-canopy resistance for dry deposition over a vegetated surface. Materials and methods  The upward mixing rate forming the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. The vertical eddy diffusivity is parameterized using the mean turbulent velocity scale that is obtained by the vertical integration within the ABL. In-canopy resistance is calculated by integration of inverse turbulent transfer coefficient inside the canopy from the effective ground roughness length to the canopy source height and, further, from its the canopy height. Results  This combination of schemes provides a less rapid mass transport out of surface layer into other layers, during convective and non-convective periods, than other local and non-local schemes parameterizing mixing processes in the ABL. The suggested method for calculating the in-canopy resistance for calculating the dry deposition over a vegetated surface differs remarkably from the commonly used one, particularly over forest vegetation. Discussion  In this paper, we studied the performance of a non-local, turbulent, kinetic energy scheme for vertical diffusion combined with a non-local, convective mixing scheme with varying upward mixing in the atmospheric boundary layer (COM) and its impact on the concentration of pollutants calculated with chemical and air-quality models. In addition, this scheme was also compared with a commonly used, local, eddy-diffusivity scheme. Simulated concentrations of NO₂ by the COM scheme and new parameterization of the in-canopy resistance are closer to the observations when compared to those obtained from using the local eddy-diffusivity scheme. Conclusions  Concentrations calculated with the COM scheme and new parameterization of in-canopy resistance, are in general higher and closer to the observations than those obtained by the local, eddy-diffusivity scheme (on the order of 15–22%). Recommendations and perspectives  To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO₂) were compared for the years 1999 and 2002. The comparison was made for the entire domain used in simulations performed by the chemical European Monitoring and Evaluation Program Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.     

杀虫剂十氯酮的多介质环境行为模拟

应用EQC模型模拟十氯酮在多介质环境中的归宿和迁移通量.结果表明:土壤是十氯酮最大的贮存库,在稳态平衡条件下,残留率达到95.0%;在稳态非平衡条件下,十氯酮单独排放到水体,有37.5%残留在于排放的水体中,其在大气的浓度水平和质量分布均很低,在沉积物中的质量则来自于水体向沉积物的沉降迁移;十氯酮主要通过水体的水平迁移和土壤的厌氧降解输出;十氯酮的主要界面迁移过程是大气向土壤的迁移,其次是水体向沉积物的沉降和大气向水体的迁移.     

Modeling coupled interactions of carbon,water, and ozone exchange between terrestrial ecosystems and the atmosphere. I: model description

A new biophysical model (FORFLUX) is presented to study the simultaneous exchange of ozone, carbon dioxide, and water vapor between terrestrial ecosystems and the atmosphere. The model mechanistically couples all major processes controlling ecosystem flows trace gases and water implementing recent concepts in plant eco-physiology, micrometeorology, and soil hydrology. FORFLUX consists of four interconnected modules-a leaf photosynthesis model, a canopy flux model, a soil heat-, water- and CO2- transport model, and a snow pack model. Photosynthesis, water-vapor flux and ozone uptake at the leaf level are computed by the LEAFC3 sub-model. The canopy module scales leaf responses to a stand level by numerical integration of the LEAFC3model over canopy leaf area index (LAI). The integration takes into account (1) radiative transfer inside the canopy, (2) variation of foliage photosynthetic capacity with canopy depth, (3) wind speed attenuation throughout the canopy, and (4) rainfall interception by foliage elements. The soil module uses principles of the diffusion theory to predict temperature and moisture dynamics within the soil column, evaporation, and CO2 efflux from soil. The effect of soil heterogeneity on field-scale fluxes is simulated employing the Bresler-Dagan stochastic concept. The accumulation and melt of snow on the ground is predicted using an explicit energy balance approach. Ozone deposition is modeled as a sum of three fluxes- ozone uptake via plant stomata, deposition to non-transpiring plant surfaces, and ozone flux into the ground. All biophysical interactions are computed hourly while model projections are made at either hourly or daily time step. FORFLUX represents a comprehensive approach to studying ozone deposition and its link to carbon and water cycles in terrestrial ecosystems.     

Simulating the temporal changes of OCP pollution in Hangzhou, China

A dynamic fugacity model was applied to simulate the changes of contents and transfer fluxes of hexachlorocyclohexane (HCHs) and dichloro-diphenyl-trichloroethane (DDTs) from 1950s in the environment of Hangzhou, China. The receptors are composed of air, surface water, soils, sediment and biota compartments. The model provides a method to combine loadings of HCHs and DDTs from various sources with a series of physical-chemical processes to estimate concentrations and transport fluxes of HCHs and DDTs. Model results suggested that the calculated concentrations were in line with the observed ones. The highest contents of HCH and DDT in the environment of study area were 523 t and 471 t before 1983, among which about 80.7% HCHs and 93.2% DDTs remained in the soil compartment. From 1984 to now, contents of HCHs and DDTs had decreased to about 0.07% and 0.40% of their highest amount (before 1983), and only about 0.001% and 0.014% will expect to be left in 2020 in the study area according to the model prediction. Before 1983, the main transfer fluxes of HCHs were deposition from air to soil, runoff from soil to water and diffusion from soil to air, but for DDTs the main transfer fluxes were deposition from air to soil and water, and transfer from water to sediment. From 1984 to now, runoff from soil to water and transfer from water to sediment became the dominant processes. Although a large amount of HCHs and DDTs had been applied to the study area, their residue levels in the soils were much lower than those in North China (had lesser HCHs and DDTs application than in South China) at present time, and close to other locations of South China (had similar HCHs and DDTs application level). It can be attributed to the high precipitation and temperature that enhances the processes of wet deposition, evaporation and degradation of OCPs. Sensitivities of the input parameters to the calculated concentrations were evaluated using coefficient-of-variation normalized sensitivity coefficients. The model was also subjected to uncertainty analyses using a Monte Carlo simulation.     

Difference in ozone uptake in grassland species between open-top chambers and ambient air

Exposure-response data from open-top chamber (OTC) experiments are often directly applied to ambient air (AA) conditions. Because microclimatic conditions are modified and pollutant uptake by plants may differ (i.e. 'chamber effect'), there is concern about the influence of OTCs on these relationships. In addition, AA concentrations are often measured at a height which differs from canopy height and correction for the concentration gradient (i.e. 'gradient effect') is necessary. To quantify the relative contribution of plant characteristics and microclimatic factors to these effects, ozone uptake by horizontal leaves at the top of the canopy was calculated for plants grown in OTCs or AA by using a resistance analogy model. Data from an OTC experiment in 1996/97 for six species typical of productive grasslands were used. Ozone concentration inside OTCs was set equal to the concentration measured at a height of 3 m above ground (C(z(ref))) or at canopy height (C(0)). The gradient effect resulted in a 16-27% lower average C(0) than C(z(ref)), depending on species. The main determinant of the chamber effect was a systematic difference in leaf-to-air vapour pressure deficit between OTCs and AA which affected stomatal resistance and ozone uptake. In case of monocultures both effects were species-specific. In species mixtures the gradient effect differed between mixing ratios, whereas the chamber effect was species-specific. Because of the inter-specific difference in the chamber effect on ozone uptake, it is concluded that ozone effects on species mixtures differ systematically between OTCs and AA. The data underline that extrapolation of ozone flux-response relationships from OTC experiments must be based on canopy-level ozone concentrations, and that these relationships should be applied only to single species under microclimatic conditions similar to those prevailing in the experiment.     

Modelling the fate of persistent organic pollutants in Europe: parameterisation of a gridded distribution model

A regionally segmented multimedia fate model for the European continent is described together with an illustrative steady-state case study examining the fate of gamma-HCH (lindane) based on 1998 emission data. The study builds on the regionally segmented BETR North America model structure and describes the regional segmentation and parameterisation for Europe. The European continent is described by a 5 degrees x5 degrees grid, leading to 50 regions together with four perimetric boxes representing regions buffering the European environment. Each zone comprises seven compartments including; upper and lower atmosphere, soil, vegetation, fresh water and sediment and coastal water. Inter-regions flows of air and water are described, exploiting information originating from GIS databases and other georeferenced data. The model is primarily designed to describe the fate of Persistent Organic Pollutants (POPs) within the European environment by examining chemical partitioning and degradation in each region, and inter-region transport either under steady-state conditions or fully dynamically. A test case scenario is presented which examines the fate of estimated spatially resolved atmospheric emissions of lindane throughout Europe within the lower atmosphere and surface soil compartments. In accordance with the predominant wind direction in Europe, the model predicts high concentrations close to the major sources as well as towards Central and Northeast regions. Elevated soil concentrations in Scandinavian soils provide further evidence of the potential of increased scavenging by forests and subsequent accumulation by organic-rich terrestrial surfaces. Initial model predictions have revealed a factor of 5-10 underestimation of lindane concentrations in the atmosphere. This is explained by an underestimation of source strength and/or an underestimation of European background levels. The model presented can further be used to predict deposition fluxes and chemical inventories, and it can also be adapted to provide characteristic travel distances and overall environmental persistence, which can be compared with other long-range transport prediction methods.     

Effect of shoreline meteorological measurements on NOAA Buoy model prediction of coastal air–sea gas transfer

The NOAA Buoy model is currently used to estimate the air–sea transfer rates of highly soluble gases over coastal water bodies, such as Tampa Bay, using offshore meteorological measurements. Since a goal of the BRACE study was to improve estimates of nitrogen deposition over Tampa Bay, our objective was to investigate if the model accurately predicts gas transfer when shoreline input data are used in lieu of offshore measurements. To accomplish this objective, we compared over-water measurements of sensible heat with NOAA Buoy model predictions using both offshore and shoreline meteorology. In the summer months, the apparent daytime influence of land surface heating on air temperature produces a higher air than water temperature at the shoreline. For the NOAA Buoy model, this yields stable atmospheric conditions and thus under-predicts the over-water exchange rates for a shallow estuary. If the data records are removed from the model for periods when air temperature is 4.8 K greater than the water temperature, the shoreline and over-water transfer rates are in reasonable agreement.     

Contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs): Application to Southeastern France

A modeling approach has been developed to estimate the contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs). It combines an Eulerian chemical transport model for atmospheric processes (Polair3D/Polyphemus) with a fate and transport model for soil and vegetation (Ourson). These two models were specifically adapted for POPs. Results are presented for benzo(a)pyrene (BaP). As expected no accumulation of BaP in leaf vegetables appears during the growth period for each harvest over the 10 years simulated. For BaP and leaf vegetables, this contamination depends primarily on direct atmospheric deposition without chemical transfer from the soil to the plant. These modeling results are compared to available data.     

Global-scale environmental transport of persistent organic pollutants

In order to realistically simulate both chemistry and transport of atmospheric organic pollutants, it is indispensable that the applied models explicitly include coupling between different components of the global environment such as atmosphere, hydrosphere, cryosphere and soil system. A model with such properties is presented.

The atmospheric part of the model is based on the equations in a general contravariant form which permits easy changes of the coordinate system by redefining the metric tensor of a specifically employed coordinate system. Considering a need to include explicitly the terrain effects, the terrain following spherical coordinate system is chosen from among many possible coordinate systems. This particular system is a combination of the Gal-Chen coordinates, commonly employed in mesoscale meteorological models, and the spherical coordinates, typical for global atmospheric models.

In addition to atmospheric transport, the model also simulates the exchange between air and different types of underlying surfaces such as water, soil, snow, and ice. This approach permits a realistic representation of absorption and delayed re-emission of pollutants from the surface to the atmosphere and, consequently, allows to capture hysteresis-like effects of the exchange between the atmosphere and the other components of the system. In this model, the most comprehensive numerical representation of the exchange is that for soil. In particular, the model includes a realistic soil module which simulates both diffusion and convection of a tracer driven by evaporation from the soil, precipitation, and gravity.

The model is applied to a long-term simulation of the transport of pesticides (hexachlorocyclohexanes in particular). Emission fluxes from the soil are rigorously computed on the basis of the realistic data of the agricultural application. All four modelled systems, i.e. atmosphere, soil, hydrosphere and cryosphere, are driven by objectively analysed meteorological data supplemented, when necessary, by climatological information. Therefore, the verification against the observed data is possible. The comparison of the model results and the observations taken at remote stations in the Arctic indicates that the presented global modelling system is able to capture both trends and short-term components in the observed time series of the concentrations, and therefore, provides a useful tool for the evaluation of the source–receptor relationships.     

Using variances in hydrocarbon concentration and carbon stable isotope to determine the important influence of irrigated water on petroleum accumulation in surface soil

Hunpu is a wastewater-irrigated area southwest of Shenyang. To evaluate petroleum contamination and identify its sources at the area, the aliphatic hydrocarbons and compound-specific carbon stable isotopes of n-alkanes in the soil, irrigation water, and atmospheric deposition were analyzed. The analyses of hydrocarbon concentrations and geochemical characteristics reveal that the water is moderately contaminated by degraded heavy oil. According to the isotope analysis, inputs of modern C3 plants and degraded petroleum are present in the water, air, and soil. The similarities and dissimilarities among the water, air, and soil samples were determined by concentration, isotope, and multivariate statistical analyses. Hydrocarbons from various sources, as well as the water/atmospheric deposition samples, are more effectively differentiated through principal component analysis of carbon stable isotope ratios (δ¹³C) relative to hydrocarbon concentrations. Redundancy analysis indicates that 57.1 % of the variance in the δ¹³C of the soil can be explained by the δ¹³C of both the water and air, and 35.5 % of the variance in the hydrocarbon concentrations of the soil can be explained by hydrocarbon concentrations of both the water and the air. The δ¹³C in the atmospheric deposition accounts for 28.2 % of the δ¹³C variance in the soil, which is considerably higher than the variance in hydrocarbon concentrations of the soil explained by hydrocarbon concentrations of the atmospheric deposition (7.7 %). In contrast to δ¹³C analysis, the analysis of hydrocarbon concentrations underestimates the effect of petroleum contamination in the irrigated water and air on the surface soil. Overall, the irrigated water exerts a larger effect on the surface soil than does the atmospheric deposition.     

Numerical Modeling of the Transport Diffusion and Deposition of Pollutants For Regions and Extended Scales

There is an emerging need to develop understanding and predictive capability for the transport, diffusion, and deposition of pollutants on regional and extended spatial scales. Some recent developments in the numerical simulation of pollutant transport and diffusion are reviewed and summarized herein, including case studies of model validation whenever’available. The efforts reported include: (a) the development and verification of a Lagrangian large-cloud diffusion code for intermediate to extended scales; (b) a hybrid Lagrangian-Eulerian transport-diffusion code for simulating pollutant distributions in transient stratified shear flow; (c) a meteorological submodel for determining a mass-consistent wind field on a regional scale suitable as input to a regional air pollution model; and (d) the development and initial verification of a multi-box regional air pollution model for the San Francisco Bay Area utilizing a mass-consistent wind field submodel.     

Heterogeneous oxidation by ozone of naphthalene adsorbed at the air-water interface of micron-size water droplets

The mass transfer of naphthalene vapor to water droplets in air was studied in the presence of ozone (O3) in the gas phase. A falling droplet reactor with water droplets of diameters 55, 91, and 182 microm was used for the study. O3 reacted with naphthalene at the air-water interface, thereby decreasing the mass transfer resistance and increasing the rate of uptake of naphthalene into the droplet. A Langmuir-Hinshelwood reaction mechanism at the air-water interface satisfactorily described the surface reaction. The first-order surface reaction rate constant, ks, increased with decreasing droplet size. Three organic intermediates were identified in the aqueous phase as a result of ozonation of naphthalene at the surface of the droplet indicating both peroxidic and nonperoxidic routes for ozonation. The presence of an organic carbon surrogate (fulvic acid) increased both the partition constant of naphthalene and the surface reaction rate of O3. The heterogeneous oxidation of naphthalene by O3 on the droplet was 15 times faster than the homogeneous oxidation by O3 in the bulk air phase, whereas it was only 0.08 times the homogeneous gas-phase oxidation by hydroxyl radicals under atmospheric conditions.     

The effect of humidity and state of water surfaces on deposition of aerosol particles onto a water surface

Deposition processes of particles with dry diameter larger than about 10 μm are dominated by gravitational settling, while molecular diffusion and Brownian motion predominate the deposition processes of particles smaller than 0.1 μm in dry diameter. Many air pollution derived elements exhibit characteristics common to sub-micron particles. The objective of the present study is to examine the effects of meteorological conditions within the turbulent transfer layer on the deposition velocity of particles with dry diameter between 0.1 and 1 μm. It is for these sub-micron particles that particle growth by condensation in the deposition layer, the broken water surface effect and the enhanced transfer process due to atmospheric turbulence in the turbulent transfer layer play important roles in controlling the particle deposition velocity. Results of the present study show that the `dry air’ assumption of Williams’ model is unrealistic. Effects of ambient air relative humidity and water surface temperature cannot be ignored in determining the deposition velocity over a water surface. Neglecting effects of ambient air relative humidity and water surface temperature will result in defining atmospheric stability incorrectly. It is found that the largest effect of air relative humidity on deposition velocity occurs at an air–water temperature difference corresponding to the point of `displaced neutral stability'. For a given wind speed of U=5 m s⁻¹ the additive effects of water surface temperature, T_w, changes from 5 to 25°C and ambient air relative humidity variations from 85 to 60%, respectively, lead to a maximum difference in v_d of about 20%. For a higher wind speed of 10 m s⁻¹, however, the corresponding change in v_d reduces to less than 5%. This is further confirmation that wind speed is one of the strongest variables that governs the magnitude of v_d. The present study also found that the broken surface transfer coefficient, k_bs, given as a multiple of the smooth surface transfer coefficient, k_ss, is physically more meaningful than assigning it a constant value independent of particle size. The method used in this study requires only a single level of atmospheric data coupled with the surface temperature measurement. The present method is applicable for determining deposition velocity not only at the conventional measurement height of 10 m but also at any other heights that are different from the measurement height.     

Chloroform – concentration gradients in soil air and atmospheric air,and emission fluxes from soil

Since we demonstrated the natural formation of chloroform in soil, the question arose to which extent this contributes to the chloroform present in the atmosphere. Concentration gradients in soil air and atmospheric air of different forests were measured. Chloroform concentration gradients indicating emission occur in forest soils and the atmosphere under the canopy, whereas this was not observed for other chlorinated solvents. Above the canopy all concentration gradients observed for chloroform and 1,1,1-trichloroethane indicate deposition. The emission flux was measured using enclosures and calculated from the observed concentration gradients in soil air and atmospheric air. Wood-degrading areas and soils with a humic layer were found to emit up to 1000 ng chloroform m⁻² h⁻¹ and seem to be larger chloroform sources than the other areas of study. Rather unexpectedly, some points of one sampling site appeared to emit 1,1,1-trichloroethane, tetrachloromethane and tetrachloroethene. A reasonable agreement was found between the fluxes using enclosures and those derived from the concentration gradients in soil air and atmospheric air.     

The interfacial mass transfer resistances of the ozone dry deposition over the field soil of Taichung County in Taiwan

This study aims to design a dry deposition chamber and to measure ozone depletion over the Taichung field soil. This study seeks to verify the phenomena by an experimental and mathematical model. It is demonstrated that interfacial mass transfer resistances of ozone dry deposition involve reactive resistance (R(sr)) and kinetic resistance (R(sk)). It reveals the chemical reaction (O3 + NO --> NO2) to produce the reactive resistance, and verifies that the interfacial mass transfer resistances depend on nitrogen oxide emission and soil temperature. It shows that the interfacial mass transfer resistances are reduced with increasing soil temperature (T(S)). The model profiles are smaller than the observed data within a relative error of 15%. The reactive resistance decreases exponentially with increasing soil temperature; R(sr)(-1) (cm x sec(-1)) = 0.0001 exp (0.1455T(S)). The kinetic resistance decreases linearly with increasing soil temperature; R(sk)(-1)(cm x sec(-1)) = 0.0108T(S) + 1.4012. This model is more accurate with higher soil temperature and larger ozone concentration. Results are consistent with thermodynamics and reaction kinetics. Ozone dry deposition over agricultural soil causes conversion of nitrogen oxide (NO) to nitrogen dioxide (NO2).     

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).     

Modeling the surface–atmosphere exchange of ammonia

New parameterizations for surface–atmosphere exchange of ammonia are presented for application in atmospheric transport models and compared with parameterizations of the literature. The new parameterizations are based on a combination of the results of three years of ammonia flux measurements over a grassland canopy (dominated by Lolium perenne and Poa trivialis) near Wageningen, the Netherlands and existing parameterizations from literature. First, a model for the surface–atmosphere exchange of ammonia that includes the concentration at the external leaf surface is derived and validated. Second, a parameterization for the stomatal compensation point (expressed as Γ_s, the ratio of [NH₄⁺]/[H⁺] in the leaf apoplast) that accounts for the observed seasonal variation is derived from the measurements. The new, temperature-dependent Γ_s describes the observed seasonal behavior very well. It is noted, however, that senescence of plants and field management practices will also influence the seasonal variation of Γ_s on a shorter timescale. Finally, a relation that links Γ_s to the atmospheric pollution level of the location through the ‘long-term’ NH₃ concentration in the air is proposed.     

Modelling the solute transport under nonequilibrium conditions on the basis of mass transfer equations

A solute transport model that describes nonequilibrium adsorption in soil/groundwater systems by mass transfer equations for film and intraparticle diffusion is presented. The model is useful in cases where breakthrough curve spreading cannot be explained by dispersion only. To evaluate its validity, the model was applied to several data sets from column experiments. The validity was also proved by a comparison with an analytical solution for the limiting case of predominating dispersion. Furthermore, a sensitivity analysis was performed to illustrate the influence of different process and sorption parameters (pore water velocity, intraparticle mass transfer coefficient, isotherm nonlinearity) on the shape of the calculated breakthrough curves. The application of the proposed model is discussed in comparison to the widely used dispersed flow/local equilibrium model, and a relationship between both models, which is based on a lumped parameter approach, is shown.