The Southeastern Aerosol Research and Characterization Study: part 1--Overview

This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O3)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O3 and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.     

Emissions from charbroiling and grilling of chicken and beef

Emission rates for fine particle (<2.5 microm) mass (PM2.5), carbon (organic/elemental), inorganic ions (SO4(2-), NO3-, NH4+), elements (primarily metals), and speciated organic compounds are reported for charbroiling hamburger, steak, and chicken. The PM2.5 rates for charbroiling meats ranged from 4.4 to 11.6 g/kg of uncooked meat in this study. No mass-emission rates are available from grilling, but the speciated organic data are available for these samples. Emission rates varied by type of appliance, meat, meat-fat content, and cooking conditions. High-fat hamburger cooked on an underfired charbroiler emitted the highest amount of PM2.5. The emissions were almost exclusively composed of organic carbon, with small amounts of elements and inorganic ions. Water-soluble K+ and Cl-, which are used as indicators of wood smoke in source apportionment studies, were also present in meat-cooking emissions. The speciated organic compounds that were measured include polycyclic aromatic hydrocarbons (PAHs), cholesterol, and the long-chain gamma-lactones. Charbroiling emissions yielded an average of approximately 3-5 times more PAHs, approximately 20 times more cholesterol, and approximately 10 times more lactones than grilling. These data were utilized in the ambient source apportionment analysis for the 1997 Northern Front Range Air Quality Study source apportionment.     

Conceptual and numerical model of uranium(VI) reductive immobilization in fractured subsurface sediments

A conceptual model and numerical simulations of bacterial U(VI) reduction in fractured subsurface sediments were developed to assess the potential feasibility of biomineralization at the fracture/matrix interface as a mechanism for immobilization of uranium in structured subsurface media. The model envisions flow of anaerobic groundwater, with or without acetate as an electron donor for stimulation of U(VI) reduction by dissimilatory metal-reducing bacteria (DMRB), within mobile macropores along a one-dimensional flow path. As the groundwater moves along the flow path, U(VI) trapped in the immobile mesopore and micropore domains (the sediment matrix) becomes desorbed and transferred to the mobile macropores (fractures) via a first-order exchange mechanism. By allowing bacterial U(VI) reduction to occur in the mesopore domain (assumed to account for 12% of total sediment pore volume) according to experimentally-determined kinetic parameters and an assumed DMRB abundance of 10(7) cells per cm3 bulk sediment (equivalent to 4 mg of cells per dm3 bulk sediment), the concentration of U(VI) in the macropore domain was reduced ca. 10-fold compared to that predicted in the absence of mesopore DMRB activity after a 6-month simulation period. The results suggest that input of soluble electron donors over a period of years could lead to a major redistribution of uranium in fractured subsurface sediments, converting potentially mobile sorbed U(VI) to an insoluble reduced phase (i.e. uraninite) in the mesopore domain that is expected to be permanently immobile under sustained anaerobic conditions.     

Copper and trace element fractionation in electrokinetically treated methanogenic anaerobic granular sludge

The effect of electrokinetic treatment (0.15 mA cm(-2)) on the metal fractionation in anaerobic granular sludge artificially contaminated with copper (initial copper concentration 1000 mg kg(-1) wet sludge) was studied. Acidification of the sludge (final pH 4.2 in the sludge bed) with the intention to desorb the copper species bound to the organic/sulfides and residual fractions did not result in an increased mobility, despite the fact that a higher quantity of copper was measured in the more mobile (i.e. exchangeable/carbonate) fractions at final pH 4.2 compared to circum-neutral pH conditions. Also addition of the chelating agent EDTA (Cu2+:EDTA4- ratio 1.2:1) did not enhance the mobility of copper from the organic/sulfides and residual fractions, despite the fact that it induced a reduction of the total copper content of the sludge. The presence of sulfide precipitates likely influences the copper mobilisation from these less mobile fractions, and thus makes EDTA addition ineffective to solubilise copper from the granules.     

A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock

The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.     

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.     

Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax)

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.     

Interactive analysis of waste recycling and energy recovery program in a small-scale incinerator

Conflicting goals affecting solid waste management are explored in this paper to find the best implementation of resource recovery with a small-scale waste-to-energy process. Recycling paper and plastic material often leaves a shortage of thermal energy to support incineration that forces operators to supplement the process with auxiliary fuels. Although there are considerable profits to be made from material recovery, the increase of fuel usage causes conflict given that it is cost prohibitive. A series of trials performed on a small-scale 1.5-t/day incineration plant with a cyclone heat recovery system found that material recycling can impede performance. Experimental results are expressed as empirical regression formulas with regard to combustion temperature, energy transfer, and heat recovery. Process optimization is possible if the waste moisture content remains <30%. To test the robustness of the optimization analysis, a series of sensitivity analyses clarify the extent of material recycling needed with regard to plastic, paper, and metal. The experiments also test whether the moisture in the waste would decrease when recycling paper because of its exceptional capacity to absorb moisture. Results show that recycling paper is strongly recommended when the moisture content is >20%, whereas plastic recycling is not necessary at that moisture condition. Notably, plastic recovery reduces the heat needed to vaporize the water content of the solid waste, thus it is recommended only when the moisture content is <10%. For above-normal incineration temperatures, plastic recycling is encouraged, because it removes excess energy. Metal is confirmed as an overall priority in material recycling regardless of the moisture content of the incoming waste.     

Insect damage influences heat and water stress resistance gene expression in field-grown popcorn: implications in developing crop varieties adapted to climate change

Warming climatic conditions can pose problems for crop production in many parts of the world, but detailed information on the expression of heat and drought stress resistance genes of potentially affected crop plants is lacking. This information is important to have in order to most efficiently guide the breeding of crops that are adapted to new climatic conditions. A maize (Zea mays) gene microarray, a method used worldwide to evaluate the expression of tens of thousands of genes at once, was used to investigate changes in expression of genes involved in resistance to heat and water stress in milk stage popcorn kernels from undamaged and insect-damaged ears. Popcorn is a form of maize that is more susceptible to heat and drought stress due to its smaller root system. In years of heat and drought stress, expression of many heat shock- and senescence-related proteins increased compared to the year when weather was closer to average conditions, but the expression of many genes related to drought stress resistance decreased in years of weather stress. A different complex of heat shock protein and water stress resistance protein genes had higher expression in kernels from undamaged compared to insect-damaged ears in years of heat and drought stress. These results indicate that the interaction of biotic components, such as insects, are important to consider in developing crop lines with adaptation to stress as this will help identify additional genes and their regulatory components involved in heat and drought stress resistance that might otherwise be overlooked, and will likely be an important strategy for the most effective development of climate stress-tolerant crops globally.     

Managing the cost of emissions for durable,carbon-containing products

We recognize that carbon-containing products do not decay and release CO₂ to the atmosphere instantaneously, but release that carbon over extended periods of time. For an initial production of a stock of carbon-containing product, we can treat the release as a probability distribution covering the time over which that release occurs. The probability distribution that models the carbon release predicts the amount of carbon that is released as a function of time. The use of a probability distribution in accounting for the release of carbon to the atmosphere realizes a fundamental shift from the idea that all carbon-containing products contribute to a single pool that decays in proportion to the size of the stock. Viewing the release of carbon as a continuous probabilistic process introduces some theoretical opportunities not available in the former paradigm by taking advantage of other fields where the use of probability distributions has been prevalent for many decades. In particular, theories developed in the life insurance industry can guide the development of pricing and payment structures for dealing with the costs associated with the oxidation and release of carbon. These costs can arise from a number of proposed policies (cap and trade, carbon tax, social cost of carbon, etc), but in the end they all result in there being a cost to releasing carbon to the atmosphere. If there is a cost to the emitter for CO₂ emissions, payment for that cost will depend on both when the emissions actually occur and how payment is made. Here we outline some of the pricing and payment structures that are possible which result from analogous theories in the life insurance industry. This development not only provides useful constructs for valuing sequestered carbon, but highlights additional motivations for employing a probability distribution approach to unify accounting methodologies for stocks of carbon containing products.