Fate modeling of phenanthrene with regional variation in Tianjin,China

A multimedia fate model with spatially resolved air and soil phases was developed and evaluated. The model was used for calculation of phenanthrene concentrations in air, water, soil, and sediment in Tianjin area and transport fluxes between the adjacent bulk phases under steady-state assumption. Both air and soil phases were divided into 3113 individual compartments of 4 km2 each to assess the spatial variation of phenanthrene concentrations and fluxes. Independently measured phenanthrene concentrations in air, water, and soil were used for model validation. The spatial variation in soil was validated using a set of measured phenanthrene concentrations of 188 surface soil samples collected from the area. Most data used either for model calculation or for model validation were collected during the last 5 years. As the results of the model validation, the calculated mean values for phenanthrene concentrations in various bulk phases are in fair agreement with those independently observed and are very close to those calculated using the model without spatial variation. The absolute difference between the calculated and the measured mean concentrations are 0.14, 0.48, and 0.13 log-units (mol/m3) for air, water, and soil, respectively. The spatial distribution patterns of phenanthrene in both air and soil were well modeled. Spatially, however, the model overestimated the soil phenanthrene level at low concentration range and underestimated it at high concentration range. The calculated distribution of phenanthrene in the air matches well with the emission from fossil fuel combustion, while the calculated distribution pattern in the soil is similar to that observed.     

Accumulation of persistent organic pollutants in canopies of different forest types: role of species composition and altitudinal-temperature gradient

Leaves from the dominant tree species in three different alpine forests were sampled along an altitudinal gradient and analyzed for HCB, alpha- and gamma-HCH, and PCBs. The mean canopy concentration was calculated, considering the relative abundance of each species in the respective forest. Compound fractionation occurred in the vegetation along the altitudinal/temperature gradient. Results were compared with air concentrations and in-field plant/air partition coefficients (K(PA)) were calculated for each species; this showed differences between broadleaves and needles. The mean canopy/air partition coefficient (K(CA)) was also calculated by averaging results from single species. The variability of persistent organic pollutants distribution in canopies is discussed considering two main factors, the altitudinal/temperature gradient and the species composition. The latter is responsible for most of the concentration variability of the more volatile compounds. A model to calculate dry gaseous deposition to different forest canopies is presented.     

A dynamic model to study the exchange of gas-phase persistent organic pollutants between air and a seasonal snowpack

An arctic snow model was developed to predict the exchange of vapor-phase persistent organic pollutants between the atmosphere and the snowpack over a winter season. Using modeled meteorological data simulating conditions in the Canadian High Arctic, a single-layer snowpack was created on the basis of the precipitation rate, with the snow depth, snow specific surface area, density, and total surface area (TSA) evolving throughout the annual time series. TSA, an important parameter affecting the vapor-sorbed quantity of chemicals in snow, was within a factor of 5 of measured values. Net fluxes for fluorene, phenanthrene, PCB-28 and -52, and alpha- and gamma-HCH (hexachlorocyclohexane) were predicted on the basis of their wet deposition (snowfall) and vapor exchange between the snow and atmosphere. Chemical fluxes were found to be highly dynamic, whereby deposition was rapidly offset by evaporative loss due to snow settling (i.e., changes in TSA). Differences in chemical behavior over the course of the season (i.e., fluxes, snow concentrations) were largely dependent on the snow/air partition coefficients (K(sa)). Chemicals with relatively higher K(sa) values such as alpha- and gamma-HCH were efficiently retained within the snowpack until later in the season compared to fluorene, phenathrene, and PCB-28 and -52. Average snow and air concentrations predicted by the model were within a factor of 5-10 of values measured from arctic field studies, but tended to be overpredicted for those chemicals with higher K(sa) values (i.e., HCHs). Sensitivity analysis revealed that snow concentrations were more strongly influenced by K(sa) than either inclusion of wind ventilation of the snowpack or other changes in physical parameters. Importantly, the model highlighted the relevance of the arctic snowpack in influencing atmospheric concentrations. For the HCHs, evaporative fluxes from snow were more pronounced in April and May, toward the end of the winter, providing evidence that the snowpack plays an important role in influencing the seasonal increase in air concentrations for these compounds at this time of year.     

Measurement of DDT fluxes from a historically treated agricultural soil in Canada

Organocohlorine pesticide (OCP) residues in agricultural soils are of concern due to the uptake of these compounds by crops, accumulation in the foodchain, and reemission from soils to the atmosphere. Although it has been about three decades since DDT was banned for agricultural uses in Canada, residues persist in soils of some agricultural areas. Emission of DDT compounds to the atmosphere from a historically treated field in southern Ontario was determined in fall 2004 and spring 2005. The sigmaDDTs concentration in the high organic matter (71%) soil was 19 +/- 4 microg g(-1) dry weight. Concentration gradients in the air were measured at 5, 20, 72, and 200 cm above soil using glass fiber filter-polyurethane foam cartridges. Air concentrations of sigmaDDTs averaged 5.7 +/- 5.1 ng m(-3) at 5 cm and decreased to 1.3 +/- 0.8 ng m(-3) at 200 cm and were 60-300 times higher than levels measured at a background site 30 km away. Soil-air fugacity fractions, fs/(fs + fa), of p,p'-DDE, p,p'-DDD, and p,p'-DDT ranged from 0.42 to 0.91 using air concentrations measured above the soil and > or = 0.99 using background air concentrations, indicating that the soil was a net source to the background air. Fractionation of DDT compounds during volatilization was predicted using either liquid-phase vapor pressures (PL) or octanol-air partition coefficients (KOA). Relative emissions of p,p'-DDE and p,p'-DDT were better described by PL than KOA, whereas either PL or KOA successfully accounted for the fractionation of p,p'-DDT and o,p'-DDT. Soil-to-air fluxes were calculated from air concentration gradients and turbulent exchange coefficients determined from micrometeorological measurements. Average fluxes of sigmaDDTs were 90 +/- 24 ng m(-2) h(-1) in fall and 660 +/- 370 ng m(-2) h(-1) in spring. Higher soil temperatures in spring accounted for the higher fluxes. A volatilization half-life of approximately 200 y was estimated for sigmaDDT in the upper 5 cm of the soil column, assuming the average flux rate for 12 h d-(1) over 8 months of the year. Thus, in the absence of other dissipation processes, the soil will continue to be a source of atmospheric contamination for a very long time.     

Impacts of lindane usage in the Canadian Prairies on the Great Lakes ecosystem. 2. Modeled fluxes and loadings to the Great Lakes

Atmospheric loadings of gamma-hexachlorocyclohexane (gamma-HCH) from May 1, 1998, to April 30, 1999, to the Great Lakes simulated by a coupled soil-air and water-air atmospheric transport model are presented. Modeling results on an annual basis indicate that Lake Superior received the highest dry deposition load of 2.17 kg yr(-1). Dry deposition to the lower Great Lakes (Lakes Erie and Ontario) was 2-6 times lower as compared to the upper Great Lakes. Greater deposition in the upper Great Lakes is due mainly to their larger surface area and greater proximity to sources of gamma-HCH. Dry deposition fluxes (pg m(-2)) to lake surfaces were much lower than to land as a result of lower deposition velocities and lower air concentrations of gamma-HCH over the lakes. The highest gamma-HCH loading (kg yr(-1), in 1998-99) due to wet deposition occurred for Lake Ontario. This was mainly attributed to greater annual rainfall over Lake Ontario. An investigation of average seasonal fluxes predicted by the model shows that deposition fluxes to the Great Lakes are considerably higher in the summer than that in the autumn and winter seasons. The net direction of gas exchange also exhibits a seasonal dependence. Lakes Michigan, Huron, and Ontario show net absorption in the summer 1998 whereas at all other times net outgassing occurred at all of the lakes. Overall, gas exchange was the dominant process affecting loadings to the Great Lakes. Model-derived loadings and total deposition flows across the Great Lakes basin due to dry and wet depositions and net gas exchange agree reasonably well with the summer estimates compiled by the Integrated Atmospheric Deposition Network whereas autumn values show greater discrepancies. Better agreement was also observed for dry deposition as compared to wet deposition. Specifically, to improve short-term loading estimates (e.g., over days to months), the model results indicate the need for better spatially and temporally resolved information on concentrations in air and surface water and better estimates of precipitation and deposition velocities over the lakes.     

Impacts of lindane usage in the Canadian prairies on the Great Lakes ecosystem. 1. Coupled atmospheric transport model and modeled concentrations in air and soil

A coupled atmospheric transport, soil-air, water-air exchange model was developed to investigate the impacts of gamma-hexachlorocyclohexane (gamma-HCH or lindane) usage in the Canadian prairies over the Great Lakes region. The fate of gamma-HCH in air and soil is governed by atmospheric dynamics and physical and chemical processes that are described by the coupled model. These processes include transport and turbulent diffusion in the atmosphere, dry and wet deposition, exchange at the interfacial boundaries of air-water and soil-air, and removal processes from the soil such as diffusion, leaching, and degradation. Numerical experiments were conducted for the period of May 1, 1998-April 30, 1999, starting with application of lindane in the spring. The coupled model was executed with two lindane emission (usage) inventories in the model domain. The first scenario contained all known fresh emission sources in Canada-98% was usage in the prairies; the second excluded emission sources from Ontario and Quebec. The model showed that, in the absence of the reemission from past application of lindane, usage of lindane in Ontario and Quebec has a negligible impact on air concentrations in these regions and that the lindane budget in the Great Lakes ecosystem is mostly attributed to applications of lindane in the canola fields in Canadian prairie provinces. Model-predicted air concentrations and seasonal trends agreed well with measured data over the same time period for several background sites operated under the Integrated Atmospheric Deposition Network. Air temperature was shown to play a key role on surface-air exchange dynamics of gamma-HCH. A future paper will assess loadings to the Great Lakes based on these validated model results.     

Influence of Asian and Western United states agricultural areas and fires on the atmospheric transport of pesticides in the Western United States

Historic and current use pesticides (HUPs and CUPs), with respect to use in the United States and Canada, were identified in trans-Pacific and regional air masses at Mt. Bachelor Observatory (MBO), a remote high elevation mountain in Oregon's Cascade Range located in the United States, during the sampling period of April 2004 to May 2006 (n = 69), including NASA's INTEX-B campaign (spring 2006). Elevated hexachlorobenzene (HCB) and alpha-hexachlorocyclohexane (alpha-HCH) concentrations were measured during trans-Pacific atmospheric transport events at MBO, suggesting that Asia is an important source region for these HUPs. Regional atmospheric transport events at MBO resulted in elevated dacthal, endosulfan, metribuzin, triallate, trifluralin, and chlorpyrifos concentrations, with episodic increases in concentration during some spring application periods, suggesting that the Western U.S. is a significant source region for these CUPs. Endosulfan I, gamma-HCH, and dacthal concentrations were significantly positively correlated (p-value < 0.05) with increased air mass time in Western U.S. agricultural areas. Elevated gamma-HCH concentrations were measured at MBO during both trans-Pacific and regional atmospheric transport events, including regional fire events. In addition to gamma-HCH, elevated sigmachlordane, alpha-HCH, HCB, and trifluralin concentrations were associated with fires in Western North America due to revolatilization of these pesticides from soils and vegetation. Trans-chlordane/cis-chlordane and alpha-HCH/gamma-HCH ratios were calculated and may be used to distinguish between free tropospheric and regional and/or Asian air masses.     

Hexachlorocyclohexanes (HCHs) in the Canadian Archipelago. 2. Air-water gas exchange of alpha- and gamma-HCH

Air and water were sampled in the Canadian Archipelago during summer on the Tundra Northwest 1999 (TNW-99) expedition and air was sampled at Resolute Bay (RB), Nunavut, to determine the gas exchange of alpha- and gamma-hexachlorocyclohexanes (HCHs) and the enantiomers of alpha-HCH. Air concentrations of sigmaHCH during TNW-99 and at RB were similar, averaging 55 and 53 pg m(-3), respectively. The net gas exchange direction was volatilization for alpha-HCH and near equilibrium or deposition for gamma-HCH, whereas actual fluxes depended on the fraction of open water. Enantiomer fractions, EF = (+)/[(+) + (-)] of alpha-HCH in air sampled from shipboard were significantly correlated to those in surface water for events with >90% open water, but were closer to racemic and not correlated to EFs in water for events with 0-50% open water. Levels of alpha-HCH in air at RB averaged 37 +/- 9 pg m(-3) from June to early July, and EFs were close to racemic (0.496 +/- 0.004). In mid-July the ice pack broke up around RB. From this point through August, air concentrations increased significantly to 53 +/- 5 pg m(-3), and the mean EF decreased significantly to 0.483 +/- 0.009. Air concentrations of gamma-HCH at RB did not differ significantly before (8.0 +/- 3.7 pg m(-3)) and after (6.6 +/- 0.76 pg m(-3)) ice breakup. Results show that alpha-HCH enantiomers are sensitive tracers for following the impact of ice cover loss on gas exchange in the Arctic.     

Some pesticides occurrence in air and precipitation in Québec, Canada

Air and precipitation samples were collected in three stations located in Quebec between January 1993 and March 1996 to determine spatial and seasonal variations of several organochlorine pesticides and metabolites (alpha-HCH, gamma-HCH, HCB, gamma-chlordane, DDT, DDE, Mirex). alpha-HCH, gamma-HCH, and HCB were more or less measured in large amounts at all sites, whereas gamma-chlordane, DDT, and DDE concentrations were lower and Mirex was undetectable. Higher concentrations levels were observed in air during hot spring/summer periods except for HCB, indicating a probable temperature dependence. Ln concentrations vs reciprocal temperature plots and Henry's law determinations helped to highlight the contribution of soil and/or water volatilization of those compounds. Itwas observed that alpha-HCH came mainly from Atlantic Ocean volatilization at Mingan, whereas sources of gamma-chlordane and DDE were mostly due to volatilization from soils in southern Quebec. DDT may be present in the atmosphere by the way of transport from remote regions. Lindane sources were multiple: it may be found in the atmosphere bythe processes of transport and volatilization coming from soil or water. Finally, a negative correlation between HCB and air temperature implies that processes other than volatilization are involved in transport of this compound.     

Illustrating sensitivity and uncertainty in environmental fate models using partitioning maps

Variations of model predictions of the environmental fate of organic contaminants are usually analyzed for only one or at most a few selected chemicals, even though parameter sensitivity and contribution to uncertainty are widely different for different chemicals. A graphical method is introduced that allows for the comprehensive investigation of model sensitivity and uncertainty for all persistent organic nonelectrolytes at the same time. This is achieved by defining a two-dimensional hypothetical "chemical space" as a function of the equilibrium partition coefficients between air, water, and octanol (KOW, KAW, KOA), and plotting sensitivity and/or uncertainty of a specific model result to each input parameter as a function of this chemical space. The approach is illustrated for the bulk phase concentrations in air, water, soil, and sediment calculated by a level III model. Colored contour maps facilitate the identification of those input parameters that cause a high output variation of hypothetical and real chemicals. They also allow for the easy categorization of chemicals in terms of common parameter sensitivities, and thus comparable environmental behavior. Sensitivity varies with the mode of emission and the degradability of the chemicals, making it necessary to develop multiple sets of contour maps. Comparison of these sets of maps in turn allows the investigation of how parameter sensitivities change as a result of changes in mode of emission and persistence. The presented method can be used for investigating the sensitivity of any prediction obtained with any linear fate model that characterizes the partitioning behavior of organic chemicals with KAW, KoW, and KOA. Once the sensitivity maps have been constructed for a given environmental scenario, it is possible to perform a sensitivity analysis for a specific chemical by simple. placement of the substances' partitioning combinations within the chemical space. The maps can further contribute to the mechanistic understanding of a model's behavior, can aid in explaining observations of divergent environmental behavior of related substances, and can provide a rationale for grouping chemicals with similar model behavior, or for selecting representative example chemicals for a model investigation. They can also help in deciding when accurate and precise knowledge of physical chemical property data is crucial and when approximate numbers suffice to conduct a model investigation.     

Hexachlorocyclohexanes in the Canadian archipelago. 1. Spatial distribution and pathways of alpha-, beta- and gamma-HCHS in surface water

Hexachlorocyclohexanes (HCHs) in the surface water of the Canadian Archipelago and south Beaufort Sea were measured in summer, 1999. Overall concentrations of HCH isomers were in order of abundance: alpha-HCH (3.5 +/- 1.2 ng L(-1)) > gamma-HCH (0.31 +/- 0.07 ng L(-1)) > beta-HCH (0.10 +/- 0.03 ng L(-1)). Concentrations and ratios of alpha-HCH/gamma-HCH decreased significantly (p < 0.001 to 0.003) from west to east, but there was no significant variation in alpha-HCH/ beta-HCH. The (+) enantiomer of alpha-HCH was preferentially degraded, with enantiomer fractions (EFs) ranging from 0.432-0.463 and increasing significantly (p < 0.001) from west to east. Concentrations also varied latitudinally for alpha-HCH and gamma-HCH (p < 0.002) but not for beta-HCH. Principal component analysis with variables alpha-HCH and gamma-HCH concentrations, EF, latitude, and longitude accounted for 71% (PC 1) and 16% (PC 2) of the variance. Mixing in the eastern Archipelago was modeled by assuming three end members with characteristic concentrations of alpha-HCH and gamma-HCH. The model accounted for the observed concentrations and higher EFs of alpha-HCH at the eastern stations.     

Accumulation of airborne hexachlorocyclohexanes and DDT in pine needles

The accumulation of alpha- and gamma-hexachlorocyclohexanes (HCHs) and p,p'-DDT in Scots pine needles was measured simultaneously with the concentrations in the surrounding air. All three compounds accumulate during the entire life span of the needles. For p,p'-DDT the general accumulation is overlaid by a concentration peak during winter, probably related to particle deposition. For the HCHs the accumulation is overlaid by a seasonal pattern with rapid accumulation during spring and summer months and constant concentrations during winter months. The concentrations of alpha-HCH in the air were more or less constant during the whole sampling period, whereas gamma-HCH shows an air concentration peak in spring and early summer. Air concentrations of p,p'-DDT were for the most part below the detection limit. There is little evidence of revolatilization from the needles, with the exception of a small decline of gamma-HCH concentration in summer after the peak air concentrations. The high accumulation rate of the HCHs during the warm season correlates with high levels of volatile organic compounds (VOCs) in the needles. We suggest that the variation of VOC content in the needles cause seasonal variation of the air-plant partitioning coefficient. An additional complicating factor is that the dry weight of the needles has to be corrected for the yearly variation of starch content. The results presented here question models of uptake of airborne contaminants by plants that assume rapid equilibria between the air and plants.     

Measurement of Air and VOC Vapor Fluxes during Gas-Driven Soil Remediation: Bench-Scale Experiments

In this laboratory study, an experimental method was developed for the quantitative analyses of gas fluxes in soil during advective air flow. One-dimensional column and two- and three-dimensional flow chamber models were used in this study. For the air flux measurement, n-octane vapor was used as a tracer, and it was introduced in the air flow entering the physical models. The tracer (n-octane) in the gas effluent from the models was captured for a finite period of time using a pack of activated carbon, which then was analyzed for the mass of n-octane. The air flux was calculated based on the mass of n-octane captured by the activated carbon and the inflow concentration. The measured air fluxes are in good agreement with the actual values for one- and two-dimensional model experiments. Using both the two- and three-dimensional models, the distribution of the air flux at the soil surface was measured. The distribution of the air flux was found to be affected by the depth of the saturated zone. The flux and flux distribution of a volatile contaminant (perchloroethene) was also measured by using the two-dimensional model. Quantitative information of both air and contaminant flux may be very beneficial for analyzing the performance of gas-driven subsurface remediation processes including soil vapor extraction and air sparging.     

Uncertainty of the sample size reduction step in pesticide residue analysis of large-sized crops

To estimate the uncertainty of the sample size reduction step, each unit in laboratory samples of papaya and cucumber was cut into four segments in longitudinal directions and two opposite segments were selected for further homogenisation while the other two were discarded. Jackfruit was cut into six segments in longitudinal directions, and all segments were kept for further analysis. To determine the pesticide residue concentrations in each segment, they were individually homogenised and analysed by chromatographic methods. One segment from each unit of the laboratory sample was drawn randomly to obtain 50 theoretical sub-samples with an MS Office Excel macro. The residue concentrations in a sub-sample were calculated from the weight of segments and the corresponding residue concentration. The coefficient of variation calculated from the residue concentrations of 50 sub-samples gave the relative uncertainty resulting from the sample size reduction step. The sample size reduction step, which is performed by selecting one longitudinal segment from each unit of the laboratory sample, resulted in relative uncertainties of 17% and 21% for field-treated jackfruits and cucumber, respectively, and 7% for post-harvest treated papaya. The results demonstrated that sample size reduction is an inevitable source of uncertainty in pesticide residue analysis of large-sized crops. The post-harvest treatment resulted in a lower variability because the dipping process leads to a more uniform residue concentration on the surface of the crops than does the foliar application of pesticides.     

An ion diffusion model in semi-permeable clay materials

Clay materials typically contain negative surface charges that induce electrostatic fields (or diffuse double layers) in electrolytes. During ion diffusion in a porous medium of clay materials, ions dynamically interact with the electrostatic fields associated with individual clay grains by depressing or expanding the electrostatic double layers, which subsequently affects ionic fluxes. Current theory of ion transport in porous media, however, cannot explicitly account for the dynamic interactions. Here we proposed a model by coupling electrodynamics and nonequilibrium thermodynamics (EDNT) to describe ion diffusion in clay materials as a complex function of factors including clay surface charge density, tortuosity, porosity, chemicoosmotic coefficient, and ion self-diffusivity. The model was validated by comparing the calculated and measured apparent ion diffusion coefficients in clay materials as a function of ionic strength. At transitional states, ion diffusive fluxes are dynamically related to the electrostatic fields, which shrink or expand as ion diffusion occurs. At steady states, the electrostatic fields are time-invariant and ion diffusive fluxes conform to flux and concentration gradient relationships; and apparent diffusivity can be approximated by the ion diffusivity in bulk electrolytes corrected by a tortuosity factor and macroscopic concentration discontinuities at the interfaces between clay materials and bulk solutions.     

Endosulfan and gamma-HCH in the arctic: an assessment of surface seawater concentrations and air-sea exchange

Arctic seawater concentrations of two currently used pesticides, endosulfan and gama-HCH, were collated from a variety of cruises undertaken throughout the 1990s up to 2000 for different regions of the Arctic Ocean. Surface seawater concentrations for alpha- and beta-endosulfan ranged from <0.1-8.8 (mean 2.3) pg/L and 0.1-7.8 (mean 1.5) pg/L, while gamma-HCH concentrations were approximately 100 fold higher than alpha-endosulfan, ranging between <0.70 and 894 (mean 250) pg/L. Geographical distributions for alpha-endosulfan revealed the highest concentrations in the western Arctic, specifically in the Bering and Chukchi Seas with lowest levels toward the central Arctic Ocean. In contrast, gamma-HCH revealed higher concentrations toward the central Arctic Ocean, with additional high concentrations in the coastal regions near Barrow, Alaska and the White Sea in northwest Russia, respectively. A fugacity approach was employed to assess the net direction of air-water transfer of these two pesticides, using coupled seawater and air concentrations. For alpha-endosulfan, water-air fugacity ratios (FR) were all <1 indicating net deposition to all regions of the Arctic Ocean, with the lowest values (0.1-0.2) evident in the Canadian Archipelago. Given the uncertainty in the temperature-adjusted Henry's Law constant (factor approximately10), it is plausible that equilibrium may have been reached for this compound in the western fringes of the Arctic Ocean where the highest water concentrations were observed. Similarly, FR values for gamma-HCH were generally <1 and in agreement     

A dynamic model of the fate of organic chemicals in a multilayered air/soil system: development and illustrative application

A new site-specific, dynamic model (SoilPlus) was developed to simulate the fate of nonionized organic chemicals in the air/litter/soil system; key features of the model are the double-layered air compartment interacting dynamically with multilayered litter and soil compartments, with seasonal dissolved organic carbon (DOC) fluxes. The model describes the soil environment calculating separate mass balances for water, chemical, and organic matter. SoilPlus underwent a process of benchmarking and evaluation in order to reach a satisfying confirmation of its predictive capability. Several simulations were performed to estimate the role of litter and DOC in affecting the fate of a model contaminant for POPs (hexachlorobenzene). The model shows that litter can behave as a buffer in the process of transferring hexachlorobenzene from air to the mineral soil and as a trap when hexachlorobenzene tends to move from a contaminated field toward clean air. DOC seems to behave as a leaching-enhancer in certain climatic conditions (heavy rainfall, high DOC concentrations), but it does not appear to move significant amounts of HCB in a year calculation.     

Assessing model uncertainty of bioaccumulation models by combining chemical space visualization with a process-based diagnostic approach

As models describing human exposure to organic chemicals gain wider use in chemical risk assessment and management, it becomes important to understand their uncertainty. Although evaluation of parameter sensitivity/uncertainty is increasingly common, model uncertainty is rarely assessed. When it is, the assessment is generally limited to a handful of chemicals. In this study, a strategy for more comprehensive model uncertainty assessment was developed. A regulatory model (EUSES) was compared with a research model based on more recent science. Predicted human intake was used as the model end point. Chemical space visualization techniques showed that the extent of disagreement between the models varied strongly with chemical partitioning properties. For each region of disagreement, the primary human exposure vector was determined. The differences between the models' process algorithms describing these exposure vectors were identified and evaluated. The equilibrium assumption for root crops in EUSES caused overestimations in daily intake of superhydrophobic chemicals (log K(OW) > 11, log K(OA) > 10), whereas EUSES's approach to calculating bioaccumulation in fish prey resulted in underestimations for hydrophobic compounds (log K(OW) ～ 6-8). Uptake of hydrophilic chemicals from soil and bioaccumulation of superhydrophobic chemicals in zooplankton were identified as important research areas to enable further reduction of model uncertainty in bioaccumulation models.     

Dechlorane plus, a chlorinated flame retardant, in the Great Lakes

A highly chlorinated flame retardant, Dechlorane Plus (DP), was detected and identified in ambient air, fish, and sediment samples from the Great Lakes region. The identity of this compound was confirmed by comparing its gas chromatographic retention times and mass spectra with those of authentic material. This compound exists as two gas chromatographically separable stereoisomers (syn and anti), the structures of which were characterized by one- and two-dimensional proton nuclear magnetic resonance. DP was detected in most air samples, even at remote sites. The atmospheric DP concentrations were higher at the eastern Great Lakes sites (Sturgeon Point, NY, and Cleveland, OH) than those at the western Great Lakes sites (Eagle Harbor, MI, Chicago, IL, and Sleeping Bear Dunes, MI). Atthe Sturgeon Point site, DP concentrations once reached 490 pg/m3. DP atmospheric concentrations were comparable to those of BDE-209 at the eastern Great Lakes sites. DP was also found in sediment cores from Lakes Michigan and Erie. The peak DP concentrations were comparable to BDE-209 concentrations in the sediment core from Lake Erie butwere about 30 times lower than BDE-209 concentrations in the core from Lake Michigan. In the sediment cores, the DP concentrations peaked around 1975-1980, and the surficial concentrations were 10-80% of peak concentrations. Higher DP concentrations in air samples from Sturgeon Point, NY, and in the sediment core from Lake Erie suggest that DP's manufacturing facility in Niagara Falls, NY, may be a source. DP was also detected in archived fish (walleye) from Lake Erie, suggesting that this compound is, at least partially, bioavailable.     

Relative importance of gas-phase diffusive and advective tichloroethene (TCE) fluxes in the unsaturated zone under natural conditions

It was hypothesized that atmospheric pressure changes can induce gas flow in the unsaturated zone to such an extent that the advective flux of organic vapors in unsaturated-zone soil gas can be significant relative to the gas-phase diffusion flux of these organic vapors. To test this hypothesis, a series of field measurements and computer simulations were conducted to simulate and compare diffusion and advection fluxes at a trichloroethene-contaminated field site at Picatinny Arsenal in north-central New Jersey. Moisture content temperature, and soil-gas pressure were measured at multiple depths (including at land surface) and times for three distinct sampling events in August 1996, October 1996, and August 1998. Gas pressures in the unsaturated zone changed significantly over time and followed changes measured in the atmosphere. Gas permeability of the unsaturated zone was estimated using data from a variety of sources, including laboratory gas permeability measurements made on intact soil cores from the site, a field air pump test, and calibration of a gas-flow model to the transient, one-dimensional gas pressure data. The final gas-flow model reproduced small pressure gradients as observed in the field during the three distinct sampling events. The velocities calculated from the gas-flow model were used in transient, one-dimensional transport simulations to quantify advective and diffusive fluxes of TCE vapor from the subsurface to the atmosphere as a function of time for each sampling event. Effective diffusion coefficients used for these simulations were determined from independent laboratory measurements made on intact soil cores collected from the field site. For two of the three sampling events (August 1996 and August 1998), the TCE gas-phase diffusion flux at land surface was significantly greater than the advection flux over the entire sampling period. For the second sampling event (October 1996), the advection flux was frequently larger than the diffusion flux. When averaged over the second sampling event, the advection and diffusion fluxes were comparable in magnitude. Sensitivity analyses indicate that diffusion fluxes increase significantly with increases in air-filled porosity near land surface, whereas advection fluxes do not. For October 1996, the comparable advection and diffusion fluxes were caused by high moisture content near land surface and a subsequent reduction in the diffusion flux relative to the advection flux. These results indicate that under certain environmental conditions, the organic vapor advection flux from the unsaturated zone to the atmosphere may be equal to or greater than the diffusion flux.