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.

Human toxicity potentials for life-cycle assessment and toxics release inventory risk screening.

The human toxicity potential (HTP), a calculated index that reflects the potential harm of a unit of chemical released into the environment, is based on both the inherent toxicity of a compound and its potential dose. It is used to weight emissions inventoried as part of a life-cycle assessment (LCA) or in the toxics release inventory (TRI) and to aggregate emissions in terms of a reference compound. Total emissions can be evaluated in terms of benzene equivalence (carcinogens) and toluene equivalents (noncarcinogens). The potential dose is calculated using a generic fate and exposure model, CalTOX, which determines the distribution of a chemical in a model environment and accounts for a number of exposure routes, including inhalation, ingestion of produce, fish, and meat, and dermal contact with water and soil. Toxicity is represented by the cancer potency q1* for carcinogens and the safe dose (RfD, RfC) for noncarcinogens. This article presents cancer and noncancer HTP values for air and surface-water emissions of 330 compounds. This list covers 258 chemicals listed in U.S. Environmental Protection Agency TRI, or 79 weight-% of the TRI releases to air reported in 1997.

Pollutant-specific scale of multimedia models and its implications for the potential dose.

The spatial range is a generic indicator for how far pollutants are likely to travel. It also indicates the appropriate, pollutant-specific area of a multimedia model, which is the square of the spatial range. Formulations of the spatial range can be based on advective or dispersive transport. They differ in whether they take the extent and shape of the earth's surface into account. We suggest the common element of the different approaches is that all account for the persistence and mobility of pollutants. The mobility is the expected travel speed and depends on the partitioning. This paper extends the concept of a pollutant-specific model scale through the introduction of a characteristic atmospheric scale height. It is the height of the atmosphere that would be needed to contain all the pollutant if the entire atmosphere had ground-level concentration, taking into account deposition and degradation. We define the spatial range as the expected advection-driven travel distance of a pollutant molecule released to a specific compartment. This novel analytical formulation is more comprehensive but encompasses all previous advection-based proposals of a spatial range. We evaluate the spatial range and scale height of 288 chemicals for releases to air, surface water, and surface soil. We find a strong correlation between the spatial range for air releases and the scale height because both depend on persistence. We investigate the effect of the spatial scale on calculations of the human toxicity potential, a screening-level risk indicator based on toxicity and potential dose. The product of model area and potential dose is found to be the same for calculations using a fixed model area and those using the pollutant-specific spatial scale. The introduction of the scale height, however, can change the potential dose by more than 1 order of magnitude.

Intermittent rainfall in dynamic multimedia fate modeling.

It has been shown that steady-state multimedia models (level III fugacity models) lead to a substantial underestimate of air concentrations for chemicals with a low Henry's law constant (H < 0.01 Pa m-3 mol-1) because they assume a steady rain. This can lead to substantial errors, especially when multimedia models are used to estimate the spatial range or inhalation exposure. A dynamic model of pollutant fate is developed for conditions of intermittent rainfall to calculate the time profile of pollutant concentrations in different environmental compartments. The model utilizes a new, mathematically efficient approach to dynamic multimedia fate modeling that is based on the convolution of solutions to the initial conditions problem. For the first time, this approach is applied to intermittent conditions. The investigation indicates that the time-averaged pollutant concentrations under intermittent rainfall can be approximated by the appropriately weighted average of steady-state concentrations under conditions with and without rainfall.

A systematic uncertainty analysis of an evaluative fate and exposure model.

Multimedia fate and exposure models are widely used to regulate the release of toxic chemicals, to set cleanup standards for contaminated sites, and to evaluate emissions in life-cycle assessment. CalTOX, one of these models, is used to calculate the potential dose, an outcome that is combined with the toxicity of the chemical to determine the Human Toxicity Potential (HTP), used to aggregate and compare emissions. The comprehensive assessment of the uncertainty in the potential dose calculation in this article serves to provide the information necessary to evaluate the reliability of decisions based on the HTP A framework for uncertainty analysis in multimedia risk assessment is proposed and evaluated with four types of uncertainty. Parameter uncertainty is assessed through Monte Carlo analysis. The variability in landscape parameters is assessed through a comparison of potential dose calculations for different regions in the United States. Decision rule uncertainty is explored through a comparison of the HTP values under open and closed system boundaries. Model uncertainty is evaluated through two case studies, one using alternative formulations for calculating the plant concentration and the other testing the steady state assumption for wet deposition. This investigation shows that steady state conditions for the removal of chemicals from the atmosphere are not appropriate and result in an underestimate of the potential dose for 25% of the 336 chemicals evaluated.

Parameter uncertainty and variability in evaluative fate and exposure models.

The human toxicity potential, a weighting scheme used to evaluate toxic emissions for life cycle assessment and toxics release inventories, is based on potential dose calculations and toxicity factors. This paper evaluates the variance in potential dose calculations that can be attributed to the uncertainty in chemical-specific input parameters as well as the variability in exposure factors and landscape parameters. A knowledge of the uncertainty allows us to assess the robustness of a decision based on the toxicity potential; a knowledge of the sources of uncertainty allows us to focus our resources if we want to reduce the uncertainty. The potential dose of 236 chemicals was assessed. The chemicals were grouped by dominant exposure route, and a Monte Carlo analysis was conducted for one representative chemical in each group. The variance is typically one to two orders of magnitude. For comparison, the point estimates in potential dose for 236 chemicals span ten orders of magnitude. Most of the variance in the potential dose is due to chemical-specific input parameters, especially half-lives, although exposure factors such as fish intake and the source of drinking water can be important for chemicals whose dominant exposure is through indirect routes. Landscape characteristics are generally of minor importance.