Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Bioavailability of 2,3,7,8-tetrachlorodibenzo-p-dioxin from municipal incinerator fly ash to freshwater fish

The bioavailability of 2,3,7,8-TCDD from municipal incinerator fly ash to freshwater fish was determined. It was observed that carp exposed to fly ash containing all 22 TCDD isomers, or the solvent extract of the fly ash, retain only 2,3,7,8-TCDD. Exposures with fly ash appears to follow a dose response relationship for bioconcentration, however, the bioavailability of 2,3,7,8-TCDD was not directly related to the level of 2,3,7,8-TCDD in fly ash for two fly ash samples studied.     

Estimation of organic carbon blank values and error structures of the speciation trends network data for source apportionment

Because the particulate organic carbon (OC) concentrations reported in U.S. Environment Protection Agency Speciation Trends Network (STN) data were not blank corrected, the OC blank concentrations were estimated using the intercept in particulate matter < or = 2.5 microm in aerodynamic diameter (PM2.5) regression against OC concentrations. The estimated OC blank concentrations ranged from 1 to 2.4 microg/m3 showing higher values in urban areas for the 13 monitoring sites in the northeastern United States. In the STN data, several different samplers and analyzers are used, and various instruments show different method detection limit (MDL) values, as well as errors. A comprehensive set of error structures that would be used for numerous source apportionment studies of STN data was estimated by comparing a limited set of measured concentrations and their associated uncertainties. To examine the estimated error structures and investigate the appropriate MDL values, PM2.5 samples collected at a STN site in Burlington, VT, were analyzed through the application of the positive matrix factorization. A total of 323 samples that were collected between December 2000 and December 2003 and 49 species based on several variable selection criteria were used, and eight sources were successfully identified in this study with the estimated error structures and min values among different MDL values from the five instruments: secondary sulfate aerosol (41%), secondary nitrate aerosol (20%), airborne soil (15%), gasoline vehicle emissions (7%), diesel emissions (7%), aged sea salt (4%), copper smelting (3%), and ferrous smelting (2%). Time series plots of contributions from airborne soil indicate that the highly elevated impacts from this source were likely caused primarily by dust storms.     

Improving source apportionment of fine particles in the eastern United States utilizing temperature-resolved carbon fractions

The objectives of this study were to examine the use of carbon fractions to identify particulate matter (PM) sources, especially traffic-related carbonaceous particle sources, and to estimate their contributions to the particle mass concentrations. In recent studies, positive matrix factorization (PMF) was applied to ambient fine PM (PM2.5) compositional data sets of 24-hr integrated samples including eight individual carbon fractions collected at three monitoring sites in the eastern United States: Atlanta, GA, Washington, DC, and Brigantine, NJ. Particulate carbon was analyzed using the Interagency Monitoring of Protected Visual Environments/Thermal Optical Reflectance method that divides carbon into four organic carbons (OC): pyrolized OC and three elemental carbon (EC) fractions. In contrast to earlier PMF studies that included only the total OC and EC concentrations, gasoline emissions could be distinguished from diesel emissions based on the differences in the abundances of the carbon fractions between the two sources. The compositional profiles for these two major source types show similarities among the three sites. Temperature-resolved carbon fractions also enhanced separations of carbon-rich secondary sulfate aerosols. Potential source contribution function analyses show the potential source areas and pathways of sulfate-rich secondary aerosols, especially the regional influences of the biogenic, as well as anthropogenic secondary aerosol. This study indicates that temperature-resolved carbon fractions can be used to enhance the source apportionment of ambient PM2.5.     

Response of Cyprinus carpio (Linn) to sublethal concentration of cypermethrin: alterations in protein metabolic profiles

Freshwater fish, Cyprinus carpio were exposed to sublethal concentration (1.2 microg l(-1)) of cypermethrin for 6, 12, 24 and 48 h to analyze various parameters of protein metabolism in functionally different tissues. Total, structural and soluble proteins showed decrement; where as free amino acids and the activities of protease, aspartate aminotransferase and alanine aminotransferase significantly increased in cypermethrin exposed fish. Interestingly, ammonia content decreased but urea and glutamine increased at all periods of exposure. It was also observed that alterations steadily increased with the period of exposure and exhibited tissue specificity. Thus variation in the protein metabolism of the fish exposed to cypermethrin indicates its toxic effect on the cellular metabolism thereby leading to impaired protein synthetic machinery.     

Source identification of atlanta aerosol by positive matrix factorization

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles < or = 2.5 microm in aerodynamic diameter) samples (PM2.5), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 microm in aerodynamic diameter) samples (PM10-2.5). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO4(2-) -rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO(3-) -rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO4(2-) -rich and NO(3-) -rich secondary aerosols were associated with NH(4+). The SO4(2-) -rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO(3-)-rich secondary aerosol (16%), SO4(2-) -rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

Experimental determination of sorption in fractured flow systems

Fracture "skins" are alteration zones on fracture surfaces created by a variety of biological, chemical, and physical processes. Skins increase surface area, where sorption occurs, compared to the unaltered rock matrix. This study examines the sorption of organic solutes on altered fracture surfaces in an experimental fracture-flow apparatus. Fracture skins containing abundant metal oxides, clays, and organic material from the Breathitt Formation (Kentucky, USA) were collected in a manner such that skin surface integrity was maintained. The samples were reassembled in the lab in a flow-through apparatus that simulated approximately 2.7 m of a linear fracture "conduit." A dual-tracer injection scheme was utilized with the sorbing or reactive tracer compared to a non-reactive tracer (chloride) injected simultaneously. Sorption was assessed from the ratio of the first temporal moments of the breakthrough curves and from the loss of reactive tracer mass and evaluated as a function of flow velocity and solute type. The breakthrough curves suggest dual-flow regimes in the fracture with both sorbing and non-sorbing flow fields. Significant sorption occurs for the reactive components, and sorption increased with decreasing flow rate and decreasing compound solubility. Based on moment analysis, however, there was little retardation of the center of solute mass. These data suggest that non-equilibrium sorption processes dominate and that slow desorption and boundary layer diffusion cause extensive tailing in the breakthrough curves.     

Modeling landfill gas potential and potential energy recovery from Thohoyandou landfill site,South Africa

ABSTRACT

The increase in solid waste generation has been a major contributor to the amount of Greenhouse gases (GHGs) present in the atmosphere. To some extent, a great chunk of these GHGs in the atmosphere is from landfill. This study assesses two theoretical models (LandGEM and Afvalzorg models) to estimate the amount of landfill gas (LFG) emitted from Thohoyandou landfill site. Also, the LFGcost Web model was used to estimate the cost and benefits of the implementation of an LFG utilization technology. The Thohoyandou landfill started operations in the year 2005 and it is proposed to reach its peak at approximately in the year 2026. The LandGEM calculates the mass of landfill gas emission using methane generation capacity, mass of deposited waste, methane generation constant and methane generation rate. Meanwhile, the Afvalzorg model determines the LFG emissions using the Methane correction factor, yearly waste mass disposal, waste composition, Degradation Organic Carbon, methane generation rate constant, LFG recovery efficiency. The study findings indicate that the methane (CH₄) and carbon dioxide (CO₂) emitted from the landfill estimated from LandGEM will peak in the year 2026 with values of 3517 Mg/year and 9649 Mg/year, respectively. Results from the Afvalzorg model show that CH₄ emission will peak in the year 2026 (3336 Mg/year). The LandGEM model showed that the total LFG, CH₄ and CO₂ emitted from the landfill between 2005 and 2040 are 293239.3 Mg/year, 78325.7 Mg/year and 214908.6 Mg/year, respectively. The simulation from the Afvalzorg model found that the CH₄ emitted from the years 2005– 2040 is 74302 Mg/year. The implementation of an LFG utilization technology was economically feasible from consideration of the sales of electricity generated and Certified Emission Reductions (CER) (carbon credits).     

Effects of storage method and duration on the toxicity of marine sediments to embryos of Crassostrea gigas oysters

The objective of laboratory sediment bioassays is to estimate in situ toxicity. This goal is difficult to achieve, as one of the main limitations of sediment toxicity tests is disruption of sediment geochemistry during sampling, handling and preservation. The effects of storage on the estimation of marine sediment toxicity to Crassostrea gigas embryos and larvae were investigated. Three storage methods and four storage periods were compared with three different sediment types contaminated by heavy metals, polycyclic aromatic hydrocarbons (PAHs) and both contaminants. Freezing and freeze-drying considerably increased the toxicity of decanted sediments and their elutriates as compared to the toxicity obtained with fresh sediments. Concerning the elutriates, the toxicity found with frozen and freeze-dried sediments was correlated with DOC, ammonia and PAH contents. However, the toxicity of fresh sediments kept at 4 degrees C increased with increasing duration of storage and was also correlated with the amount of ammonia in the elutriates.