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.     

Spatial variability in compartmental fate modelling

A new approach is presented which is designed to address the spatial heterogeneity of the environment in compartmental mass balance models of chemical fate in the environment. It rests on the assumption of chemical equilibration within one phase despite prevailing environmental heterogeneity. Composite D- and Z-values are derived from sub-unit specific environmental parameters and are used to solve mass balance equations which can be adopted essentially unchanged from existing compartmental fugacity models. With the resulting common fugacity value for each compartment, sub-unit specific concentrations and process rates can be calculated. The approach is illustrated using the QWASI lake model to calculate the fate of hexachlorobenzene in a hypothetical lake sub-divided in four distinct sub-units. The approach allows the subdivision of each compartment in a large number of sub-units with distinct environmental characteristics without substantially increasing model complexity. This is a necessary condition for linking fugacity models to geographical information systems.     

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.     

Using fugacity to predict volatile emissions from layered materials with a clay/polymer diffusion barrier

Structural insulated panels (SIPs) have significant environmental and energy advantages. However, the tight structure that results may cause degraded indoor air quality and the potential release of volatile organic compounds (VOCs) from these layered materials must be considered. A physically based model for predicting VOC emissions from multi-layer materials is described. Fugacity is used to eliminate the concentration discontinuities at the interface between layers. This avoids an obstacle associated with numerically simulating mass transfer in composite materials. The numerical model is verified for a double-layer system by comparing predicted concentrations to those obtained with a previously published analytical model. In addition, hexanal emissions from multi-layer SIPs are simulated to demonstrate the usefulness of the fugacity approach. Finally, the multi-layer model is used to investigate the impact that clay/polyurethane nanocomposite diffusion barriers can have on VOC emissions. Indoor gas-phase concentrations can be greatly reduced with a barrier layer on the surface, thereby minimizing the environmental impact of SIPs.     

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.     

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.     

Modelling of the fate of selected endocrine disruptors in a municipal wastewater treatment plant in South East Queensland, Australia

The aim of this study was to develop a fugacity-based analysis of the fate of selected industrial compounds (alkylphenols and phthalates) with endocrine disrupting properties in a conventional activated sludge wastewater treatment plant (WWTP A) in South East Queensland, Australia. Using mass balance principles, a fugacity model was developed for correlating and predicting the steady-state-phase concentrations, the process stream fluxes, and the fate of four phthalates and four alkylphenols in WWTP A. Input data are the compound's physicochemical properties, measured concentrations and the plant's operating design and parameters. The relative amounts of chemicals that are likely to be volatilized, sorbed to sludge, biotransformed, and discharge in the effluent water was determined. Since it was difficult to predict biotransformation, measured concentrations were used to calibrate the model in terms of biotransformation rate constant. Results obtained by applying the model for the eight compounds showed <40% differences between most of the estimated and measured data from WWTP A. All eight compounds that were modelled in this study had high removal efficacy from WWTP A. Apart from benzyl butyl phthalate and bisphenol A, the majority is removed via biotransformation followed by a lesser proportion removed with the primary sludge. Fugacity analysis provides useful insight into compound fate in a WWTP and with further calibration and validation the model should be useful for correlative and predictive purposes.     

Strategies for including vegetation compartments in multimedia models

The incentives for including vegetation compartments in multimedia Level I, II and III fugacity calculations are discussed and equations and parameters for undertaking the calculations suggested. Model outputs with and without vegetation compartments are compared for 12 non-ionic organic chemicals with a wide variety of physical-chemical properties. Inclusion of vegetation compartments is shown to have a significant effect on two classes of chemicals: (1) those that are taken up by atmospheric deposition and (2) those that are taken up by transpiration through the plant roots. It is suggested that uptake from the atmosphere is important for chemicals with logK(OA) greater than 6 and a logK(AW) of greater than -6. Plant uptake by transpiration is important for chemicals with logK(OW) less than 2.5 and a logK(AW) of less than -1. At logK(OA) > 9 atmospheric uptake is dominated by particle-bound deposition and the importance of partitioning to vegetation is largely dependent on the relative magnitude of the particle deposition velocities to soil and vegetation. These property ranges can be used to determine if a chemical will significantly partition to vegetation. If the chemical falls outside the property ranges of the two classes it will probably be unnecessary to include vegetation in models for assessing environmental fate. The amount of chemical predicted to partition to vegetation compartments in the model is shown to be highly sensitive to certain model assumptions. Further experimental research is recommended to obtain more reliable equations describing equilibrium partitioning and uptake/depuration kinetics.     

Progestagens for human use, exposure and hazard assessment for the aquatic environment

Little information is available on the environmental occurrence and ecotoxicological effects of pharmaceutical gestagens released in the aquatic environment. Since eighteen different gestagens were found to be used in France, preliminary exposure and hazard assessment were done. Predicted environmental concentrations (PECs) suggest that if parent gestagens are expected to be found in the ng l⁻¹ range, some active metabolites could be present at higher concentrations, although limited data on metabolism and environmental fate limit the relevance of PECs. The biological effects are not expected to be restricted to progestagenic activity. Both anti-androgenic activity (mainly for cyproterone acetate, chlormadinone acetate and their metabolites) and estrogenic activity (mainly for reduced metabolites of levonorgestrel and norethisterone) should also occur. All these molecules are likely to have a cumulative effect among themselves or with other xenoestrogens. Studies on occurrence, toxicity and degradation time are therefore needed for several of these compounds.     

Estimation of PCDD/F distribution and fluxes in the Venice Lagoon,Italy: combining measurement and modelling approaches

The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment-water-air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air-water-sediment) appears to be occurring for the heaviest (hepta- and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment re-suspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.     

Environmental impact assessment (EIA): Equilibrium fugacity calculations and worst case approach

A mathematical model UNITRISK which can be used for screening purposes and risk ranking was set up to calculate relative risk values of single chemicals and mixtures of chemicals towards single or mixtures of organisms via contamination of air, water, soil and food dose. The concentration values are calculated by applying the fugacity concept or a dose must be defined. The dose-response is assumed to be linear versus concentration and degradative processes are not considered which is the worst case. The assumption that equilibria between the environmental phases exist is simplifying the model and is also representing the worst case. A mean risk factor is calculated which is 1 if the endpoint values (LC₅₀, LD₅₀, ADI, etc.) are exceeded for the investigated organisms and man.     

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.     

Human population intake fractions and environmental fate factors of toxic pollutants in life cycle impact assessment

The present paper outlines an update of the fate and exposure part of the fate, exposure and effects model USES-LCA. The new fate and exposure module of USES-LCA was applied to calculate human population intake fractions and fate factors of the freshwater, marine and terrestrial environment for 3393 substances, including neutral organics, dissociating organics and inorganics, emitted to 7 different emission compartments. The human population intake fraction is on average 10(-5)-10(-8) for organics and 10(-3)-10(-4) for inorganics, depending on the emission compartment considered. Chemical-specific human population intake fractions can be 1-2.7 orders of magnitude higher or lower compared to the typical estimates. For inorganics, the human population intake fractions highly depend on the assumption that exposure via food products can be modelled with constant bioconcentration factors. The environmental fate factor is on average 10(-11)-10(-18) days m(-3) for organics and 10(-10)-10(-12) days m(-3) for inorganics, depending on the receiving environment and the emission compartment considered. Chemical-specific environmental fate factors can be 1-8 orders of magnitude higher or lower compared to the typical estimates. The largest differences between the new and old version of USES-LCA are found for emissions to air and soil. This is caused by a significant change in the structure of the air and soil compartments in the new version of USES-LCA, i.e. the distinction between rural and urban air, including rain-no rain conditions and including soil depth dependent intermedia transport.     

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.     

Prediction of overall persistence and long-range transport potential with multimedia fate models: robustness and sensitivity of results

The hazard indicators persistence (P) and long-range transport potential (LRTP) are used in chemicals assessment to characterize chemicals with regard to the temporal and spatial extent of their environmental exposure. They are often calculated based on the results of multimedia fate models. The environmental and substance-specific input parameters of such models are subject to a range of methodological uncertainties and also influenced by natural variability. We employed probabilistic uncertainty analysis to quantify variance in P and LRTP predictions for chemicals with different partitioning and transport behavior. Variance found in the results is so large that it prevents a clear distinction between chemicals. Additionally, only small improvements are observed when evaluating the results relative to a benchmark chemical. This can be explained by the dominance of substance-specific parameters and the only small direct influence of environmental parameters on P and LRTP as model outcomes. The findings underline the importance of learning how environmental conditions cause variability in substance behavior for improved substance ranking and classification.