Impact of the Knudsen number and mass-transfer expression on multi-phase kinetic modeling

Three different mass-transfer expressions are employed within the Model of Aerosol, Gas, and Interfacial Chemistry (MAGIC) to study gas-phase molecular chlorine and bromine production from NaCl and NaBr aerosols, respectively. Simulations of chamber experiments are performed in which NaCl aerosols react with gas-phase ozone in the presence of UV light, in order to identify the importance of the Knudsen number and mass-transfer expression in systems with varying contributions from gas-phase, aqueous-phase, and interfacial chemistry. In the case of NaBr aerosols, simulations are performed of both dark and photolytic conditions. A range of Knudsen numbers spanning the continuum, transition and free-molecular regimes is studied. Particle size is varied over three orders of magnitude, and particle concentration is changed to keep either (a) total aerosol volume or (b) total aerosol surface area constant. When total aerosol volume is constant, the total amount of surface area available for interfacial reaction increases linearly with Knudsen number. Consequently peak gas-phase Cl₂ and Br₂ concentrations increase by two orders of magnitude from the continuum regime to the free-molecular regime. When total aerosol surface area is constant, total aerosol volume is inversely proportional to Knudsen number, with lesser volume being available at higher Knudsen numbers. Consequently Cl^? depletion in the kinetic regime leads to most gas-phase Cl₂ being produced in the transition regime. Gas-phase Br₂ concentration trends are determined by aqueous-phase reaction mechanisms, leading to a monotonic decrease in production with Knudsen number. At all Knudsen numbers, more gas-phase bromine is produced in the photolytic case than in the dark case, the difference being significant in the transition regime. Results of this study suggest that halogen production is insensitive to the mass-transfer expression used in the simulations.     

Effect of water treatment residuals on soil phosphorus, copper and aluminium availability and toxicity

Water treatment residuals (WTRs) are produced by the treatment of potable water with coagulating agents. Beneficial recycling in agriculture is hampered by the fact that WTRs contain potentially toxic contaminants (e.g. copper and aluminium) and they bind phosphorus strongly. These issues were investigated using a plant bioassay (Lactuca sativa), chemical extractions and an isotopic dilution technique. Two WTRs were applied to an acidic and a neutral pH soil at six rates. Reductions in plant growth in amended soils were due to WTR-induced P deficiency, rather than Al or Cu toxicity. The release of potentially toxic Al from WTRs was found to be mitigated by their alkaline nature and pH buffering capacity. However, acidification of WTRs was shown to release more soluble Al than soil naturally high in Al. Copper availability was relatively low in all treatments. However, the lability of WTR-Cu increased when the WTR was applied to the soil.     

Evaluation of Vegetation Near Coal-burning Power Plants in Southwestern Pennsylvania. II. Ozone Injury on Foliage of Hybrid Poplar

The objective of this study was to determine if the incidence or severity of foliar injury induced by regional, ambient ozone was influenced by local emissions from a complex of coal-burning power plants in southwestern Pennsylvania. Plantings of an ozonesensitive hybrid poplar clone {Populus maximowizii x trichocarpa, clone NE 388) were established in 1972 at various distances and directions from the power plants. Foliar injury caused by ambient ozone was evaluated annually from 1973 to 1990 in early to mid- August. Data are presented for the 12-year period, 1979 to 1990 inclusive, for which the most complete data sets were available. Injury from ambient ozone varied spatially and temporally, but with little relationship to power plant location. There was an apparent negative relationship between emission trends and ozone-induced symptoms, but only for one power plant. The correlation between annual mean levels of ozone-induced stipple and frequency of days (per year) with a 1-hr ozone maximum exceeding 0.04 ppm was weak, but significant. Ozone-induced bifacial necrosis was not observed on the foliage of the hybrid poplar during the drought year of 1988 in spite of record high levels of ozone; however, ozoneinduced stipple was observed.     

A Load Shifting Model for Air Pollution Control in the Electric Power Industry

Load-shifting, a relatively inexpensive approach to air pollution control, involves transferring the generating load from one power plant to another according to meteorological conditions. In this paper, an atmospheric dispersion model is adapted to estimate the exposure of the urban population to sulfur dioxide from operating the power system in different ways. Then a mathematical model of the power system of a metropolitan area is constructed to determine the reduction in pollution exposure which could be achieved, and the costs involved. As a case study, the application of the model to St. Louis, Missouri, is simulated. Under favorable conditions, load shifting could reduce pollution exposure up to 95%, while increasing the costs of electric power generation by only 4%. The load-shifting model has use not only as an operational control strategy, but also as an analytical tool to evaluate alternative pollution control measures in the electric power industry.     

Environmental contaminants in freshwater fish and their risk to piscivorous wildlife based on a national monitoring program

Organochlorine chemical residues and elemental concentrations were measured in piscivorous and benthivorous fish at 111 sites from large U.S. river basins. Potential contaminant sources such as urban and agricultural runoff, industrial discharges, mine drainage, and irrigation varied among the sampling sites. Our objectives were to provide summary statistics for chemical contaminants and to determine if contaminant concentrations in the fish were a risk to wildlife that forage at these sites. Concentrations of dieldrin, total DDT, total PCBs, toxaphene, TCDD-EQ, cadmium, chromium, mercury, lead, selenium, and zinc exceeded toxicity thresholds to protect fish and piscivorous wildlife in samples from at least one site; most exceedences were for total PCBs, mercury, and zinc. Chemical concentrations in fish from the Mississippi River Basin exceeded the greatest number of toxicity thresholds. Screening level wildlife risk analysis models were developed for bald eagle and mink using no adverse effect levels (NOAELs), which were derived from adult dietary exposure or tissue concentration studies and based primarily on reproductive endpoints. No effect hazard concentrations (NEHC) were calculated by comparing the NOAEL to the food ingestion rate (dietary-based NOAEL) or biomagnification factor (tissue-based NOAEL) of each receptor. Piscivorous wildlife may be at risk from a contaminant if the measured concentration in fish exceeds the NEHC. Concentrations of most organochlorine residues and elemental contaminants represented no to low risk to bald eagle and mink at most sites. The risk associated with pentachloroanisole, aldrin, Dacthal, methoxychlor, mirex, and toxaphene was unknown because NOAELs for these contaminants were not available for bald eagle or mink. Risk differed among modeled species and sites. Our screening level analysis indicates that the greatest risk to piscivorous wildlife was from total DDT, total PCBs, TCDD-EQ, mercury, and selenium. Bald eagles were at greater risk to total DDT and total PCBs than mink, whereas risks of TCDD-EQ, mercury, and selenium were greater to mink than bald eagle.     

Long-Term Community Dynamics of Small Landbirds with and Without Exposure to Extensive Disturbance from Military Training Activities

Military training activities are known to impact individual species, yet our understanding of how such activities influence animal communities is limited. In this study, we used long-term data in a case study approach to examine the extent to which the local small landbird community differed between a site in northeast Kansas that experienced intensive disturbance from military training activities (Ft. Riley Military Installation) and a similar, nearby site that experienced minimal human disturbance (Konza Prairie Biological Station). In addition, we characterized how the regional pool of potential colonizers influenced local community dynamics using Breeding Bird Survey data. From 1991 to 2001, most species of small terrestrial landbirds (73%) recorded during breeding surveys were found at both sites and the mean annual richness at Ft. Riley (39.0 ± 2.86 [SD]) was very similar to that of Konza Prairie (39.4 ± 2.01). Richness was maintained at relatively constant levels despite compositional changes because colonizations compensated local extinctions at both sites. These dynamics were driven primarily by woodland species that exhibited stochastic losses and gains and were present at a low local and regional abundance. Our results suggest that military training activities may mimic natural disturbances for some species in this area because the small landbird community did not differ markedly between sites with and sites without extensive human disturbance. Although our results suggest that military training is not associated with large changes in the avian community, additional studies are needed to determine if this pattern is found in other ecological communities.     

Mass conservative,positive definite integrator for atmospheric chemical dynamics

Air quality models compute the transformation of species in the atmosphere undergoing chemical and physical changes. The numerical algorithms used to predict these transformations should obey mass conservation and positive definiteness properties. Among all physical phenomena, the chemical kinetics solver provides the greatest challenge to attain these two properties. In general, most chemical kinetics solvers are mass conservative but not positive definite. In this article, a new numerical algorithm for the computation of chemical kinetics is presented. The integrator is called Split Single Reaction Integrator (SSRI). It is both mass conservative and positive definite. It solves each chemical reaction exactly and uses operator splitting techniques (symmetric split) to combine them into the entire system.The method can be used within a host integrator to fix the negative concentrations while preserving the mass, or it can be used as a standalone integrator that guarantees positive definiteness and mass conservation. Numerical results show that the new integrator, used as a standalone integrator, is second order accurate and stable under large fixed time steps when other conventional integrators are unstable.     

Developmental toxicity of two common corn pesticides to the endangered southern bell frog (Litoria raniformis)

To examine the link between corn agriculture and the observed decline of the endangered southern bell frog (SBF), the effects of two corn crop pesticides on larval growth and development were investigated. Tadpoles were exposed to terbufos sulfone (10 μg/L), a major breakdown product of the insecticide terbufos, and the herbicide atrazine (25 μg/L) individually and as a mixture until the completion of metamorphosis. Atrazine did not interact synergistically with terbufos sulfone or result in significant effects on growth and development alone, although there was some indication of accelerated metamorphosis in the pilot study. Terbufos sulfone alone and as a mixture (terbufos/atrazine) significantly slowed larval development and ultimately delayed metamorphosis. The observed developmental effects from an environmentally relevant concentration of terbufos sulfone indicates a risk posed by this persistent degradation product to the endangered SBF, which breeds and develops in the rice bays adjacent to corn fields treated with pesticides.