Global fate of POPs: current and future research directions

For legacy and emerging persistent organic pollutants (POPs), surprisingly little is still known in quantitative terms about their global sources and emissions. Atmospheric transport has been identified as the key global dispersal mechanism for most legacy POPs. In contrast, transport by ocean currents may prove to be the main transport route for many polar, emerging POPs. This is linked to the POPs' intrinsic physico-chemical properties, as exemplified by the different fate of hexachlorocyclohexanes in the Arctic. Similarly, our current understanding of POPs' global transport and fate remains sketchy. The importance of organic carbon and global temperature differences have been accepted as key drivers of POPs' global distribution. However, future research will need to understand the various biogeochemical and geophysical cycles under anthropogenic pressures to be able to understand and predict the global fate of POPs accurately.     

Current issues and uncertainties in the measurement and modelling of air-vegetation exchange and within-plant processing of POPs

Air-vegetation exchange of POPs is an important process controlling the entry of POPs into terrestrial food chains, and may also have a significant effect on the global movement of these compounds. Many factors affect the air-vegetation transfer including: the physicochemical properties of the compounds of interest; environmental factors such as temperature, wind speed, humidity and light conditions; and plant characteristics such as functional type, leaf surface area, cuticular structure, and leaf longevity. The purpose of this review is to quantify the effects these differences might have on air/plant exchange of POPs, and to point out the major gaps in the knowledge of this subject that require further research. Uptake mechanisms are complicated, with the role of each factor in controlling partitioning, fate and behaviour process still not fully understood. Consequently, current models of air-vegetation exchange do not incorporate variability in these factors, with the exception of temperature. These models instead rely on using average values for a number of environmental factors (e.g. plant lipid content, surface area), ignoring the large variations in these values. The available models suggest that boundary layer conductance is of key importance in the uptake of POPs, although large uncertainties in the cuticular pathway prevents confirmation of this with any degree of certainty, and experimental data seems to show plant-side resistance to be important. Models are usually based on the assumption that POP uptake occurs through the lipophilic cuticle which covers aerial surfaces of plants. However, some authors have recently attached greater importance to the stomatal route of entry into the leaf for gas phase compounds. There is a need for greater mechanistic understanding of air-plant exchange and the 'scaling' of factors affecting it. The review also suggests a number of key variables that researchers should measure in their experiments to allow comparisons to be made between studies in order to improve our understanding of what causes any differences in measured data between sites.     

Chemical fate,latitudinal distribution and long-range transport of cyclic volatile methylsiloxanes in the global environment: A modeling assessment

Cyclic volatile methylsiloxanes (cVMS) such as octamethycyclotetrasiloxane (D4), decamethycyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are widely used as intermediates in the synthesis of high-molecular weight silicone polymers or as ingredients in the formulation of personal care products. The global environmental fate, latitudinal distribution, and long range transport of those cVMS were analyzed by two multimedia chemical fate models using the best available physicochemical properties as inputs and known persistent organic pollutants (POPs) and highly persistent volatile organic chemicals (“fliers”) as reference. The global transport and accumulation characteristics of cVMS differ from those of typical POPs in three significant ways. First, a large fraction of the released cVMS tends to become airborne and is removed from the global environment by degradation in air, whereas known POPs have a tendency to be distributed and persistent in all media. Secondly, although cVMS can travel a substantial distance in the atmosphere, they have little potential for deposition to surface media in remote regions. This contrasts with a deposition potential of known POPs that exceeds that of cVMS by 4–5 orders of magnitude. Thirdly, cVMS have short global residence times with the majority of the global mass removed within 3 months of the end of release. Global residence times of POPs on the other hand are in years. The persistent fliers resemble the cVMS with respect to the first two attributes, but their global residence times are more like those of the POPs.     

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.     

Contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs): Application to Southeastern France

A modeling approach has been developed to estimate the contribution of atmospheric emissions to the contamination of leaf vegetables by persistent organic pollutants (POPs). It combines an Eulerian chemical transport model for atmospheric processes (Polair3D/Polyphemus) with a fate and transport model for soil and vegetation (Ourson). These two models were specifically adapted for POPs. Results are presented for benzo(a)pyrene (BaP). As expected no accumulation of BaP in leaf vegetables appears during the growth period for each harvest over the 10 years simulated. For BaP and leaf vegetables, this contamination depends primarily on direct atmospheric deposition without chemical transfer from the soil to the plant. These modeling results are compared to available data.     

Testing common sediment-porewater distribution models for their ability to predict dissolved concentrations of POPs in The Grenlandsfjords, Norway

This study compares in situ observed porewater concentration of persistent organic pollutants (POPs) with predictions by common solid-water phase distribution models. Bottom sediments were sampled in The Grenlandsfjords, Norway, and the interstitial porewater was isolated from the solids by centrifugation and filtration. Both phases were analysed for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F), polycyclic aromatic hydrocarbons (PAH), and organic carbon. Based on the sediments' solid phase content of POPs, organic carbon, and soot carbon, we used the organic matter partitioning (OMP), and also the soot and organic matter partitioning (SOMP) model to estimate the porewater concentration. The OMP model gave better agreement to observations than the SOMP model for both PCDD/Fs and PAHs. The observed concentration of the PCDD/Fs in the sediments' porewater was much higher than in the deep water of the fjord. The logarithm of the organic matter-water partitioning coefficent (log K(OC)) in the porewater had positive linear regression on the logarithm of the octanol-water partitioning coefficient (log K(OW)). The slope of the regression model was indistinguishable from 1, except for the PAHs as a group which had a slope less than 1. This contrasts to previous studies undertaken in The Grenlandsfjords water column, where the slopes were higher than 1 for PCDD/Fs, and the K(OC) were much higher than the K(OW). One explanation may be that the influence of POPs adsorption to soots decrease because competitive sorption by other compounds in the sediment are higher than in the water column. This indicates that the sorption isotherms for these POPs need better understanding in order to be applicable in both the water column and the porewater.     

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.     

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.     

QSAR models for estimating properties of persistent organic pollutants required in evaluation of their environmental fate and risk

The molecular connectivity indices (MCIs) have been successfully used for over 20 years in quantitative structure activity relationships (QSAR) modelling in various areas of physics, chemistry, biology, drug design, and environmental sciences. With this review, we hope to assist present and future QSAR practitioners to apply MCIs more wisely and more critically. First, we have described the methods of calculation and systematics of MCIs. This section should be helpful in rational selection of MCIs for QSAR modelling. Then we have presented our long-term experience in the application of MCIs through several characteristic and successful QSAR models for estimating partitioning and chromatographic properties of persistent organic pollutants (POPs). We have also analysed the trends in calculated MCIs and discussed their physical interpretation. In conclusion, several practical recommendations and warnings, based on our research experience, have been given for the application of MCIs in the QSAR modelling.     

Evaluating multimedia/multipathway model intake fraction estimates using POP emission and monitoring data

This paper presents a structured evaluation of a novel multimedia chemical fate and multi-pathway human exposure model for Western Europe, IMPACT 2002, using data for PCDD/F congeners. PCDD/F congeners provide an illustration of the potential use of POPs (Persistent Organic Pollutant) data for the evaluation of such models. Based on available emission estimates, model predictions with and without spatial resolution are evaluated at three different stages against monitored data: at environmental contamination levels, food exposure concentration, and in terms of human intake fractions (iF): the fraction of an emission that is taken in by the population. The iF is approximately 3.5.10(-3) for emissions of dioxin in Western Europe. This iF compares well to the traditional non-spatial multi-media/-pathway model predictions of 3.9.10(-3) for the same region and to 2.10(-3) for the USA. Approximately 95% of the intake from Western European emissions occurs within the same region, 5% being transferred out of the region in terms of food contaminants and atmospheric advective transport.     

Primary sources of selected POPs: regional and global scale emission inventories

During the last decade, a number of studies have been devoted to the sources and emissions of Persistent Organic Pollutants (POPs) at regional and global scales. While significant improvements in knowledge have been achieved for some pesticides, the quantitative understanding of the emission processes and emission patterns for "non-pesticide" POPs are still considered limited. The key issues remaining for the non-pesticide POPs are in part determined by their general source classification. For industrial chemicals, such as the polychlorinated biphenyls (PCBs), there is considerable uncertainty with respect to the relative importance of atmospheric emissions from various source categories. For PCBs, temperature is discussed as a potential key factor influencing atmospheric emission levels and patterns. When it comes to the unintentional by-products of combustion and industrial processes (PCDD/Fs), there is still a large uncertainty with respect to the relative contribution of emissions from unregulated sources such as backyard barrel burning that requires further consideration and characterisation. For hexachlorobenzene (HCB), the relative importance of primary and secondary atmospheric emissions in controlling current atmospheric concentrations remains one of the key uncertainties. While these and other issues may remain unresolved, knowledge concerning the emissions of POPs is a prerequisite for any attempt to understand and predict the distribution and fate of these chemicals on a regional and global scale as well as to efficiently minimise future environmental burdens.     

Passive air sampler as a tool for long-term air pollution monitoring: Part 1. Performance assessment for seasonal and spatial variations

The potential of passive air sampling devices (polyurethane foam disks) to assess the influence of local sources on the quality of the surrounding environment was investigated. DEZA Valasske Mezirici, a coal tar and mixed tar oils processing plant, and Spolana Neratovice, a chemical factory with the history of high production of organochlorinated pesticides (OCPs), were selected as the point sources of PAHs, and OCPs, respectively. Levels of PCBs, OCPs and PAHs were determined for all sampling sites and sampling periods. The study brought useful data about the air concentrations of POPs in the investigated regions. More important, it provided information on the transport and fate of POPs in the vicinity of local sources of contamination useful for the estimation of their influence. Very good capability of passive samplers to reflect temporal and spatial fluctuation in concentrations of persistent organic pollutants in the ambient air was confirmed which makes them applicable for monitoring on the local scale.     

Partitioning of polychlorinated biphenyls in octanol/water, triolein/water, and membrane/water systems

The use of the octanol/water partition constant (Kow) as a surrogate parameter for lipid/water partitioning of persistent organic pollutants (POPs) was reassessed by comparing the measured Kow of 12 selected polychlorinated biphenyl congeners (PCBs) with partition constants in triolein/water (Ktw) and membrane/water (Kmw) systems. Kow and Ktw were measured by the slow-stirring method. Kmw was measured by an adaptation of the slow-stirring method using suspensions of phosphatidylcholine and phosphatidylserine liposomes. Partitioning of POPs to octanol, triolein, and liposomes is similar but not equal. The log-log correlation for Kow and Ktw is excellent (r2 = 0.982) and that for Kow and Kmw is somewhat weaker (r2 = 0.856). Ktw values are greater than Kow by a factor of 1.6. Kmw of some PCB congeners exceed both Kow and Ktw by an order of magnitude. The differences are attributed to different PCB activity coefficients in the different lipid phases. The results imply that Kow can be used as a reasonable conservative estimate of lipid/water partitioning. But the observed differences between Kow and Kmw also indicate that using Kow to predict accumulation of POPs, particularly highly hydrophobic ones, in the polar lipids of organisms will underestimate their concentrations at equilibrium.     

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.     

Multicompartmental fate of persistent substances

Background, Aim and Scope Modelling of the fate of environmental chemicals can be done by relatively simple multi-media box models or using complex atmospheric transport models. It was the aim of this work to compare the results obtained for both types of models using a small set of non-ionic and non-polar or moderately polar organic chemicals, known to be distributed over long distances. Materials and Methods Predictions of multimedia exposure models of different types, namely three multimedia mass-balance box models (MBMs), two in the steady state and one in the non-steady state mode, and one non-steady state multicompartment chemistry-atmospheric transport model (MCTM), are compared for the first time. The models used are SimpleBox, Chemrange, the MPI-MBM and the MPI-MCTM. The target parameters addressed are compartmental distributions (i.e. mass fractions in the compartments), overall environmental residence time (i.e. overall persistence and eventually including other final sinks, such as loss to the deep sea) and a measure for the long-range transport potential. These are derived for atrazine, benz-[a]-pyrene, DDT, α and γ-hexachlorocyclohexane, methyl parathion and various modes of substance entry into the model world. Results and Discussion Compartmental distributions in steady state were compared. Steady state needed 2–10 years to be established in the MCTM. The highest fraction of the substances in air is predicted by the MCTM. Accordingly, the other models predict longer substance persistence in most cases. The results suggest that temperature affects the compartmental distribution more in the box models, while it is only one among many climate factors acting in the transport model. The representation of final sinks in the models, e.g. burial in the sediment, is key for model-based compartmental distribution and persistence predictions. There is a tendency of MBMs to overestimate substance sinks in air and to underestimate atmospheric transport velocity as a consequence of the neglection of the temporal and spatial variabilities of these parameters. Therefore, the long-range transport potential in air derived from MCTM simulations exceeds the one from Chemrange in most cases and least for substances which undergo slow degradation in air. Conclusions and Perspectives MBMs should be improved such as to ascertain that the significance of the atmosphere for the multicompartmental cycling is not systematically underestimated. Both types of models should be improved such as to cover degradation in air in the particle-bound state and transport via ocean currents. A detailed understanding of the deviations observed in this work and elsewhere should be gained and multimedia fate box models could then be ‘tuned in’ to match better the results of comprehensive multicompartmental transport models. ESS-Submission Editor: Prof. Dr. Michael Matthies (matthies@uos.de)     

A numerical study on the seasonal variability of polychlorinated biphenyls from the atmosphere in the East China Sea

A three-dimensional/high-resolution transport model for persistent organic pollutants (POPs) has been developed for the East China Sea (ECS). The POPs model has four compartments (gaseous, dissolved, phytoplankton-bound, and detritus-bound phases) and includes processes for diffusive air-water exchange, phytoplankton uptake/depuration to POPs, decomposition of dissolved phase, vertical sinking of phytoplankton, detritus production by phytoplankton mortality, and vertical sinking and decomposition of detritus. The POPs model is coupled with an ocean circulation model that can reproduce the seasonal variation in physical variables to represent the advection and diffusion of POPs. We applied the POPs model to the polychlorinated biphenyl congener 153 (PCB 153) from the atmosphere and examined the behavior of PCB 153 in the ocean. The model showed a remarkable seasonal variability of PCB 153. Concentrations in the dissolved and particulate phases are high in winter (January-March) and low in summer (July-September). In coastal regions, where chlorophyll a concentration is high, horizontal and vertical distributions in the dissolved and particulate PCB 153 concentrations are strongly affected by phytoplankton uptake. The sensitivity experiments on the dynamics of PCB 153 suggested that a change of Henry’s law constant associated with water temperature is the major factor controlling the seasonal variability of PCB 153. The model-based yearly mass balance of PCB 153 in the ECS indicated that most of the atmospheric input (35.5 kg year⁻¹) is removed by the horizontal advection outside the ECS (19.0 kg year⁻¹) and accumulates to the sea bottom by vertical sinking (15.7 kg year⁻¹). For comparison with PCB 153, we also conducted simulations for PCB 52, 101, and 180. The seasonal variations are similar to that of PCB 153. The mass balance of PCB 52 that has short half-life time and less hydrophobic property shows the different results compared with PCB 101, 153, and 180.     

The spatial scale of organic chemicals in multimedia fate modeling. Recent developments and significance for chemical assessment

In the last years, the spatial range (SR) or characteristic travel distance (CTD) of organic chemicals has found increasing scientific interest as an indicator of the long-range transport (LRT) potential and, in combination with persistence, as a kind of 'hazard' indicator on the exposure level. This development coincides with European debates about more effective and more preventive approaches to the chemicals assessment, and about an international, legally-binding instrument for the phase out of persistent organic pollutants (POPs). Persistence and LRT potential are important issues in these debates. Here, the development of the concept of assessing the spatial scale from early ideas in the 1970s and 1980s to recent studies in the field of multimedia fate and transport modeling is summarized. Different approaches to the modeling of environmental transport (advective and dispersive) and different methods for quantifying the SR or CTD are compared. Relationships between SR or CTD and different persistence measures are analyzed. Comparison of these relationships shows that conclusions for chemical assessment should be based on an evaluation of different persistence and spatial scale measures. The use of SR or CTD and persistence as hazard indicators in the chemicals assessment is illustrated.     

Modelling of an enhanced PAH attenuation experiment and associated biogeochemical changes at a former gasworks site in southern Germany

Former manufactured gas plant sites often form a widespread contaminant source in the subsurface, leading to large plumes that contain a wide variety of tar-oil related compounds. Although most of these compounds eventually degrade naturally, the relevant processes tend to be slow and inefficient, often leaving active remediation as the only viable option to eliminate the risks of toxic substances to reach potential receptors such as surface waters or drinking water wells. In this study we use a reactive transport model to analyse the fate of a contaminant plume containing acenaphthene, methylbenzofurans and dimethylbenzofurans (i) prior to the installation of an active remediation scheme and (ii) for an enhanced remediation experiment during which O(2) and H(2)O(2) were added to the contaminated groundwater through a recirculation well. The numerical model developed for this study considers the primary contaminant degradation reactions (i.e., microbially mediated redox reactions) as well as secondary and competing mineral precipitation/dissolution reactions that affect the site's hydrochemistry and/or contaminant fate. The model was calibrated using a variety of constraints to test the uncertainty on model predictions resulting from the undocumented presence of reductants such as pyrite. The results highlight the important role of reactive transport modelling for the development of a comprehensive process understanding.     

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

It is useful to have available a variety of catchment-scale water quality models that range in complexity, spatial resolution and data requirements. In a previous paper [Warren, C., Mackay, D., Whelan, M., Fox, K., 2005. Mass balance modelling of contaminants in river basins: a flexible matrix approach. Chemosphere 61, 1458-1467] a series of simple to intermediately complex mass balance models was presented which can be used for tiered exposure assessments in river basins. The connectivity of the segments is expressed using a matrix that permits flexibility in application, enabling the model to be re-segmented and applied to different catchments as required. In this paper, the intermediate models, QWASI matrix-rate constant (QMX-R) and QWASI matrix-fugacity (QMX-F) are used to estimate concentrations of linear alkylbenzene sulfonates (LAS) in the rivers Aire and Calder, UK, and of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in the Fraser River basin, Canada. The results compare satisfactorily with monitoring data, suggesting that these QWASI-based models for exposure and risk assessment may be applicable under data-limited conditions. The use of QWASI-based models for regulatory purposes in an evaluative river system is also discussed with reference to assessments of para-dichlorobenzene (pDCB), trichloroethylene (TCE), bis(2-ethylhexyl) phthalate (DEHP) and toluene. It is shown that multi-media QWASI model predictions can be usefully depicted graphically on chemical space diagrams and used to highlight regions in which advection, partitioning to sediments and volatilization may be important determinants of chemical fate in river systems.