Development of a black carbon-inclusive multi-media model: application for PAHs in Stockholm

A multi-media model was developed for predicting the fate of organic chemicals in the Greater Stockholm Area, Sweden, and applied to selected polycyclic aromatic hydrocarbons (PAHs). Although urban models have been previously developed, this model is novel in that it includes sorption to pyrogenically-derived particles, commonly termed "black carbon" (BC), within the model structure. To examine the influence of BC sorption on environmental fate of PAHs, two versions of the model were generated and run: one in which sorption to BC was included and one in which BC sorption was excluded. The inclusion of BC sorption did not cause any significant variations to air levels, but it did cause an average 20-30% increase in sediment concentrations related to increased sediment solids partitioning. The model also predicted reduced advective losses out of the model domain, as well as chemical potential to diffuse from sediments, whilst total chemical inventory increased. In all cases, the lighter PAHs were more affected by BC inclusion than their heavier counterparts. We advocate the addition of sorption to BC in future multi-media fate and exposure models, which as well as influencing fate will also alter (lower) chemical availability and, thus, wildlife exposure to hydrophobic chemicals. A quantification of the latter was derived with the help of the soot-inclusive model version, which estimated a lowering of dissolved water concentrations between five and >200 times for the different PAHs of this study.     

Calculation of environmental concentration and comparison of output for existing chemicals using regional multimedia modeling

The environmental fate of 40 existing chemicals is discussed using the EUSES multimedia distribution and risk assessment model with site-specific parameter setting in an urban area of Japan including a highly industrial region. There has been a strong need to assess the environmental fate of a huge number of existing chemicals. Data on the emission amounts of chemicals are essential for such prediction, and PRTR surveys may yield this data. The study delivered the following results: (1) Volatile compounds with large amounts of emission showed higher predicted concentrations in air, and the concentrations of several compounds agreed well with averaged monitoring data within an order of magnitude. (2) A close relationship was found between the concentration of water and that of sediment, suggesting that the fate of chemicals in sediment essentially depended on the water environment. (3) A group of volatile solvents had high mass distribution ratio to air. Some compounds having high solubility in water were also included in that group due to the high ratio of air emission. Highly hydrophobic compounds with logK(OW) larger than 6.0 showed a high distribution ratio to soil and sediment. (4) Volatile compounds were mostly taken through air. The exposure through fish is a dominant pathway for highly hydrophobic compounds. (5) Exposure ratio could be gathered from physicochemical properties. The exposure from fish intake was roughly estimated by logK(OW), whereas exposure from air and water intake was difficult to estimate simply by vapor pressure and solubility in water, respectively.     

Effects of input uncertainty and variability on the modelled environmental fate of organic pollutants under global climate change scenarios

Global climate change (GCC) is expected to influence the fate, exposure and risks of organic pollutants to wildlife and humans. Multimedia chemical fate models have been previously applied to estimate how GCC affects pollutant concentrations in the environment and biota, but previous studies have not addressed how uncertainty and variability of model inputs affect model predictions. Here, we assess the influence of climate variability and chemical property uncertainty on future projections of environmental fate of six polychlorinated biphenyl congeners under different GCC scenarios using a spreadsheet version of the ChemCAN model and the Crystal Ball® software. Regardless of emission mode, results demonstrate: (i) uncertainty in degradation half-lives dominates the variance of modelled absolute levels of PCB congeners under GCC scenarios; (ii) when the ratios of predictions under GCC to predictions under present day climate are modelled, climate variability dominates the variance of modelled ratios; and (iii) the ratios also indicate a maximum of about a factor of 2 change in the long-term average environmental concentrations due to GCC that is forecasted between present conditions and the period between 2080 and 2099. We conclude that chemical property uncertainty does not preclude assessing relative changes in a GCC scenario compared to a present-day scenario if variance in model outputs due to chemical properties and degradation half-lives can be assumed to cancel out in the two scenarios.     

Evaluation and comparison of multimedia mass balance models of chemical fate: application of EUSES and ChemCAN to 68 chemicals in Japan

The European Union System for Evaluation of Substances (EUSES) and the ChemCAN chemical fate model are applied to describe the fate of 68 chemicals on two spatial scales in Japan. Emission information on the chemicals has been obtained from Japan's Pollutant Release and Transfer Registry and available monitoring data gathered from government reports. Environmental concentrations calculated by the two models for the four primary environmental media of air, water, soil and sediment agree within a factor of 3 for over 70% of the data, and within a factor of 10 for over 87% of the data. Reasons for certain large discrepancies are discussed. Concentrations calculated by the models are generally consistent with the lower range of concentrations that are observed in the environment. Agreement between modeled and observed concentrations is considerably improved by including an estimate of the advective input of chemicals in air from outside Japan. The agreement between the EUSES and ChemCAN models suggests that results of individual chemical assessments are not likely to be significantly affected by the choice of chemical fate model. Primary sources of discrepancy between modeled and observed concentrations are believed to be uncertainties in emission rates, degradation half-lives, and the lack of data on advective inflow of contaminants in air.     

Model selection and evaluation for risk assessment of dioxin-contaminated sites

The general European population has a total intake of dioxins and dioxin-like chemicals near the limit recommended by the European Union, making additional exposure above background levels undesirable. For populations living near dioxin-contaminated sites, additional exposure may occur by intake of locally produced food, inhalation of particles, dermal contact with soils, or other exposure pathways. Risk assessment tools are required to estimate risks associated with contaminated sites and to set priorities for site remediation. Here, we review several multimedia models that can be applied as tools to support risk assessment. We then present a strategy to select, apply, evaluate, and adapt a model to address a specific situation. The case study we consider is a risk assessment of generic background dioxin exposure in Sweden, and we compare the predictions with environmental observations and exposure data from Sweden. Arguments are presented for selecting the CalTOX model for this case study. We demonstrate the application, evaluation, and adaptation of the model and discuss the requirements for extending the analysis to conduct risk assessment for subpopulations living near dioxin-contaminated sites.     

Trends of TCDD and related compounds in the Great Lakes: The Lake Ontario ecosystem

The Laurentian Great Lakes represent 20 percent of the surface fresh water of the world. They are unique because of their long flushing times (in excess of 175 years for Lake Superior), their relatively short mixing times and their consequent propensity to accumulate persistent chemicals and respond very slowly to decreased chemical loadings. Lake Ontario, as the last lake in the system, receives the drainage from the other four Great Lakes in addition to significant chemical contributions from within its drainage basin particularly from its main tributary, the Niagara River.

This paper evaluates environmental levels of TCOD and related compounds within the Lake Ontario ecosystem by considering temporal trends, the application of mass loading principles for large lake ecosystems and the examination of a holistic ecosystem perspective on exposure routes.     

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.     

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.     

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.     

An updated state of the science EQC model for evaluating chemical fate in the environment: application to D5 (decamethylcyclopentasiloxane)

The EQuilibrium Criterion (EQC) model developed and published in 1996 has been widely used for screening level evaluations of the multimedia, fugacity-based environmental fate of organic chemicals for educational, industrial, and regulatory purposes. Advances in the science of chemical partitioning and reactivity and the need for more rigorous regulatory evaluations have resulted in a need to update the model. The New EQC model is described which includes an improved treatment of input partitioning and reactivity data, temperature dependence and an easier sensitivity and uncertainty analysis but uses the same multi-level approach, equations and environmental parameters as in the original version. A narrative output is also produced. The New EQC model, which uses a Microsoft Excel platform, is described and applied in detail to decamethylcyclopentasiloxane (D5; CAS No. 541-02-6). The implications of these results for the more detailed exposure and risk assessment of D5 are discussed. The need for rigorous evaluation and documentation of the input parameters is outlined.     

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.     

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.     

Development of continental scale multimedia contaminant fate models: integrating GIS

The incentives and approaches for modelling chemical fate at a continental scale are discussed and reviewed. It is suggested that a multi-media model consisting of some 20-30 regions, each of which contains typically seven environmental compartments represents a reasonable compromise between the issues of the need for detailed resolution, avoidance of excessive data demands and inherent complexity and transparency. Strategies adopted in compiling the Berkley-Trent (BETR) model for North America are discussed and used to illustrate the issues of selecting appropriate number and nature of segments, treatment of air and water flows and the acquisition of environmental data. It is suggested that GIS software can play a valuable role in gathering and processing such data and in the display and interpretation of the results of the model assessment. The BETR model will be a useful tool for describing the nature of persistence and long-range transport of chemicals of concern in the North American environment.     

Scientific activities of Euro Chlor in monitoring and assessing naturally and man-made organohalogens

In this paper a review of the scientific activities and research programmes carried out by Euro Chlor, the European Federation of chlor-alkali producers is presented according to two main axes: marine risk assessments with statistical analysis of monitoring data, temporal trends of emission levels and environmental concentrations. The methodology applied in each field is briefly presented and then illustrated by several practical examples. As a large part of the uncertainties in assessing the risk of a chemical to a given species or ecosystem often comes from the difficulty in evaluating the exposure level, Euro Chlor has chosen to use a monitoring approach, the exposure level being estimated from a statistical analysis of measured concentrations levels in water and sediment from rivers, estuaries and coastal areas. As the modelling approach often used by the authorities to estimate the predicted environmental concentration value is starting from roughly estimated emission levels, Euro Chlor collated emissions data from about 80 production plants in order to reduce the uncertainty associated with the default values introduced in the modelling approach.A brief review of the European emission levels for chlorinated organic substances is given as well as the temporal trends of both emission and environmental levels. A methodology to quantify the trends in measured concentrations at local and regional scales is briefly described. The observed decreasing trends demonstrate the continuous progress made by the Euro Chlor member companies in protecting the environment.Finally, the problems linked to the simultaneous presence in the environment of naturally and man-made chlorinated substances are briefly reviewed. To stimulate further research in the field, two key questions are raised which have not yet found a satisfactory answer: how to quantify natural background levels and how to quantify global persistence in the environment?     

Exposure patterns of UV filters, fragrances, parabens, phthalates, organochlor pesticides, PBDEs, and PCBs in human milk: correlation of UV filters with use of cosmetics

In order to assess potential risks of exposure to environmental chemicals, more information on concomitant exposure to different chemicals is needed. We present data on chemicals in human milk of a cohort study (2004, 2005, 2006) of 54 mother/child pairs, where for the first time, cosmetic UV filters, synthetic musks, parabens and phthalate metabolites were analyzed in the same sample along with persistent organochlor pollutants (POPs), i.e., organochlor pesticides and metabolites, polybrominated diphenylethers and polychlorinated biphenyls (PCBs). The two groups of chemicals exhibited different exposure patterns. Six out of seven PCB congeners and a majority of pesticides were present in all milk samples, with significant correlations between certain PCB congener and pesticide levels, whereas the cosmetic-derived compounds, UV filters, parabens and synthetic musks, exhibited a more variable exposure pattern with inter-individual differences. UV filters were present in 85.2% of milk samples, in the range of PCB levels. Comparison with a questionnaire revealed a significant correlation between use of products containing UV filters and their presence in milk for two frequently used and detected UV filters, 4-methylbenzylidene camphor and octocrylene, and for the whole group of UV filters. Concentrations of PCBs and organochlor pesticides were within ranges seen in Western and Southern European countries. For several POPs, mean and/or maximum daily intake calculated from individual concentrations was above recent US EPA reference dose values. Our data emphasize the need for analyses of complex mixtures to obtain more information on inter-individual and temporal variability of human exposure to different types of chemicals.