Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

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.     

Atmospheric fate of non-volatile and ionizable compounds

A modified version of the Multimedia Activity Model for Ionics MAMI, including two-layered atmosphere, air-water interface partitioning, intermittent rainfall and variable cloud coverage was developed to simulate the atmospheric fate of ten low volatility or ionizable organic chemicals. Probabilistic simulations describing the uncertainty of substance and environmental input properties were run to evaluate the impact of atmospheric parameters, ionization and air-water (or air-ice) interface enrichment.The rate of degradation and the concentration of OH radicals, the duration of dry and wet periods, and the parameters describing air-water partitioning (K_AW and temperature) and ionization (pK_a and pH) are the key parameters determining the potential for long range transport. Wet deposition is an important removal process, but its efficiency is limited, primarily by the duration of the dry period between precipitation events.Given the underlying model assumptions, the presence of clouds contributes to the higher persistence in the troposphere because of the capacity of cloud water to accumulate and transport non-volatile (e.g. 2,4-D) and surface-active chemicals (e.g. PFOA). This limits the efficiency of wet deposition from the troposphere enhancing long-range transport.     

Trajectory analysis of wet deposition at Whiteface Mountain: A sensitivity study

Meteorological trajectory analysis, MAP3S precipitation chemistry data, and hourly precipitation data at Whiteface Mountain (WFM) were used to determine the source direction of sulfate deposited in precipitation for 1978. A sensitivity study was done on source direction from different trajectory models, using different transport layers, and different precipitation information to determine the time deposition occurred. Results obtained from the different precipitation information indicate that precipitation data in 6-h increments or less are essential to correctly identify the trajectories associated with the wet deposition. Bias resulted when trajectories were not only associated with wet deposition. The direction of source regions, defined by 30° sectors, was much less dependent on the trajectory model or transport layer. Results suggest that over one-third of the wet sulfate deposition at WFM in 1978 arrived from the west-southwest, passing through the eastern Great Lakes region.     

Toxaphene congeners in the Canadian Great Lakes basin: temporal and spatial food web dynamics

Samples of a top predator fish species, lake trout (Salvelinus namaycush) and predominant forage species including smelt (Osmerus mordax), alewife (Alosa pseudoharengus), slimy sculpin (Cottus cognatus), deepwater sculpin (Myoxocephalus quadricornis) and lake herring (Coregonus artedii) were, collected from throughout 4 of the 5 Great Lakes (Superior, Huron, Erie and Ontario) (Fig. 1). Lake trout were also collected from three isolated lake systems (Lakes Nipigon, Simcoe and Opeongo), all located within the basin. All the samples were analysed for body burdens of total toxaphene and 22 toxaphene congeners. In addition, from each of the Great Lakes sites samples of major invertebrate dietary items, which included Mysis relicta, Diporeia hoyi and plankton, were similarly analysed. Whole lake trout samples, archived at -80 degrees C, were reanalysed to determine historical trends of toxaphene congeners plus carbon and nitrogen stable isotope signatures. The Lake Superior food web consistently had the highest levels of total toxaphene of all the Great Lakes monitored. The primary source of toxaphene to Lake Superior has been identified as atmospheric transport and deposition from sites in the southern US, Mexico and Central America (Hoff, R.M., Strachan, W.M.J., Sweet, C.W., Chan, C.H., Shackelton, M., Bidleman, T.F., Brice, K.A., Burnison, D.A., Cussion, S., Gatz, D.F., Harlin, K., Schroeder, W.H., 1996. Atmospheric deposition of toxic chemicals to the Great Lakes: A review of data through 1994. Atmospheric Environ. 30, 3505-3527). Of the offsystem lakes surveyed. Lake Nipigon, situated due north of Lake Superior and with a Lake Basin area of about 6% of Lake Superior (Hendendorf, C.E., 1982. J. Great Lakes Res. 8(3), 379-412) had total toxaphene levels in lake trout equivalent to about 50% of those found in lake trout from Lake Superior. Temporal trend toxaphene congener analysis was conducted on archived whole fish samples collected over the period 1980 through to the 1990's. Initially a nonachlorobornane congener (Parlar #50) was predominant, with congeners #40, #62 and #21 being the next most prominent in the 1980 samples. Samples from the 1990's showed a significant decline in the presence of lower chlorinated congeners #40 and #21. Analysis of total toxaphene in food webs, indicated elevated levels in lower trophic level species such as Diporeia and Cottus sp. which have a benthic association. The stable isotope temporal trend 13C signature identified a significant shift in the lake trout diet over the period 1993 to 1996.     

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.     

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.     

Organochlorine contaminants in eggs of Common Terns from the Canadian Great Lakes, 1981

To determine if contaminant levels in Common Terns had changed over the last decade, we collected and analyzed eggs from four nesting colonies on the three lower Great Lakes during 1981. DDE and PCBs were detected in every egg from the four colonies. Dieldrin, mirex and trans-nonachlor were detected in more than 45% of the eggs. Seven other organochlorine contaminants (DDD, DDT, hexachlorobenzene, oxychlordane, cis-chlordane, cis-nonachlor and toxaphene) were detected in less than 25% of the eggs. Eggs from the Lake Ontario colony were generally the most heavily contaminated. Comparisons of DDE and PCB data with earlier studies of Common Terns indicated that contaminant levels in eggs from the four sampled colonies, or nearby sites, have decreased by up to 80-90% from 1969-1973 to 1981. Interspecies comparisons showed that Common Tern eggs have lower organochlorine residue levels than eggs of Caspian Terns or Herring Gulls. Dietary variation and migratory status are possible explanations for the differences in residue levels among species. Eggshell thickness, log-PCBs, and log-DDE were not significantly intercorrelated. Elevated contaminant levels in the early 1970s might be at least partly responsible for the decline of the Great Lakes Common Tern population over the past decade. Stabilization of population numbers during the early 1980s suggests that organochlorine pollution levels have been reduced to a point where they are no longer an important factor in the population dynamics of this species on the Great Lakes.     

Trends of brominated diphenyl ethers in fresh and archived Great Lakes fish (1979-2005)

While few environmental measurements of brominated diphenyl ethers (BDEs) were completed prior to the mid-1990s, analysis of appropriately archived samples might enable the determination of contaminant trends back to the introduction of these chemicals. In this paper, we first investigate the stability of BDEs in archived frozen and extracted fish samples, and then characterize trends of these chemicals in rainbow smelt (Osmerus mordax) and lake trout (Salvelinus namaycush) in each of the Great Lakes between 1979 and 2005. We focus on the four most common congeners (BDE-47, 100, 99 and 153) and use a change-point analysis to detect shifts in trends. Analyses of archived fish samples yielded precise BDE concentration measurements with only small losses (0.8% per year in frozen fish tissues, 2.2% per year in refrigerated extracts). Trends in fish from all Great Lakes showed large increases in BDE concentrations that started in the early to mid-1980s with fairly consistent doubling times (generally 2-4 years except in Lake Erie smelt where levels increased very slowly), though concentrations and trends show differences by congener, fish species and lake. The most recent data show that accumulation rates are slowing, and concentrations of penta- and hexa-congeners in trout from Lakes Ontario and Michigan and smelt from Lake Ontario started to decrease in the mid-1990s. Trends in smelt and trout are evolving somewhat differently, and trout concentrations in the five lakes are now ranked as Michigan>Superior=Ontario>Huron=Erie, and smelt concentrations as Michigan>Ontario>Huron>Superior>Erie. The analysis of properly archived samples permits the reconstruction of historical trends, congener distributions, biomagnification and other information that can aid the understanding and management of these contaminants.     

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.     

A multimedia environmental model of chemical distribution: fate, transport, and uncertainty analysis

This paper presented a framework for analysis of chemical concentration in the environment and evaluation of variance propagation within the model. This framework was illustrated through a case study of selected organic compounds of benzo[alpha]pyrene (BAP) and hexachlorobenzene (HCB) in the Great Lakes region. A multimedia environmental fate model was applied to perform stochastic simulations of chemical concentrations in various media. Both uncertainty in chemical properties and variability in hydrometeorological parameters were included in the Monte Carlo simulation, resulting in a distribution of concentrations in each medium. Parameters of compartmental dimensions, densities, emissions, and background concentrations were assumed to be constant in this study. The predicted concentrations in air, surface water and sediment were compared to reported data for validation purpose. Based on rank correlations, a sensitivity analysis was conducted to determine the influence of individual input parameters on the output variance for concentration in each environmental medium and for the basin-wide total mass inventory. Results of model validation indicated that the model predictions were in reasonable agreement with spatial distribution patterns, among the five lake basins, of reported data in the literature. For the chemical and environmental parameters given in this study, parameters associated to air-ground partitioning (such as moisture in surface soil, vapor pressure, and deposition velocity) and chemical distribution in soil solid (such as organic carbon partition coefficient and organic carbon content in root-zone soil) were targeted to reduce the uncertainty in basin-wide mass inventory. This results of sensitivity analysis in this study also indicated that the model sensitivity to an input parameter might be affected by the magnitudes of input parameters defined by the parameter settings in the simulation scenario. Therefore, uncertainty and sensitivity analyses for environmental fate models was suggested to be conducted after the model output was validated based on an appropriate input parameter settings.     

Estimation of nitrogen balance between the atmosphere and Lake Balaton and a semi natural grassland in Hungary

The paper summarises the results to determine the fluxes of different N-compounds within the atmosphere and an aquatic and a terrestrial ecosystems, in Hungary. In the exchange processes of N-compounds between atmosphere and various ecosystems the deposition dominates. The net deposition fluxes are -730, -1270 and -1530 mg Nm(-2)yr(-1) for water, grassland, and forest ecosystems, respectively. For water, the main source of nitrogen compounds is the wet deposition. Ammonia gas is close to the equilibrium between the water and the air. For grassland the dry flux of nitric acid and ammonia is also an important term beside the wet deposition. Dry deposition to terrestrial ecosystems is roughly two times higher than wet deposition. A total of 8-10% of the nitrates and NH(x) deposited to terrestrial ecosystems are re-emitted into the air in the form of nitrous oxide (N2O) greenhouse gas.     

Multimedia emissions inventory of polychlorinated biphenyls for the U.S. Great Lakes states

Polychlorinated biphenyls (PCBs) were banned in the United States in 1979, and since then a significant decline in their release to the environment has been observed. This decline has now reached a plateau. Several new regulatory programs have been put in place to further reduce PCB emissions/releases. However, our ability to measure the effectiveness of these regulatory/voluntary programs and to support regional fate/transport and source/receptor modeling efforts depend on reliable emission information. In this study, we attempt to improve the emission inventory for PCBs by compiling and analyzing the multimedia total PCB emission/release data reported for the U.S Great Lakes states for each year from 1990 to 2000. Although Toxic Release Inventory (TRI), National Emissions Inventory (NEI), Great Lakes Regional Air Toxic Emissions Inventory (GLRATEI), and Integrated Atmospheric Deposition Network (IADN) data formed the basis of estimating air emissions, we used the TRI, National Response Center (NRC), and PCB transformer inventory data to estimate PCB releases to land. We used the Permit Compliance System and NRC data to obtain estimates of PCB discharges to water systems in the Great Lakes states. The Remedial Action Plans for each area of concern were the primary source for estimating PCB loads of dredged sediments. On the basis of the NEI, IADN, and GLRATEI data, the total air emissions within the decade were approximately 126 t. The regionwide discharges to water systems and releases to land in the form of landfills and accidental spills in 1990-2000 were estimated as approximately 170 and 3225 t, respectively. We estimated that approximately 1.3 million t of PCB-contaminated sediment were removed or targeted for removal in five lakes of the U.S. portion of the Great Lakes basin. We stress that these estimates were based on reported amounts and the unreported PCB releases/emissions could result in significantly higher estimates.     

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.     

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.     

A new sampler for collecting separate dry and wet atmospheric depositions of trace organic chemicals

Studies conducted in Saskatchewan and elsewhere have demonstrated the atmospheric transport of agricultural pesticides and other organic contaminants and their deposition into aquatic ecosystems. To date these studies have focused on ambient concentrations in the atmosphere and in wet precipitation. To measure the dry deposition of organic chemicals, a new sampler was designed which uses a moving sheet of water to passively trap dry particles and gasses. The moving sheet of water drains into a reservoir and, during recirculation through the sampler, is passed through an XAD-2 resin column which adsorbs the trapped organic contaminants. All surfaces which contact the process water are stainless steel or Teflon. Chemicals collected can be related to airborne materials depositing into aquatic ecosystems. The sampler has received a United States patent (number 5,413,003 – 9 May 1996) with the Canadian patent pending.XAD-2 resin adsorption efficiencies for 10 or 50 μg fortifications of ten pesticides ranged from 76% for atrazine (2-chloro-4-ethylamino-6-isopropylamino-S-triazine) to 110% for triallate [S-(2,3,3-trichloro-2-phenyl)bis(1-methylethyl)carbamothioate], dicamba (2-methoxy-3,6-dichlorobenzoic acid) and toxaphene (chlorinated camphene mixture). Field testing using duplicate samplers showed good reproducibility and amounts trapped were consistent with those from high volume and bulk pan samplers located on the same site. Average atmospheric dry deposition rates of three chemicals, collected for 5 weeks in May and June, were: dicamba, 69 ng m^-2 da^-1; 2,4-D (2,4-dichlorophenoxyacetic acid), 276 ng m^-2 da^-1: and, γ-HCH (γ-1, 2, 3, 4, 5, 6-hexachlorocyclohexane), 327 ng m^-2 da^-1.     

The effect of export to the deep sea on the long-range transport potential of persistent organic pollutants

BACKGROUND: Export to the deep sea has been found to be a relevant pathway for highly hydrophobic chemicals. The objective of this study is to investigate the influence of this process on the potential for long-range transport (LRT) of such chemicals. METHODS: The spatial range as a measure of potential for LRT is calculated for seven PCB congeners with the multimedia fate and transport model ChemRange. Spatial ranges for cases with and without deep sea export are compared. RESULTS AND DISCUSSION: Export to the deep sea leads to increased transfer from the air to the surface ocean and, thereby, to lower spatial ranges for PCB congeners whose net deposition rate constant is similar to or greater than the atmospheric degradation rate constant. This is fulfilled for the PCB congeners 101, 153, 180, and 194. The spatial ranges of the congeners 8, 28, and 52, in contrast, are not affected by deep sea export. With export to the deep sea included in the model, the spatial ranges of the heavier congener are similar to those of the lighter ones, while the intermediate congeners 101 and 153 have the highest potential for long-range transport. CONCLUSIONS: Transfer to the deep ocean affects the mass balance and the potential for LRT of highly hydrophobic chemicals and should be included in multimedia fate models containing a compartment for ocean water.