Modelling of the long-term fate of pesticide residues in agricultural soils and their surface exchange with the atmosphere: Part II. Projected long-term fate of pesticide residues.

In the first part of this paper, a simple coupled dynamic soil-atmosphere model for studying the gaseous exchange of pesticide soil residues with the atmosphere is described and evaluated by comparing model results with published measurements of pesticide concentrations in air and soil. In Part II, the model is used to study the concentration profiles of pesticide residues in both undisturbed and annually tilled agricultural soils. Future trends are estimated for the measured air and soil concentrations of lindane and six highly persistent pesticides (toxaphene, p,p'-DDE, dieldrin, cis- and trans-chlordane and trans-nonachlor) over a twenty-year period due to volatilization and leaching into the deeper soil. Wet deposition and particle associated pesticide deposition (that increase soil residue concentrations) and soil erosion, degradation in the soil (other than for lindane) and run-off in precipitation are not considered in this study. Estimates of the rain deposition fluxes are reported that show that, other than for lindane, net volatilization fluxes greatly exceed rain deposition fluxes. The model shows that the persistent pesticides studied are highly immobile in soil and that loss of these highly persistent residues from the soil is by volatilization rather than leaching into the deeper soil. The soil residue levels of these six pesticides are currently sources of net volatilization to the atmosphere and will remain so for many years. The maximum rate of volatilization from the soil was simulated by setting the atmospheric background concentration to zero; these simulations show that the rates of volatilization will not be significantly increased since soil resistance rather than the atmospheric concentration controls the volatilization rates. Annual tilling of the soils increases the volatilization loss to the atmosphere. Nonetheless, the model predicts that, if only air-soil exchange is considered, more than 76% of current persistent pesticide residues will remain after 20 years in the top 7 cm of annually tilled soils. In contrast, lindane is relatively mobile in soil due to weaker binding to soil carbon and leaching of lindane into soil is the main removal route for current lindane residues near the soil surface. The model predicts that the soil is a sink for lindane in the atmosphere and that soil residue levels of lindane in the surface soil are determined by a balance between dry gaseous deposition to the soil from the atmosphere and leaching from the surface soil into the deeper soil where degradation is the dominant loss route. The model suggests that deposition of lindane from the atmosphere will sustain residues in the soil and, in the absence of fresh applications of lindane to the soil, eliminating lindane from the atmosphere would lead to a rapid decline of lindane residues in agricultural soils of the southern U.S.

Modelling of the long term fate of pesticide residues in agricultural soils and their surface exchange with the atmosphere: Part I. Model description and evaluation.

Sources of pesticides in the atmosphere can be releases of new material through current use, or emission/reemission from soil residues resulting from historical use. It is the latter aspect, soil residues, that is the focus of this study. This paper describes the application of a simple coupled atmosphere-soil pesticide exchange model that can assist in the interpretation of soil residue and air concentration measurements, and in the projection of short period field measurements to larger spatial scales and longer time periods. Only dry gaseous exchange (emission and deposition) between bare agricultural lands and the atmosphere is modelled. Wet deposition and particle associated deposition of pesticide are not included. Model results are compared with published co-located air and soil pesticide concentration measurements made on agricultural lands in the southern U.S. that have soil residues of lindane and the following six highly persistent pesticides: cis-, trans-chlordane, p,p'-DDE, dieldrin, trans-nonachlor and toxaphene. The study results show: (i) that measured air concentrations of toxaphene and p,p'-DDE above agricultural soils in the southern U.S. can be attributed to emissions due to local soil residues of these pesticides rather than to the regional background air concentrations; (ii) that both soil emissions and background air concentrations of dieldrin contribute significantly to the measured air concentrations; (iii) that measured air concentrations of cis- and trans-chlordane as well as trans-nonachlor and lindane are mainly due to the regional background with little contribution from local soil residues. An analysis of modelled summer day and night average soil-air exchange fluxes shows that toxaphene and p,p'-DDE soil residues are strong sources of emission to the atmosphere during both the day and night while the chlordanes, trans-nonachlor, lindane and dieldrin are deposited from the atmosphere to the soil during the night hours and emitted to the atmosphere during the day time. This result illustrates the model's capability to simulate the processes that lead to the 'grasshopper' effect whereby persistent pesticides in soils can be transported in the atmosphere by successive periods of emission and deposition to terrestrial surfaces. In the second part to this paper, the model is used to study the trends of pesticide residues and air concentrations over a twenty year period.

Modelling of mercury emissions from background soils.

Emissions of volatile mercury species from natural soils are believed to be a significant contributor to the atmospheric burden of mercury, but only order-of-magnitude estimates of emissions from these sources are available. The scaling-up of mercury flux measurements to regional or global scales is confounded by a limited understanding of the physical, chemical and biochemical processes that occur in the soil, a complex environmental matrix. This study is a first step toward the development of an air-surface exchange model for mercury (known as the mercury emission model (MEM)). The objective of the study is to model the partitioning and movement of inorganic Hg(II) and Hg(0) in open field soils, and to use MEM to interpret published data on mercury emissions to the atmosphere. MEM is a multi-layered, dynamic finite-element soil and atmospheric surface-layer model that simulates the exchange of heat, moisture and mercury between soils and the atmosphere. The model includes a simple formulation of the reduction of inorganic Hg(II) to Hg(0). Good agreement was found between the meteorological dependence of observed mercury emission fluxes, and hourly modelled fluxes, and it is concluded that MEM is able to simulate well the soil and atmospheric processes influencing the emission of Hg(0) to the atmosphere. The heretofore unexplained close correlation between soil temperature and mercury emission flux is fully modelled by MEM and is attributed to the temperature dependence of the Hg(0) Henry's Law coefficient and the control of the volumetric soil-air fraction on the diffusion of Hg(0) near the surface. The observed correlation between solar radiation intensity and mercury flux, appears in part to be due to the surface-energy balance between radiation, and sensible and latent heat fluxes which determines the soil temperature. The modelled results imply that empirical correlations that are based only on flux chamber data, may not extend to the open atmosphere for all weather scenarios.