Enzymatic synthesis of bromo- and chlorocarbazoles and elucidation of their structures by molecular modeling

3-Chlorocarbazole, 3,6-dichlorocarbazole, dibromocarbazole, and 1,3,6,8-tetrabromocarbazole are emerging environmental contaminants which have been detected recently in water, sediment, and soil samples. However, their sources and occurrence have not been explained. Here, we report an enzymatic synthesis of bromo- and chlorocarbazoles by chloroperoxidase from Caldariomyces fumago in water. Density functional theory (DFT) method was used to predict the most stable products. Carbazole and chloroperoxidase were assayed in vitro in the presence of hydrogen peroxide, bromide, and chloride ions in different substrate ratio treatments against constant and varying enzyme concentrations. Halogenated carbazoles formed were identified by high-resolution gas chromatography coupled to mass spectrometry. In all treatments, bromination and chlorination took place, but the composition and concentration of compounds formed varied from one treatment to another. Mono-, di-, tri-, and tetra-substituted bromo- and chlorocarbazoles which include the reported environmental contaminants were synthesized. 3-Substituted and 3,6-substituted congeners were relatively higher in concentration. Enzyme concentration did not favor preferential formation of any of the compounds synthesized. However, their synthesis was influenced by halide concentration. Congeners with bromine and chlorine at position of C-3, C-3,6, C-1,3,6, and C-1,3,6,8 were calculated as the stable intermediate sigma complexes by DFT method. Regioselectivity in halogenation is discussed and hypothesis of the likely stable products in the environment explained. This study provides evidence that bromo- and chlorocarbazoles reported previously can be formed enzymatically in the environment, demonstrating the need to consider aromatic pollutants transformation and their potential toxicity enhancements in the management of water pollution and contaminated sites.     

Control of Asphaltic Concrete Plants in Los Angeles County

Characteristics of maximum short-term ground level concentrations from an elevated point source, namely, the effective plume height, the critical wind speed, the distance to the point of maximum concentration, and the maximum concentration, are derived from the gaussian plume model. Both phases of plume development—before and after it has reached its final height—are considered. The plume rise treatment includes both thermal buoyancy and momentum effects. Certain limitations on critical wind speed are discussed. The dispersion model whose basis is established in this paper should be especially useful in applications where on site meteorological data are unavailable.     

Problems in Judging Plume Opacity—A Simple Device for Measuring Opacity of Wet Plumes

The discoloration of exterior paint, has been shown to occur when H₂S in the air reacts with heavy metal salts used as pigments or fungicides in the paint. Simple field tests can give an indication whether H₂S was involved. An electron diffraction technique is described to identify the discolored compound in paint samples. Field experience in Jacksonville using this method is described.     

Effect of nitrogen fertilizer application on growing season soil carbon dioxide emission in a corn-soybean rotation

Nitrogen application can have a significant effect on soil carbon (C) pools, plant biomass production, and microbial biomass C processing. The focus of this study was to investigate the short-term effect of N fertilization on soil CO(2) emission and microbial biomass C. The study was conducted from 2001 to 2003 at four field sites in Iowa representing major soil associations and with a corn (Zea mays L.)-soybean (Glycine max L. Merr.) rotation. The experimental design was a randomized complete block with four replications of four N rates (0, 90, 180, and 225 kg ha(-1)). In the corn year, season-long cumulative soil CO(2) emission was greatest with the zero N application. There was no effect of N applied in the prior year on CO(2) emission in the soybean year, except at one of three sites, where greater applied N decreased CO(2) emission. Soil microbial biomass C (MBC) and net mineralization in soil collected during the corn year was not significantly increased with increase in N rate in two out of three sites. At all sites, soil CO(2) emission from aerobically incubated soil showed a more consistent declining trend with increase in N rate than found in the field. Nitrogen fertilization of corn reduced the soil CO(2) emission rate and seasonal cumulative loss in two out of three sites, and increased MBC at only one site with the highest N rate. Nitrogen application resulted in a reduction of both emission rate and season-long cumulative emission of CO(2)-C from soil.     

Estimated occupational risk from bioaerosols generated during land application of class B biosolids

Some speculate that bioaerosols from land application of biosolids pose occupational risks, but few studies have assessed aerosolization of microorganisms from biosolids or estimated occupational risks of infection. This study investigated levels of microorganisms in air immediately downwind of land application operations and estimated occupational risks from aerosolized microorganisms. In all, more than 300 air samples were collected downwind of biosolids application sites at various locations within the United States. Coliform bacteria, coliphages, and heterotrophic plate count (HPC) bacteria were enumerated from air and biosolids at each site. Concentrations of coliforms relative to Salmonella and concentrations of coliphage relative to enteroviruses in biosolids were used, in conjunction with levels of coliforms and coliphages measured in air during this study, to estimate exposure to Salmonella and enteroviruses in air. The HPC bacteria were ubiquitous in air near land application sites whether or not biosolids were being applied, and concentrations were positively correlated to windspeed. Coliform bacteria were detected only when biosolids were being applied to land or loaded into land applicators. Coliphages were detected in few air samples, and only when biosolids were being loaded into land applicators. In general, environmental parameters had little impact on concentrations of microorganisms in air immediately downwind of land application. The method of land application was most correlated to aerosolization. From this large body of data, the occupational risk of infection from bioaerosols was estimated to be 0.78 to 2.1%/yr. Extraordinary exposure scenarios carried an estimated annual risk of infection of up to 34%, with viruses posing the greatest threat. Risks from aerosolized microorganisms at biosolids land application sites appear to be lower than those at wastewater treatment plants, based on previously reported literature.     

Thirty-year trends in suspended sediment in seven Lake Erie tributaries

Sediment is an important pollutant for Lake Erie and its tributaries as a carrier of other substances and as a pollutant in its own right. Environmental managers have called for major reductions in sediment loadings in Lake Erie tributaries. In this study, 30-yr (1975-2005) datasets with daily resolution are analyzed to identify and interpret trends in sediment concentrations and loads in major US tributaries to Lake Erie. The Maumee and Sandusky Rivers in agricultural northwest Ohio show continual decreases throughout this period, but the River Raisin shows increases, especially in the last decade. The urban and forested Cuyahoga River shows little trend before 2000 but shows increases since then. The mostly forested Grand River shows strong decreases before 1995, little change thereafter until the early 2000s, and then increases. In most cases, the greatest decreases or smallest increases, depending on the river, are associated with summer and fall and with low flow conditions, whereas the smallest decreases or greatest increases are associated with the spring and with high flow conditions. Analysis of concentration-flow relationships indicates that these changes are not due to weather but reflect positive and negative anthropogenic influences. Sediment decreases in the northwestern Ohio tributaries seem to reflect the successful use of agricultural practices to reduce erosion and prevent sediment loss. Opportunities for further reductions in sediment loads and concentrations lie in better management of sediment losses during winter and spring.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

Analyzing the cost effectiveness of Santiago, Chile's policy of using urban forests to improve air quality

Santiago, Chile has the distinction of having among the worst urban air pollution problems in Latin America. As part of an atmospheric pollution reduction plan, the Santiago Regional Metropolitan government defined an environmental policy goal of using urban forests to remove particulate matter less than 10 microm (PM(10)) in the Gran Santiago area. We used cost effectiveness, or the process of establishing costs and selecting least cost alternatives for obtaining a defined policy goal of PM(10) removal, to analyze this policy goal. For this study, we quantified PM(10) removal by Santiago's urban forests based on socioeconomic strata and using field and real-time pollution and climate data via a dry deposition urban forest effects model. Municipal urban forest management costs were estimated using management cost surveys and Chilean Ministry of Planning and Cooperation documents. Results indicate that managing municipal urban forests (trees, shrubs, and grass whose management is under the jurisdiction of Santiago's 36 municipalities) to remove PM(10) was a cost-effective policy for abating PM(10) based on criteria set by the World Bank. In addition, we compared the cost effectiveness of managing municipal urban forests and street trees to other control policies (e.g. alternative fuels) to abate PM(10) in Santiago and determined that municipal urban forest management efficiency was similar to these other air quality improvement measures.     

EPA worst case water microcosms for testing phage biocontrol of Salmonella

A microplate method was developed as a tool to test phages for their ability to control Salmonella in aqueous environments. The method used EPA (U.S. Environmental Protection Agency) worst case water (WCW) in 96-well plates. The WCW provided a consistent and relatively simple defined turbid aqueous matrix, high in total organic carbon (TOC) and total dissolved salts (TDS), to simulate swine lagoon effluent, without the inconvenience of malodor and confounding effects from other biological factors. The WCW was originally defined to simulate high turbidity and organic matter in water for testing point-of-use filtration devices. Use of WCW to simulate lagoon effluent for phage testing is a new and innovative application of this matrix. Control of physical and chemical parameters (TOC, TDS, turbidity, temperature, and pH) allowed precise evaluation of microbiological parameters (Salmonella and phages). In a typical application, wells containing WCW were loaded with Salmonella enterica susp. enterica serovar Typhimurium (ATCC14028) and treated with phages alone and in cocktail combinations. Mean Salmonella inactivation rates (k, where the lower the value, the greater the inactivation) of phage treatments ranged from -0.32 to -1.60 versus -0.004 for Salmonella controls. Mean log(10) reductions (the lower the value, the greater the reduction) of Salmonella phage treatments were -1.60 for phage PR04-1, -2.14 for phage PR37-96, and -2.14 for both phages in a sequential cocktail, versus -0.08 for Salmonella controls. The WCW microcosm system was an effective tool for evaluating the biocontrol potential of Salmonella phages.     

An Evaluation of Techniques to Control Problem Bird Species on Landfill Sites

Birds feeding on landfill sites cause problems in terms of nuisance to neighbors, flight safety, a threat to public health, and affecting the day to day site operation. A number of control measures exist to deter problem species; however, research into their effectiveness across sites and for multiple species has been limited. We use a modeling approach in order to assess the effectiveness of nine techniques — pyrotechnics, hand-held distress calls, static distress calls, blank ammunition, a combination of blank and lethal use of ammunition, the use of falcons, the use of hawks, wailers and helium-filled bird-scaring kites — at deterring three commonly recorded species — the Black-headed Gull (Larus ridibundus), the Herring Gull (Larus argentatus) and the Lesser Black-backed Gull (Larus fuscus) — from six landfill sites across the United Kingdom. The use of distress calls, falconry, and combinations of lethal and nonlethal use of ammunition were the most effective techniques for initially deterring birds from these sites. However, when habituation is considered, there is a clear difference between techniques such as falconry, which have a lethal aspect and may act to reinforce the deterrence, and the use of techniques such as distress calls, which do not. However there are problems related to legislation and public perception when lethal techniques are used.