Column- and catchment-scale transport of cadmium: effect of dissolved organic matter

In the Ellen catchment on the Pinjarra Plain, NE of Perth in Western Australia, cadmium from fertilisers is starting to leach from soils. About 70% of surface soils in the Ellen catchment are sandy and often on top of a shallow ephemeral water table. Adsorption of Cd in the sandy soils of the Ellen catchment was studied by batch adsorption and by leaching small columns of soil. Adsorption of Cd increases linearly with increasing soil organic matter content and exponentially with increasing pH. Cadmium is significantly mobilised in the sandy soils by dissolved organic matter.The capacity of most of the sandy soils in the Ellen catchment to adsorb phosphate from fertiliser has been saturated. Resulting concentrations in Ellen Brook average 500 μg L⁻¹ P. Cadmium is adsorbed more strongly in the sandy soils than phosphate and is just starting to leach into Ellen Brook. From a comparison of Cd/P ratios in water, soils and fertiliser, cadmium concentrations in Ellen Brook are estimated to be at 10–30% of their maximum for complete breakthrough from soils. Present concentrations of Cd in Ellen Brook average 0.1 μg L⁻¹ and are estimated to approach the maximum for complete breakthrough in 100 yr. Maximum Cd concentrations in Ellen Brook could range from 0.6 to 2 μg L⁻¹, depending on rates of input with fertiliser and future increases in agricultural land use in the catchment.Breakthrough curves, resulting from leaching Cd through small columns of sandy soil, indicate that adsorption significantly increases the effective hydrodynamic dispersion of Cd. Longitudinal dispersivities, measured at pore-water velocities of 0.7–14 m day⁻¹, were 5 cm for Cd and 0.1–0.2 cm for chloride. The much greater dispersion of Cd in the sandy soils than of chloride is shown not to be caused by non-equilibrium adsorption.     

On-road vehicle particulate matter and gaseous emission distributions in Las Vegas, Nevada, compared with other areas

During the spring and summer of 2000, 2001, and 2002, gaseous and particulate matter (PM) fuel-based emission factors for approximately 150,000 low-tailpipe, individual vehicles in the Las Vegas, NV, area were measured via on-road remote sensing. For the gaseous pollutants (carbon monoxide, hydrocarbons, and nitrogen oxide), a commercial vehicle emissions remote sensing system (VERSS) was used. The PM emissions were determined using a Lidar-based VERSS. Emission distributions and their shapes were analyzed and compared with previous studies. The large skewness of the distributions is evident for both gaseous pollutants and PM and has important implications for emission reduction policies, because the majority of emissions are attributed to a small fraction of vehicles. Results of this Las Vegas study and studies at other geographical locations were compared. The gaseous pollutants were found to be close to those measured by VERSS in other U.S. cities. The PM emission factors for spark ignition and diesel vehicles are in the range of previous tunnel and dynamometer studies.     

Potential role of fire retardant-treated polyurethane foam as a source of brominated diphenyl ethers to the US environment

Five tetra- to hexabrominated diphenyl ether (BDE) congeners (BDE-47, -99, -100, -153 and -154) are the most frequently reported in wildlife and humans. The commercial penta-BDE product, used predominantly to flame-retard polyurethane foam, consists primarily of these same congeners. In 1999, North American demand accounted for 98% of the total global penta-market of 8500 metric tons. Frogs, housed with flame retardant-treated polyurethane foam as a dry substrate, accumulated 10,100 microg/kg (wet weight) of the above BDEs. Crickets kept therein as food contained 14,400 microg/kg. The crickets are believed to have browsed directly on the foam and, in turn, were consumed by the frogs. BDE congener composition in all three matrices matched that of the penta-commercial product. Similar congeners were also observed in soil and stream sediments collected near a polyurethane foam manufacturing plant. Summed concentrations of BDE-47, -99 and -100, the dominant congeners observed in these samples, ranged from < 1 to 132 microg/kg (dry weight basis). Sunfish fillets obtained from a nearby, off-site pond contained a total of 624 microg/kg (lipid basis). Sewage treatment plant (STP) sludge exhibited these same congeners at 1370 microg/kg (dry weight). BDE-209, the fully brominated congener predominant in the commercial deca-BDE product, was also present at 1470 microg/kg. While no known polyurethane foam manufacturers discharged to this plant, the distribution pattern of the low brominated congeners in the sludge matched that of the penta-product. After four weeks of exposure to ambient outdoor conditions, the surface of flame-retarded polyurethane foam became brittle and began to disintegrate. Subsequent dispersal of these penta-containing foam fragments may be one mechanism by which these BDEs reach the environment.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.     

Spatial inhomogeneity in pollutant concentrations, and their implications for air quality model evaluation

The Southern California Air Quality Study database provides a valuable resource with which to test urban-scale photochemical models and to achieve a better understanding of the atmospheric dynamics of pollutant formation. The CIT model was evaluated using the SCAQS database according to traditional model performance guidelines. A first application, reported previously, focused on model enhancement and application of the model to the 27–29 August 1987 episode. This study evaluates the CIT model using the 24–25 June SCAQS episode, providing further evaluation of the model. Results show that the CIT airshed model can follow the diurnal variations of reactive species and the transport for relatively unreactive species. The normalized gross error for ozone was 31 % in June compared to 38% in August. However, to fully judge model performance in proper perspective, a question arises: “How well do the measurements reflect the air quality surrounding the monitoring station, not just in that location?” This is an important but seldom quantitatively considered factor, not only in model evaluation but in the study of health effects as well. Analyses indicate that individual concentration measurements only approximately represent the true volume-averaged concentrations within a computational grid cell and that significant spatial variations exist. Thus any evaluation of models using these data sets should take these local variations into consideration. A series of tests found that the local inhomogeneities had a normalized gross error in the range of 25–45% depending on the pollutant. In this context, the performance of the CIT model is consistent with known modeling limitations such as emissions inventories and sub-grid scale variation of observations.     

A status report on the U.S. national dioxin study

In 1983, the US Environmental Protection Agency (EPA) embarked on an extensive investigation of the presence and extent of contamination of the national environment by CDDs/CDFs. This status report is a prelude to a final report to be delivered to the US Congress in December, 1985.     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.     

The development and application of a simplified ozone modeling system (SOMS)

This paper describes the development and evaluation of a computationally efficient semi-empirical photochemical model that can be used as a screening tool to obtain quick estimates of the effect of a large number of VOC and NO_x emission control strategies on ozone concentrations. Selected control strategies can subsequently be examined with a more complex model. The model is one component of an ozone management system, the regional ozone decision model (RODM), designed to examine the costs and environmental consequences of alternate ozone abatement strategies.The model was developed by systematic simplification of a detailed photochemical model. At each step of the simplification, the simplified model was tested against observations and against results from the detailed model. The first major simplification was the introduction of a highly parameterized chemistry mechanism, originally developed by Azzi et al. (1992 Proc. 11th Int. Clean Air Conf., 4th Regional IUAPPA Conf.). This modification resulted in a factor of 5 improvement in the computational efficiency of the model. The model with the simplified chemistry was then tested by applying it to a photochemical oxidant episode in the San Joaquin Valley of California. Further improvements in computational speed and efficiency were obtained by uncoupling the chemistry from the transport of VOC and NO_x.     

Modeling mercury fluxes and concentrations in a Georgia watershed receiving atmospheric deposition load from direct and indirect sources

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 microg/m2. Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.