Modeling urban films using a dynamic multimedia fugacity model.

A thin film coats impervious urban surfaces that can act as a source or sink of organic pollutants to the greater environment. We review recent developments in the understanding of film and film-associated pollutant behavior and incorporate them into an unsteady-state version of the fugacity based Multimedia Urban Model (MUM), focusing on detailed considerations of surface film dynamics. The model is used to explore the conditions under which these atmospherically-derived films act as a temporary source of chemicals to the air and/or storm water. Assuming film growth of 2.1 nm d(-1) (Wu et al., 2008a), PCB congeners 28 and 180 reach air-film equilibrium within hours and days, respectively. The model results suggest that the film acts as a temporary sink of chemicals from air during dry and cool weather, as a source to air in warmer weather, and as a source to storm water and soil during rain events. Using the downtown area of the City of Toronto Canada, as a case study, the model estimates that nearly 1 g d(-1) of ∑(5)PCBs are transferred from air to film to storm water.

PAH repartitioning in field-contaminated sediment following removal of the labile chemical fraction.

The effect of removing the labile chemical fraction associated with sediment particles followed by internal chemical redistribution was examined in a field-contaminated sediment. Using data from desorption equilibrium (organic carbon-water partition coefficients, K(OC)) and kinetic (rate of release) experiments, estimates of polynuclear aromatic hydrocarbon biphasic partitioning and desorption rates for both the labile and nonlabile chemical fractions or organic matter compartments were obtained. Sediment K(OC) values increased between 50 and 150% after removal of the labile chemical fraction. Following depletion of the labile chemical fraction during desorption experiments, sediment was stored 30 and 90 days to allow for chemical redistribution between the labile and nonlabile compartments. The subsequent desorption data indicated repartitioning had occurred with the nonlabile chemical fraction recharging the labile compartment. The results provide evidence that chemical transfer between organic matter compartments, either through interparticle porewater or via direct intraparticle compartmental exchange, is a real phenomenon that occurs over relatively short times (weeks to months). This calls into question the idea that hydrophobic organic pollutants in the nonlabile chemical fraction are sequestered or less bioavailable over the long-term and has implications for water quality impacts during contaminated sediment resuspension events, risk assessment of polluted sites, and selection of sediment remediation strategies.

Elevated in-home sediment contaminant concentrations - the consequence of a particle settling-winnowing process from Hurricane Katrina floodwaters.

Sediment samples were collected from two homes which were flooded in the wake of Hurricane Katrina in August 2005. The samples were analyzed for trace metals and semi-volatile organic compounds using techniques based on established EPA methods. The data showed higher concentrations of some metals and semi-volatile organic pollutants than reported in previous outdoor sampling events of soils and sediments. The Lake Pontchartrain sediments became resuspended during the hurricane, and this material subsequently was found in the residential areas of New Orleans following levee breaches. The clay and silt particles appear to be selectively deposited inside homes, and sediment contaminant concentrations are usually greatest within this fraction. Re-entry advisories based on outdoor sample concentration results may have under-predicted the exposure levels to homeowners and first responders. All contaminants found in the sediment sampled in this study have their origin in the sediments of Lake Pontchartrain and other localized sources.

Desorption kinetics of hydrophobic organic chemicals from sediment to water: a review of data and models.

Resuspension of contaminated sediment can lead to the release of toxic compounds to surface waters where they are more bioavailable and mobile. Because the timeframe of particle resettling during such events is shorter than that needed to reach equilibrium, a kinetic approach is required for modeling the release process. Due to the current inability of common theoretical approaches to predict site-specific release rates, empirical algorithms incorporating the phenomenological assumption of biphasic, or fast and slow, release dominate the descriptions of nonpolar organic chemical release in the literature. Two first-order rate constants and one fraction are sufficient to characterize practically all of the data sets studied. These rate constants were compared to theoretical model parameters and functionalities, including chemical properties of the contaminants and physical properties of the sorbents, to determine if the trends incorporated into the hindered diffusion model are consistent with the parameters used in curve fitting. The results did not correspond to the parameter dependence of the hindered diffusion model. No trend in desorption rate constants, for either fast or slow release, was observed to be dependent on K(OC) or aqueous solubility for six and seven orders of magnitude, respectively. The same was observed for aqueous diffusivity and sediment fraction organic carbon. The distribution of kinetic rate constant values was approximately log-normal, ranging from 0.1 to 50 d(-1) for the fast release (average approximately 5 d(-1)) and 0.0001 to 0.1 d(-1) for the slow release (average approximately 0.03 d(-1)). The implications of these findings with regard to laboratory studies, theoretical desorption process mechanisms, and water quality modeling needs are presented and discussed.

Field observation and modeling of dissolved fraction sediment-water exchange coefficients for PCBs in the Hudson River.

Chemical fate and transport models that simulate sediment-water exchange of contaminants typically employ empirically determined sediment-water exchange coefficients for the dissolved fraction to describe the net effect of poorly understood mechanisms. This paper presents field-derived observations of the coefficient for 12 PCB congeners and two PCB mixtures in the Thompson Island Pool, Hudson River, and also presents an evaluation of a theoretical sediment-water exchange model. An extensive PCB data set was used to compute apparent coefficients for PCBs in the pool. Average exchange coefficients for the 12 congeners ranged from 2.6 to 18.8 cm/ day, and results showed a strong seasonal dependence. Peak coefficient values occurred in mid-May to early July, preceding peak water temperatures by 1 month and lagging the spring high-flow period. The coefficients increase with increasing partition coefficients, suggesting a dependence on congener properties. The large magnitude of the coefficients and the variation among the congeners is inconsistent with the pore-water molecular-diffusion transport process. A theory-based, mechanistic two-layer model reproduces the nonlinear relationship between the sediment-water exchange coefficients and partition coefficients. This model includes transfer through the mixed sediment layer by bioturbation and diffusion transfer through a water-side boundary layer governed by flow velocity. Results suggest that this algorithm can provide increased accuracyto future system-level fate and transport models for hydrophobic chemicals. The seasonal variation in the transfer coefficient appears to be a poorly understood interaction of physical and biological processes and merits further study.

Obtaining quantitative vapor emissions estimates of polychlorinated biphenyls and other semivolatile organic compounds from contaminated sites.

Soils contaminated with polychlorinated biphenyls (PCBs) and other semivolatile organic compounds (SVOCs) represent a potentially major, ongoing source of these compounds to the environment, especially during warmer temperatures. A great deal of work has been devoted to understanding the mechanisms that govern the vaporization of SVOCs from soil, but to date, few quantitative estimates have been published regarding emissions from contaminated sites. The present paper describes methods for obtaining quantitative estimates of SVOCs from soils based on flux chamber measurements, modeling, and ambient air measurements. On wet (i.e., H2O) soils, SVOCs at very low chemical loading levels on the adsorption sites (the so-called critical chemical concentration, critical loading, or saturation concentration) will behave, for volatilization purposes, as the pure-liquid substance would. For one soil, the PCB critical concentration was determined to be 775 ppm (95% confidence interval, 5.40E+02). Flux chamber-measured emissions from two contaminated sites were used and compared to model estimated values. The results agree reasonably well and indicate that the modeling approach used provided a conservative upper bound on the emissions. These approaches can be used to develop emissions estimates for SVOC-contaminated sites and inputs to air dispersion models.

Volatilization of contaminants from suspended sediment in a water column during dredging.

Remedial dredging of contaminated bed sediments in rivers and lakes results in the suspension of sediment solids in the water column, which can potentially be a source for evaporation of hydrophobic organic compounds (HOCs) associated with the sediment solids. Laboratory experiments were conducted in an oscillating grid chamber to simulate the suspension of contaminated sediments and flux to air from the surface of the water column. A contaminated field sediment from Indiana Harbor Canal (IHC) and a laboratory-inoculated University Lake (UL) sediment, Baton Rouge, LA, were used in the experiments, where water and solids concentration and particle size distribution were measured in addition to contaminant fluxes to air. A transient model that takes into account contaminant desorption from sediment to water and evaporation from the water column was used to simulate water and sediment concentrations and air fluxes from the solids suspension. In experiments with both sediments, the total suspended solids (TSS) concentration and the average particle diameter of the suspended solids decreased with time. As expected, the evaporative losses were higher for compounds with higher vapor pressure and lower hydrophobicity. For the laboratory-inoculated sediment (UL), the water concentrations and air fluxes were high initially and decreased steadily implying that contaminant release to the water column from the suspended solids was rapid, followed by evaporative decay. For the field sediments (IHC), the fluxes and water concentrations increased initially and subsequently decreased steadily. This implied that the initial desorption to water was slow and that perhaps the presence of oil and grease and aging influenced the contaminant release. Comparison of the model and experimental data suggested that a realistic determination of the TSS concentration that can be input into the model was the most critical parameter for predicting air emission rates.