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.     

Models of multi-media partitioning of multi-species chemicals: The fugacity/aquivalence approach

The fugacity or aquivalence approach to environmental modelling is extended to treat chemicals which may be present as several inter-converting species in a multi-media environment. Species-specific and total Z values are defined expressing the capacity of each phase for each species of chemical. Similarly, species-specific and total D values are defined to quantify transport and transformation rates. Fugacity or aquivalence is used as the criterion for partitioning behaviour or physical equilibrium. By defining species proportions on an aquivalence or fugacity fraction basis, the equations for multiple species can be consolidated into a single “pseudo single-component” mass balance equation. Steady-state multi-species, multi-compartment mass balance models can be assembled for such systems and solved in various ways to give mass balances and distributions for all species amounts, concentrations, fluxes and species conversion rates.

Examples are presented for a hypothetical substance present as three species in a system under equilibrium and non-equilibrium, steady-state conditions.     

A multimedia environmental model of chemical distribution: fate, transport, and uncertainty analysis

This paper presented a framework for analysis of chemical concentration in the environment and evaluation of variance propagation within the model. This framework was illustrated through a case study of selected organic compounds of benzo[alpha]pyrene (BAP) and hexachlorobenzene (HCB) in the Great Lakes region. A multimedia environmental fate model was applied to perform stochastic simulations of chemical concentrations in various media. Both uncertainty in chemical properties and variability in hydrometeorological parameters were included in the Monte Carlo simulation, resulting in a distribution of concentrations in each medium. Parameters of compartmental dimensions, densities, emissions, and background concentrations were assumed to be constant in this study. The predicted concentrations in air, surface water and sediment were compared to reported data for validation purpose. Based on rank correlations, a sensitivity analysis was conducted to determine the influence of individual input parameters on the output variance for concentration in each environmental medium and for the basin-wide total mass inventory. Results of model validation indicated that the model predictions were in reasonable agreement with spatial distribution patterns, among the five lake basins, of reported data in the literature. For the chemical and environmental parameters given in this study, parameters associated to air-ground partitioning (such as moisture in surface soil, vapor pressure, and deposition velocity) and chemical distribution in soil solid (such as organic carbon partition coefficient and organic carbon content in root-zone soil) were targeted to reduce the uncertainty in basin-wide mass inventory. This results of sensitivity analysis in this study also indicated that the model sensitivity to an input parameter might be affected by the magnitudes of input parameters defined by the parameter settings in the simulation scenario. Therefore, uncertainty and sensitivity analyses for environmental fate models was suggested to be conducted after the model output was validated based on an appropriate input parameter settings.     

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.     

Assessment of the environmental fate of linear alkylbenzenesulphonates

Fugacity models, as developed previously, are applied to the chemical linear alkylbenzenesulphonate (LAS) to predict its ultimate fate in the environment. The behaviour of LAS is illustrated using unit worlds or evaluative environments at three successive levels of complexity (Levels I, II, and III). LAS is shown to have a short environmental life of two days attributable to rapid biodegradation in water. Reported concentration data for LAS in Rapid Creek, South Dakota, downstream from a municipal sewage treatment plant, are compared to expected concentrations as generated by the QWASI (Quantitative Water Air Sediment Interaction) fugacity model; the model being based solely on the physical, chemical, reactivity and transport properties of LAS and the emission rate of the chemical into the river. The data are found to fit the model when a sediment-water mass transfer coefficient of 7.80 × 10⁻³ m/h and an effective sediment bed depth of 3 mm are used. The generally satisfying agreement between environmental observations and the QWASI fugacity models lends credibility to the use of evaluative models.     

The predicted environmental distribution of some PCB replacements

Physical and chemical properties which control the environmental distribution of five PCB replacement chemicals (di-isopropylnaphthalenes, phenylxylylethanes, butylated monochlorodiphenyl ethers, isopropylbiphenyls and tetrachloroethylene) have been obtained. These data are used to predict the distribution of these chemicals, a pentachlorobiphenyl and $\text{p,p′}$-DDE in an evaluative environment using a fugacity approach. This simple model gives no information about reactivity or persistence. More complex fugacity models are used to compare these additional features of a di-isopropylnaphthalene PCB replacement with those of a PCB.     

An assessment of the environmental fate and exposure of benzene and the chlorobenzenes in Canada

Systematic modelling of the fate of benzene and the chlorobenzenes is presented which follows a four-stage process of chemical classification, quantifying discharge rates and environmental concentrations, evaluative assessment of fate and regional mass balance modelling has been carried out for the southern Ontario region. The EQC model was applied to determine the principal transport and transformation processes experienced by this group of chemicals, which vary considerably in volatility and hydrophobicity. Observed environmental concentrations are in satisfactory agreement with the predictions of the steady state Level III ChemCAN model of chemical fate. A multiple pathway human exposure model which estimates intake of contaminants by residents of southern Ontario has been developed and applied to these chemicals. A novel method of deducing maximum tolerable environmental concentrations is presented. Results suggest that benzene and 1,4-dichlorobenzene are present in the environment at levels sufficient to cause exposures near allowable daily intake (ADI) levels for the general population, but the other substances are present at levels which result in exposure ranging from 1/10 to 1/1000 of the ADI.     

水环境数学模型的研究进展

在作者多年研究工作和查阅大量文献资料的基础上,本文综述了环境数学模型国内外的研究现状、发展历史及未来趋势。重点介绍了这方面研究的最新进展。该文还介绍了本领域所涉及的理论和实际应用问题,提出了今后值得进行研究的若干前沿课题,给出了60余篇关于水环境数学模型研究的主要参考文献目录。     

Evaluating the environmental fate of atrazine in France

Atrazine is used in large quantities in U.S. and European countries as a weed-control agent. As a result, numerous data on its environmental fate and hazards have been published. Analysis of the literature shows that this herbicide can be found with appreciable concentrations in groundwaters, rivers, lakes, and estuaries. This contamination principally results from leaching and runoff processes. Atrazine can also pollute fog and rain due to its release into the atmosphere through spray applications. This large amount of information constitutes a very attractive basis for assessing the simulation performances of environmental fate models. In this context, CHEMFRANCE, a regional fugacity model level III which calculates the environmental distribution of organic chemicals in twelve defined regions of France has been used to estimate the environmental fate of atrazine. The calculated values are comparable with field and laboratory results. Therefore, CHEMFRANCE can be considered as a useful tool for simulating the environmental fate of this agrochemical.     

A carbon budget of a small humic lake: an example of the importance of lakes for organic matter cycling in boreal catchments

Lakes play an important role in the cycling of organic matter in the boreal landscape, due to the frequently high extent of bacterial respiration and the efficient burial of organic carbon in sediments. Based on a mass balance approach, we calculated a carbon budget for a small humic Swedish lake in the vicinity of a potential final repository for radioactive waste in Sweden, in order to assess its potential impact on the environmental fate of radionuclides associated with organic matter. We found that the lake is a net heterotrophic ecosystem, subsidized by organic carbon inputs from the catchment and from emergent macrophyte production. The largest sink of organic carbon is respiration by aquatic bacteria and subsequent emission of carbon.dioxide to the atmosphere. Although the annual burial of organic carbon in the sediment is a comparatively small sink, it results in the build-up of the largest carbon pool in the lake. Hence, lakes may simultaneously disperse and accumulate organic-associated radionuclides leaking from a final repository.     

Geographical scenario uncertainty in generic fate and exposure factors of toxic pollutants for life-cycle impact assessment

In environmental life-cycle assessments (LCA), fate and exposure factors account for the general fate and exposure properties of chemicals under generic environmental conditions by means of 'evaluative' multi-media fate and exposure box models. To assess the effect of using different generic environmental conditions, fate and exposure factors of chemicals emitted under typical conditions of (1).Western Europe, (2). Australia and (3). the United States of America were compared with the multi-media fate and exposure box model USES-LCA. Comparing the results of the three evaluative environments, it was found that the uncertainty in fate and exposure factors for ecosystems and humans due to choice of an evaluative environment, as represented by the ratio of the 97.5th and 50th percentile, is between a factor 2 and 10. Particularly, fate and exposure factors of emissions causing effects in fresh water ecosystems and effects on human health have relatively high uncertainty. This uncertainty is mainly caused by the continental difference in the average soil erosion rate, the dimensions of the fresh water and agricultural soil compartment, and the fraction of drinking water coming from ground water.     

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.     

Mass balance model of source apportionment, transport and fate of PAHs in Lac Saint Louis, Quebec

A mass balance model has been developed and calibrated to describe the sources, transport and fate of seven polycyclic aromatic hydrocarbons (PAHs; anthracene, benzo(a)pyrene, benzo(b)fluoranthene, chrysene, fluoranthene, phenanthrene, and pyrene) in the water and sediments of, and atmosphere over Lac Saint Louis, Quebec. The model uses specified input rates from background advective flows and emissions from the Alcan aluminum smelting facility at Beauharnois to deduce atmospheric concentrations and rates of wet and dry deposition to the three segment lake. Concentrations in water and sediment as well as relevant mass fluxes and residence times are computed and compared satisfactorily with monitoring data for five of the seven PAHs. Underestimation of concentrations for anthracene and phenanthrene is attributed to unquantified additional sources. The sources of the PAH burden in the lake are apportioned, and the implications of these results are discussed including likely response times to changes in loadings. It is suggested that this mass balance approach is more widely applicable to situations in which water bodies are impacted by a variety of contaminant sources.     

Mercury cycling and species mass balances in four North American lakes

A mass balance model for mercury based on the fugacity concept is applied to Lake Superior, Lake Michigan, Onondaga Lake and Little Rock Lake to evaluate model performance, analyze cycling of three mercury species groups (elemental, divalent and methyl mercury), and identify important processes that determine the source-to-concentration relationship of the three mercury species groups in these lakes. This model application to four disparate ecosystems is an extension of previous applications of fugacity-based models describing mercury cycling. The model performs satisfactorily following site-specific parameterization, and provides an estimate of minimum rates of species interconversion that compare well with literature. Volatilization and sediment burial are the main processes removing mercury from the lakes, and uncertainty analyses indicate that air-water exchange of elemental mercury and water-sediment exchange of divalent mercury attached to particles are influential in governing mercury concentrations in water. Any new model application or field campaign to quantify mercury cycling in a lake should consider these processes as important.     

Mass balance modelling of contaminants in river basins: a flexible matrix approach

A novel and flexible approach is described for simulating the behaviour of chemicals in river basins. A number (n) of river reaches are defined and their connectivity is described by entries in an n x n matrix. Changes in segmentation can be readily accommodated by altering the matrix entries, without the need for model revision. Two models are described. The simpler QMX-R model only considers advection and an overall loss due to the combined processes of volatilization, net transfer to sediment and degradation. The rate constant for the overall loss is derived from fugacity calculations for a single segment system. The more rigorous QMX-F model performs fugacity calculations for each segment and explicitly includes the processes of advection, evaporation, water-sediment exchange and degradation in both water and sediment. In this way chemical exposure in all compartments (including equilibrium concentrations in biota) can be estimated. Both models are designed to serve as intermediate-complexity exposure assessment tools for river basins with relatively low data requirements. By considering the spatially explicit nature of emission sources and the changes in concentration which occur with transport in the channel system, the approach offers significant advantages over simple one-segment simulations while being more readily applicable than more sophisticated, highly segmented, GIS-based models.