The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

Relationships between aqueous solubility and octanol-water partition coefficients

The physical chemical equations relating solubility to octanol water partition coefficient are presented and used to develop a new correlation between these quantities which includes a melting point (fugacity ratio) correction. The correlation is satisfactory for 45 organic compounds but it is not applicable to organic acids. When applied to very high molecular weight (> 290) compounds the correlation is less satisfactory; either it is believed because the data are inaccurate or because the tendency for these compounds to partition into organic phases is less than expected. This may have profound environmental implications.     

Environmental Persistence of Chemicals

- DOI: http://dx.doi.org/10.1065/espr2006.01.008 Background The hazard criterion of persistence as it applies to chemicals in the environment is reviewed and discussed. This quantity can not be measured directly in the environment, thus it must be estimated using models that synthesise information on chemical half-lives and partitioning properties, the nature of the environment and how the chemical is released into the environment. Main Features It is suggested that the preferred criterion is the average residence time of the chemical in the environment, i.e. conceptually the sum of the life-times of all molecules (attributable only to losses by degrading reactions) divided by the number of molecules. If all chemical fate processes are first order, this persistence is independent of the quantity of chemical introduced and whether introduction is steady- or unsteady-state in nature. It is shown that in a multimedia environment persistence is affected not only by degradation kinetics, but also by mode-of-entry and partitioning. For screening level purposes a Level II equilibrium model may be adequate but a Level III model is generally preferable for estimating the average persistence. If a distribution of persistences is required a dynamic Level IV model must be used. Discussion The implications for regulating chemicals on the basis of persistence are discussed. Conclusion It is concluded that the preferred strategy is to use Level II, III, and IV models and that the use of only degradation kinetics or media-specific half-lives can be misleading and uneconomical.     

BETR-World: a geographically explicit model of chemical fate: application to transport of alpha-HCH to the Arctic

The Berkeley-Trent (BETR)-World model, a 25 compartment, geographically explicit fugacity-based model is described and applied to evaluate the transport of chemicals from temperate source regions to receptor regions (such as the Arctic). The model was parameterized using GIS and an array of digital data on weather, oceans, freshwater, vegetation and geo-political boundaries. This version of the BETR model framework includes modification of atmospheric degradation rates by seasonally variable hydroxyl radical concentrations and temperature. Degradation rates in all other compartments vary with seasonally changing temperature. Deposition to the deep ocean has been included as a loss mechanism. A case study was undertaken for alpha-HCH. Dynamic emission scenarios were estimated for each of the 25 regions. Predicted environmental concentrations showed good agreement with measured values for the northern regions in air, and fresh and oceanic water and with the results from a previous model of global chemical fate. Potential for long-range transport and deposition to the Arctic region was assessed using a Transfer Efficiency combined with estimated emissions. European regions and the Orient including China have a high potential to contribute alpha-HCH contamination in the Arctic due to high rates of emission in these regions despite low Transfer Efficiencies. Sensitivity analyses reveal that the performance and reliability of the model is strongly influenced by parameters controlling degradation rates.     

Study of oil-water partitioning of a chemical dispersant using an acute bioassay with marine crustaceans

The toxicity of seawater dispersions of a chemical dispersant to two marine crustaceans was investigated in the presence and absence of various quantities of a non-toxic mineral oil. From the results and a physical-chemical partitioning analysis, a limiting value of the oil-water partition coefficient of the toxic compounds is deduced suggesting that essentially all of the toxic compounds in the dispersant will partition into solution in water following dispersant application to an oil spill. This conclusion simplifies interpretation and prediction of the toxic effects of a dispersed oil spill.The combined bioassay-partitioning procedure may have applications to the study of the toxicity of other complex mixtures such as industrial effluents.     

Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.     

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.     

Water and sediment quality of dry season pools in a dryland river system: the upper Leichhardt River, Queensland, Australia

This article presents the geochemical characteristics and physicochemical properties of water and sediment from twelve semi-permanent, dryland pools in the upper Leichhardt River catchment, north-west Queensland, Australia. The pools were examined to better understand the quality of sediments and temporary waters in a dryland system with a well-established metal contamination problem. Water and sediment sampling was conducted at the beginning of the hydroperiod in May and September 2007. Water samples were analyzed for major solute compositions (Ca, Na, K, Mg, Cl, SO(4), HCO(3)) and water-soluble (operationally defined as the <0.45 μm fraction) metals (Cd, Cu, Pb, Zn). Sediment samples were analyzed for total extractable and bioaccessible metals (As, Cd, Cu, Pb, Zn), elemental composition and grain morphology. At the time of sampling a number of pools contained water and sediment with elevated concentrations, compared to Australian regulatory guidelines, of Cu (maximum: water 28 μg L(-1); sediment 770 mg kg(-1)), Pb (maximum: water 3.4 μg L(-1); sediment 630 mg kg(-1)) and Zn (maximum: water 150 μg L(-1); sediment 780 mg kg(-1)). Concentrations of Cd and As in pools were relatively low and generally within Australian regulatory guideline values. Localized factors, such as the interaction of waters with anthropogenic contaminants from modern and historic mine wastes (i.e. residual smelter and slag materials), exert influence on the quality of pool waters. Although the pools of the upper Leichhardt River catchment are contaminated, they do not appear to be the primary repository of water and sediment associated metals when compared to materials in the remainder channel and floodplain. Nevertheless, a precautionary approach should be adopted to mitigating human exposure to contaminated environments, which might include the installation of appropriate warning signs by local health and environmental authorities.