Geo-referenced multimedia environmental fate model (G-CIEMS): model formulation and comparison to the generic model and monitoring approaches

A spatially resolved and geo-referenced dynamic multimedia environmental fate model, G-CIEMS (Grid-Catchment Integrated Environmental Modeling System) was developed on a geographical information system (GIS). The case study for Japan based on the air grid cells of 5 x 5 km resolution and catchments with an average area of 9.3 km2, which corresponds to about 40,000 air grid cells and 38,000 river segments/catchment polygons, were performed for dioxins, benzene, 1,3-butadiene, and di-(2-ethyhexyl)phthalate. The averaged concentration of the model and monitoring output were within a factor of 2-3 for all the media. Outputs from G-CIEMS and the generic model were essentially comparable when identical parameters were employed, whereas the G-CIEMS model gave explicit information of distribution of chemicals in the environment. Exposure-weighted averaged concentrations (EWAC) in air were calculated to estimate the exposure ofthe population, based on the results of generic, G-CIEMS, and monitoring approaches. The G-CIEMS approach showed significantly better agreement with the monitoring-derived EWAC than the generic model approach. Implication for the use of a geo-referenced modeling approach in the risk assessment scheme is discussed as a generic-spatial approach, which can be used to provide more accurate exposure estimation with distribution information, using generally available data sources for a wide range of chemicals.     

Estimating the influence of forests on the overall fate of semivolatile organic compounds using a multimedia fate model

On the basis of recently reported measurements of semivolatile organic compound (SOC) uptake in forest canopies, simple expressions are derived that allow the inclusion of a canopy compartment into existing non-steady-state multimedia fate models based on the fugacity approach. One such model is used to assess how the inclusion of the canopy compartment in the model affects the calculated overall behavior of SOCs with specific physical--chemical properties. The primary effect of the forest is an increase in the net atmospheric deposition to the terrestrial environment, reducing atmospheric concentrations and accordingly the extent of deposition to the agricultural and aquatic environments. This effect was most pronounced for chemicals with log KOA around 9-10 and log KAW -2 to -3; their average air concentrations during the growing season decreased by a factor of 5 when the canopy compartment was included. Concentration levels in virtually all compartments are decreased at the expense of increased concentrations in the forest soil. The effect of the forest lies not in a large capacity for these chemicals but in the efficiency of pumping the chemicals from the atmosphere to the forest soil, a storage reservoir with high capacity from which the chemicals can return to the atmosphere only with difficulty. Because of seasonal variability of canopy size and atmospheric stability, uptake into forests is higher during spring and summer than in winter. The model suggests that this may dampen temperature-driven seasonal fluctuations of air concentrations and in regions with large deciduous forests may lead to a temporary, yet notable dip in air concentrations during leaf development in spring. A sensitivity analysis revealed a strong effect of forest cover, forest composition, and degradation half-lives. A high degradation loss on the plant surface has the effect of preventing the saturation of the small plant reservoir and can cause very significant reductions in atmospheric concentrations of those SOCs for which uptake in the canopy is limited by the size of the reservoir.     

Winter-time climatic control on dissolved organic carbon export and surface water chemistry in an Adirondack forested watershed

Although most of forested watersheds in temperate and boreal regions are snow-covered for a substantial portion of the year, responses of biogeochemical processes under the snow pack to climatic fluctuations are poorly understood. We investigated responses of dissolved organic carbon (DOC) and surface water chemistry in stream and lake discharge waters draining the Arbutus Lake Watershed in the Adirondacks of New York State to climatic fluctuations during the snow-covered months from December through April. Interannual variability in stream discharge corresponded to changes in air temperature and snow pack depth across the winter months. Concentrations of DOC in stream water draining a subcatchment showed immediate positive responses to rising temperatures and subsequent increases in runoff during most snowmelt events. Increases in DOC concentrations usually coincided with decreases in pH and increases in total aluminum (Al) concentrations, while the correlations between concentrations of DOC and SO4(2-) or base cations were negative. Although changes in air temperature, snow pack depth, and runoff were all significantly correlated with stream water concentrations of major solutes, stepwise linear regression found that runoff was the best predictor of solute concentrations. Results of stepwise linear regression with long-term monthly monitoring data collected at the lake outlet showed weaker but still consistent climatic effects on interannual variations in concentrations of DOC and other solutes. Over the 17 winter periods from December 1983 through April 2000, changes in seasonal average concentrations of DOC, H+, and Al in lake discharge generally corresponded to interannual variations in temperature, precipitation, and runoff, while SO4(2-) and base cations displayed an opposite trend. The results suggest that snowmelt-mediated DOC responses to temperature fluctuations during the winter months might offset increases in the surface water pH caused by decreasing acidic deposition and pose a potential hazard of Al toxicity in surface waters.     

Fate of perfluorinated carboxylates and sulfonates during snowmelt within an urban watershed

The transport dynamics of perfluorinated carboxylic acids and sulfonates during snowmelt in the highly urbanized Highland Creek watershed in Toronto, Canada was investigated by analyzing river water, bulk snow, and groundwater, sampled in February and March 2010, by means of liquid chromatography-tandem mass spectrometry. Perfluorohexanoate, perfluorooctanoate, and perfluorooctane sulfonate were dominant in river water, with concentrations of 4.0-14 ng·L(-1), 2.2-7.9 ng·L(-1), and 2.1-6.5 ng·L(-1), respectively. Relatively high levels of perfluorohexanoate may be related to the recent partial replacement in various consumer products of perfluorooctyl substances with shorter-chained perfluorinated compounds (PFCs). Highest PFC concentrations were found within the more urbanized part of the drainage area, suggestive of residential, industrial, and/or traffic-related sources. The riverine flux of PFCs increased during the snowmelt period, but only approximately one-fifth of the increased flux can be attributed to PFCs present in the snowpack, mostly because concentration in snow are generally quite low compared to those in river water. The remainder of the increased flux must be due to the mobilization of PFCs by the high flow conditions prevalent during snowmelt. Run-off behavior was clearly dependent on perfluoroalkyl chain length: Dilution with relatively clean snowmelt water caused a drop in the river water concentrations of short-chain PFCs at high flow during early melting. This prevented an early concentration peak of those water-soluble PFCs within the stream, as could have been expected in response to their early release from a melting snowpack. Instead, concentrations of particle-associated long-chain PFCs in creek water peaked early in the melt, presumably because high flow mobilized contaminated particles from impervious surfaces in the more urbanized areas of the watershed. The ability to enter the subsurface and deeper groundwater aquifers increased with the PFCs' water solubility, that is, was inversely related to perfluoroalkyl chain length.     

Coastal water quality impact of stormwater runoff from an urban watershed in southern California

Field studies were conducted to assess the coastal water quality impact of stormwater runoff from the Santa Ana River, which drains a large urban watershed located in southern California. Stormwater runoff from the river leads to very poor surf zone water quality, with fecal indicator bacteria concentrations exceeding California ocean bathing water standards by up to 500%. However, cross-shore currents (e.g., rip cells) dilute contaminated surf zone water with cleaner water from offshore, such that surf zone contamination is generally confined to < 5 km around the river outlet. Offshore of the surf zone, stormwater runoff ejected from the mouth of the river spreads out over a very large area, in some cases exceeding 100 km2 on the basis of satellite observations. Fecal indicator bacteria concentrations in these large stormwater plumes generally do not exceed California ocean bathing water standards, even in cases where offshore samples test positive for human pathogenic viruses (human adenoviruses and enteroviruses) and fecal indicator viruses (F+ coliphage). Multiple lines of evidence indicate that bacteria and viruses in the offshore stormwater plumes are either associated with relatively small particles (< 53 microm) or not particle-associated. Collectively, these results demonstrate that stormwater runoff from the Santa Ana River negatively impacts coastal water quality, both in the surf zone and offshore. However, the extent of this impact, and its human health significance, is influenced by numerous factors, including prevailing ocean currents, within-plume processing of particles and pathogens, and the timing, magnitude, and nature of runoff discharged from river outlets over the course of a storm.     

Flow fingerprinting fecal pollution and suspended solids in stormwater runoff from an urban coastal watershed

Field studies were conducted to characterize the concentration vs streamflow relationships (or "flow fingerprints") of fecal pollution and suspended solids in stormwater runoff from the Santa Ana River watershed, the largest watershed in southern California. The concentrations of fecal indicator bacteria and F+ coliphages (viruses infecting E. coli) exhibit little-to-no dependence on streamflow rates, whereas the concentrations of total suspended solids (TSS) exhibit a very strong (power-law) dependence on streamflow rates. The different flow fingerprints observed for fecal pollutants, on one hand, and TSS, on the other hand, reflect different sources and transport pathways for these stormwater constituents. The flow-independent nature of fecal indicator bacteria and F+ coliphages is consistent with the idea that these contaminants are ubiquitously present on the surface of the urban landscape and rapidly partition into the surface water as the landscape is wetted by rainfall. The flow-dependent nature of TSS, on the other hand, is usually ascribed to the shear-induced erosion of channel bed sediments and/or the expansion of drainage area contributing to runoff. The apparent ubiquity of fecal indicator bacteria and F+ coliphages, together with the very high storm-loading rates of fecal indicator bacteria and the low detection frequency of human adenovirus and human enterovirus, suggest that fecal pollution in stormwater runoff from the Santa Ana River watershed is primarily of nonhuman waste origin.     

Guidance on the selection of efficient computational methods for multimedia fate models

Dynamic multimedia fate models (MFMs) have to deal with the temporal and spatial variation of physical-chemical properties, environmental scenarios, and chemical emissions. In such complex simulation tools, an analytical solution is not practically feasible, and even a numerical approach requires a suitable choice of the method in order to obtain satisfying speed and reliability, particularly when certain combinations of modeling scenarios and chemical properties occur. In this paper, considering some examples of a wide range of realistic chemical and scenario properties, some sources of stiffness in MFM equations are pinpointed. Next, a comparison of the performances of several numerical schemes (chosen as representatives of three wide classes) is performed. The accuracy and the computational effort required by each method is evaluated, illustrating the general effectiveness of automatically adapted timesteps in numerical algorithms and the pros and cons of implicit timestepping. The results show that automatic error control methods can significantly improve the quality of the computed solutions and most often lead to relevant savings in computing time. Additionally, explicit and implicit methods are compared, indicating that an implicit method of medium order (around 5) is the best choice as a general purpose MFM computing engine.     

The role of the snowpack on the fate of alpha-HCH in an atmospheric chemistry-transport model

A dynamic snowpack module was implemented in the Danish Eulerian Hemispheric Model Persistant Organic Pollutants (DEHM-POP), an atmospheric chemistry-transport model designed to study the environmental fate of persistent organic pollutants in the Northern Hemisphere. The role of the snowpack on the fate of alpha-hexachlorocyclohexane (alpha-HCH) was investigated by making simulations both with and without the formation of a snowpack and comparing model results with data from 21 air monitoring sites. The inclusion of a dynamic snowpack module in the DEHM-POP model generally improves the fit between modeled and observed alpha-HCH air concentrations for the winter and spring seasons and the overall correlation coefficient between predicted and observed concentrations are improved at 8 of the sites. The predicted snowpack concentrations are in good agreement with the few available snow measurements from the Arctic. The presence of a snowpack increases surface boundary layer air concentrations of alpha-HCH at midlatitudes, while the effect is more pronounced in the Arctic due to the longer periods of snow cover. The results indicate that the snowpack module in DEHM-POP acts as a fast-exchanging temporary storage medium for alpha-HCH, as significant fractions were rapidly revolatilized back into the atmosphere following deposition with snowfall, although the current parametrization for vapor-exchange probably over emphasizes this process. Nonetheless, increased air concentrations observed between March and May ("spring maximum events"; SME) at several high latitude monitoring stations are also predicted by the model. The model results indicate that the SMEs are associated with the revolatilization of previously deposited chemical from the snowpack, following a reduction in the capacity of the snowpack to retain alpha-HCH with increasing temperatures toward the end of the winter period, rather than the actual melting of the snowpack. The SMEs are not predicted at all the Arctic monitoring sites by the model, and the significance of the snowpack in controlling these in the model is, therefore, open to question given the uncertainties in the snow-air partition coefficient (K(sa)) and the reliance of the model on a one-layer snowpack rather than a multilayered snowpack.     

Optimization of stormwater filtration at the urban/watershed interface

Environmental pollution from cities is a major ecological problem attributed to contaminated runoff from nonpoint sources. The U.S. Environmental Protection Agency's guidance on implementation of total maximum daily loads (TMDL) does not adequately cover methods to improve waters impaired by nonpoint sources. To comply with TMDLs, cities may install filters in curb inlets, or use other Best Management Practices (BMPs). We tested 10 different filters and found their effectiveness in retaining pollutants ranged from 0 to >90%, depending on combinations of pollutant types (metals, pathogens, and total suspended sediments (TSS)) and filter materials. Hence, the decision to deploy filters into curb inlets must consider land use patterns associated with specific categories of pollutants generated within cities. We developed a geographic information system (GIS)-enabled model for estimating and mitigating emissions of pollutants from urban regions into watersheds. The model uses land use categories and pollutant loadings to optimize strategic placement of filters to accommodate TMDLs. For example, in a city where the landuse pattern generates 4 x 10(6) kg of TSS, 55 kg of Cd, and 2 x 10(3) kg of Zn per year into 498 curb inlets that discharge into a sensitive watershed, the optimized placement of 137, 92, and 148 filters can achieve TMDL endpoints for each pollutant, respectively. We show further that 158 strategically placed filters effectively meet the requirements simultaneously for all three pollutants, a result at least 5 times more effective than random placement of filters.     

Occurrence and fate of macrolide antibiotics in wastewater treatment plants and in the Glatt Valley watershed, Switzerland

An analytical method was developed for determining macrolide antibiotics in treated wastewater effluents and in ambient water based on solid-phase extraction and LC/MS analysis as well as on LC/MS/MS for structural confirmation. In wastewater treatment plants (WWTPs) macrolides are only partly eliminated and can therefore reach the aquatic environment. In treated effluents from three WWTPs in Switzerland, clarithromycin, roxithromycin, and erythromycin-H2O, the main degradation product of erythromycin, were found. The most abundant, clarithromycin, reflects the consumption pattern of macrolide antibiotics. Summer concentrations of clarithromycin varied between 57 and 330 ng/L in treated WWTP effluents. In the WWTP Kloten-Opfikon seasonal differences revealed a load two times higher in winter than in summer. The higher abundance of erythromycin-H2O in the effluent of WWTP Kloten-Opfikon can be explained by distinct consumption patterns due to the main international airport of Switzerland in the catchment area. In the Glatt River clarithromycin reached concentrations of up to 75 ng/L. Mass flux determinations in treated effluents and in river water in the Glatt Valley watershed showed that elimination of clarithromycin along the river stretch of 36 km is insignificant (<20%). Investigations in the Glatt River before and after the diversion of the largest WWTP revealed an observable decrease in clarithromycin loads.     

Cyclic exchanges and level of coupling between environmental media: intermedia feedback in multimedia fate models

The importance of cyclic transport of chemicals between media in the environment can be expressed in terms of the Feedback correction factor--a multiplier that accounts for the fraction of an emission that returns to the medium of release after transfer to other media. This factor is calculated analytically by explicitly solving the appropriate system of mass balance equations or using matrix techniques. It generalizes the concept of stickiness, the ratio between the net and the overall deposition rate constants, to multipathway feedback, while providing a clearer view of the level of coupling between media and analyzing the importance of coupling. This paper first shows the usefulness of the total removal rate coefficient in each media (sum of degradation rate and all intermedia transfer rates) as a baseline to determine the chemical mass in different media, the characteristic travel distance and to understand the cyclic behavior, rather than starting from the degradation lifetimes or the overall persistence in the environment. Starting from this baseline, the importance of feedback is limited for most organic chemicals. The predicted media concentrations are influenced by less than 10% due to the cyclic nature of the intermedia transport for more than 90% of the 317 tested chemicals in a 4-compartment, steady-state, closed-system multimedia model. The Feedback correction factor is always less than a factor of 5 with the greatest values when transfer fractions are important in both directions for adjacent media. This corresponds to a restricted range in the K(AW) and K(OA) space with long chemical lifetimes in both adjacent media. This analysis of the importance of the Feedback correction factor, in conjunction with resultant criteria for when cyclic exchanges between media are likely to be significant, facilitates a more transparent understanding of how substance masses are distributed in the modeled system. It is one of the important criteria to determine to what extent media can be independently modeled.     

Polybrominated diphenyl ethers in watershed soils of the Pearl River Delta, China: occurrence, inventory, and fate

Soils play an important role in the distribution and biogeochemical cycling of polybrominated diphenyl ethers (PBDEs) as they are a major reservoir and sink for PBDEs due to their large sorption capacity. In this study, concentrations, compositional profiles, mass inventories, and fate of sigma9PBDEs (28, 47, 66, 100, 99, 154, 153, 138, 183) and BDE 209 were investigated in 33 surface soils, six profile soils, and three point-source polluted soils (close to e-waste dismantling sites) from the Pearl River Delta (PRD), China. The concentrations of sigma9PBDEs and BDE 209 in the surface soils ranged from 0.13 to 3.81 ng/g with an average of 1.02 ng/g and from 2.38 to 66.6 ng/g with an average of 13.8 ng/g, respectively, and ranged from 1.93 to 19.5 ng/g and from 25.7 to 102 ng/g, respectively, in the point-source contaminated soils. The PBDE compositional patterns in the surface soils indicated deca-BDE, penta-BDE, and octa-BDE products as the main sources, but those in the point-source samples suggested deca-BDE and octa-BDE technical mixtures as the dominant sources. The mass inventories of PBDEs in soils of the PRD were estimated at 3.98 and 44.4 t for sigma9PBDEs and BDE 209, respectively. The average loading of PBDEs in the soils was comparable to that in the sediments of the Pearl River Estuary, suggesting that soil erosion and surface runoff are an important mode to transport PBDEs from terrestrial sources to oceans in the PRD. Individual BDE congeners, sigma9PBDEs, and PBDE 209, were significantly correlated with total organic carbon (TOC), and a good regression (except for BDE 47) between the logarithms of TOC-normalized BDE average concentrations and their log K(ow) was also obtained, indicating that sorption of PBDEs on soil organic matter governed their spatial distribution, transportation, and fate in the soils. Predicted aqueous and gaseous concentrations of PBDEs were derived from the soil-water and soil-air partitioning models, respectively, and good agreements were obtained between the predicted and previously reported values. BDE 47 and/or 28 did not appear to follow the same trend for these models, an indication that an portion of them was likely the biodegradation byproducts in soils.     

Screening level risk assessment model for chemical fate and effects in the environment

A screening level risk assessment model is developed and described to assess and prioritize chemicals by estimating environmental fate and transport, bioaccumulation, and exposure to humans and wildlife for a unit emission rate. The most sensitive risk endpoint is identified and a critical emission rate is then calculated as a result of that endpoint being reached. Finally, this estimated critical emission rate is compared with the estimated actual emission rate as a risk assessment factor. This "back-tracking" process avoids the use of highly uncertain emission rate data as model input. The application of the model is demonstrated in detail for three diverse chemicals and in less detail for a group of 70 chemicals drawn from the Canadian Domestic Substances List. The simple Level II and the more complex Level III fate calculations are used to "bin" substances into categories of similar probable risk. The essential role of the model is to synthesize information on chemical and environmental properties within a consistent mass balance framework to yield an overall estimate of screening level risk with respect to the defined endpoint. The approach may be useful to identify and prioritize those chemicals of commerce that are of greatest potential concern and require more comprehensive modeling and monitoring evaluations in actual regional environments and food webs.     

Scaling and management of fecal indicator bacteria in runoff from a coastal urban watershed in southern California

This paper describes a series of field studies aimed at identifying the spatial distribution and flow forcing of fecal indicator bacteria in dry and wet weather runoff from the Talbert watershed, a highly urbanized coastal watershed in southern California. Runoff from this watershed drains through tidal channels to a popular public beach, Huntington State Beach, which has experienced chronic surf zone water quality problems over the past several years. During dry weather, concentrations of fecal indicator bacteria are highest in inland urban runoff, intermediate in tidal channels harboring variable mixtures of urban runoff and ocean water, and lowest in ocean water at the base of the watershed. This inland-to-coastal gradient is consistent with the hypothesis that urban runoff from the watershed contributes to coastal pollution. On a year round basis, the vast majority (>99%) of fecal indicator bacteria loading occurs during storm events when runoff diversions, the management approach of choice, are not operating. During storms, the load of fecal indicator bacteria in runoff follows a power law of the form L approximately Qn, where L is the loading rate (in units of fecal indicator bacteria per time), Q is the volumetric flow rate (in units of volume per time), and the exponent n ranges from 1 to 1.5. This power law and the observed range of exponent values are consistent with the predictions of a mathematical model that assumes fecal indicator bacteria in storm runoff originate from the erosion of contaminated sediments in drainage channels or storm sewers. The theoretical analysis, which is based on a conventional model for the shear-induced erosion of particles from land and channel-bed surfaces, predicts that the magnitude of the exponent n reflects the geometry of the stormwater conveyance system from which the pollution derives. This raises the possibility that the scaling properties of pollutants in stormwater runoff (i.e., the value of n) may harbor information about the origin of nonpoint source pollution.