The Regulation of Toxic Air Pollutants A Critical Review

ABSTRACT

Passage of the 1990 Clean Air Act Amendments launched the Acid Rain Program in the United States. This initiative, based on the market mechanism of a sulfur dioxide tradable “allowance” system, was a dramatic departure from traditional command and control strategies designed to reduce air pollution emissions. Power plant managers have flexibility under the program to select and implement a variety of options to reduce emissions below mandated levels. Federal agencies have collected annual performance data for affected facilities covered by the program for a number of years. Coal-burning plants are typically greater generators of sulfur dioxide (SO₂) than oil burners of equivalent size. This study examined the effect of fuel type as a significant factor influencing a plant's achievement in reducing pollution emissions. Achievement was measured by using a derived variable, delta (A), defined as the difference between pounds of SO₂ produced divided by the energy (in million Btu) generated, for the years 1990 and 1995. Rigorous nonparametric statistical analyses were used to compare the two populations of coal-fired and oil-fired plants. Results indicated that coal-burning facilities achieved greater program success, measured by the expected value of delta, than the oil combustors for the five-year period reviewed. Since utility managers must take steps to ensure all applicable requirements of the program are met, findings of the inquiry should prove to be useful in assessing achievable emissions reductions and aid in long-range facility planning.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

Rapid measurement of emissions from military aircraft turbine engines by downstream extractive sampling of aircraft on the ground: Results for C-130 and F-15 aircraft

Aircraft emissions affect air quality on scales from local to global. More than 20% of the jet fuel used in the U.S. is consumed by military aircraft, and emissions from this source are facing increasingly stringent environmental regulations, so improved methods for quickly and accurately determining emissions from existing and new engines are needed. This paper reports results of a study to advance the methods used for detailed characterization of military aircraft emissions, and provides emission factors for two aircraft: the F-15 fighter and the C-130 cargo plane. The measurements involved outdoor ground-level sampling downstream behind operational military aircraft. This permits rapid change-out of the aircraft so that engines can be tested quickly on operational aircraft. Measurements were made at throttle settings from idle to afterburner using a simple extractive probe in the dilute exhaust. Emission factors determined using this approach agree very well with those from the traditional method of extractive sampling at the exhaust exit. Emission factors are reported for CO₂, CO, NO, NO_x, and more than 60 hazardous and/or reactive organic gases. Particle size, mass and composition also were measured and are being reported separately. Comparison of the emissions of nine hazardous air pollutants from these two engines with emissions from nine other aircraft engines is discussed.     

Potential of Corporate Social Responsibility for Poverty Alleviation among Contract Sugarcane Farmers in the Nzoia Sugarbelt, Western Kenya

Although contract sugarcane farming is the most dominant and popular land use among farmers in Nzoia Sugarbelt, results from a 2007 study suggests that the intended goal of increasing farmers’ incomes seems to have failed. With a mean monthly income of Kenya Shillings 723 (US $ 10) from an average cane acreage of 0.38 hectares, it would be difficult for a household of eight family members to meet their basic needs and lead a decent life. Analysis of farmer statements showed that up to 86% of the changes in net income were significantly determined by six cost variables as a group (i.e., acreage, tillage costs, seedcane costs, transport costs, yield, and farmer’s education level). Area under sugarcane had the greatest influence on net income whereby an increase in one hectare under cane would result in an increase of Kenya Shillings 110,427 in net income (per crop cycle of 21 months), holding other variables constant. This translates into Kenya shillings 5,258 per month (or 175 per day per household, or for a family of eight people—KES 22 or US $ 10) from an average cane acreage of 0.38 hectares, it would be difficult for a household of eight family members to meet their basic needs and lead a decent life. Analysis of farmer statements showed that up to 86% of the changes in net income were significantly determined by six cost variables as a group (i.e., acreage, tillage costs, seedcane costs, transport costs, yield, and farmer’s education level). Area under sugarcane had the greatest influence on net income whereby an increase in one hectare under cane would result in an increase of Kenya Shillings 110,427 in net income (per crop cycle of 21 months), holding other variables constant. This translates into Kenya shillings 5,258 per month (or 175 per day per household, or for a family of eight people—KES 22 or US 0.3) per member, which is far below the international standard of absolute poverty. Key net income depressors were tillage, seedcane, and transportation costs, all of which were determined by the company with no input from farmers. To bridge income gaps between the company and farmers in favor of sustainable community livelihoods, this paper argues strongly for the need to institutionalize Corporate Social Responsibility within the daily operations of the company particularly to address net-income depressors. Ten key building blocks for such a policy for Nzoia Sugar Company are suggested, based on farmers’ responses and ethical considerations.     

Remediation of chlorinated ethenes,ethanes, and methanes in groundwater using carbon‐ and iron‐based electron donor

Field‐scale pilot tests were performed to evaluate enhanced reductive dechlorination (ERD) of dissolved chlorinated solvents at a former manufacturing facility located in western North Carolina (the site). Results of the site assessment indicated the presence of two separate chlorinated solvent–contaminated groundwater plumes, located in the northern and southern portions of the site. The key chlorinated solvents found at the site include 1,1,2,2‐tetrachloroethane, trichloroethene, and chloroform. A special form of EHC^® manufactured by Adventus Americas was used as an electron donor at this site. In this case, EHC is a pH‐buffering electron donor containing controlled release carbon and ZV Iron MicroSphere 200, a micronscale zero‐valent iron (ZVI) manufactured by BASF. Approximately 3,000 pounds of EHC were injected in two Geoprobe^® boreholes in the saprolite zone (southern plume), and 3,500 pounds of EHC were injected at two locations in the partially weathered rock (PWR) zone (northern plume) using hydraulic fracturing techniques. Strong reducing conditions were established immediately after the EHC injection in nearby monitoring wells likely due to the reducing effects of ZV Microsphere 200. After approximately 26 months, the key chlorinated VOCs were reduced over 98 percent in one PWR well. Similarly, the key chlorinated solvent concentrations in the saprolite monitoring wells decreased 86 to 99 percent after initial increases in concentrations of the parent chlorinated solvents. The total organic carbon and metabolic acid concentrations indicated that the electron donor lasted over 26 months after injection in the saprolite aquifer. © 2009 Wiley Periodicals, Inc.     

Recovery of rare and precious metals from urban mines—A review

Urban mining is essential for continued natural resource extraction. The recovery of rare and precious metals (RPMs) from urban mines has attracted increasing attention from both academic and industrial sectors, because of the broad application and high price of RPMs, and their low content in natural ores. This study summarizes the distribution characteristics of various RPMs in urban mines, and the advantages and shortcomings of various technologies for RPM recovery from urban mines, including both conventional (pyrometallurgical, hydrometallurgical, and biometallurgical processing), and emerging (electrochemical, supercritical fluid, mechanochemical, and ionic liquids processing) technologies. Mechanical/physical technologies are commonly employed to separate RPMs from nonmetallic components in a pre-treatment process. A pyrometallurgical process is often used for RPM recovery, although the expensive equipment required has limited its use in small and medium-sized enterprises. Hydrometallurgical processing is effective and easy to operate, with high selectivity of target metals and high recovery efficiency of RPMs, compared to pyrometallurgy. Biometallurgy, though, has shown the most promise for leaching RPMs from urban mines, because of its low cost and environmental friendliness. Newly developed technologies—electrochemical, supercritical fluid, ionic liquid, and mechanochemical—have offered new choices and achieved some success in laboratory experiments, especially as efficient and environmentally friendly methods of recycling RPMs. With continuing advances in science and technology, more technologies will no doubt be developed in this field, and be able to contribute to the sustainability of RPM mining.

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Validation of the Digital Opacity Compliance System under Regulatory Enforcement Conditions

Abstract

U.S. Environmental Protection Agency (EPA) Emission Measurement Center in conjunction with EPA Regions VI and VIII, the state of Utah, and the U.S. Department of Defense have conducted a series of long-term pilot and field tests to determine the accuracy and reliability of a visible opacity monitoring system consisting of a conventional digital camera and a separate computer software application for plume opacity determination. This technology, known as the Digital Opacity Compliance System (DOCS), has been successfully demonstrated at EPA-sponsored Method-9 “smoke schools,” as well as at a number of government and commercially operated industrial facilities.

Results from the current DOCS regulatory pilot study demonstrated that, under regulatory enforcement conditions, the average difference in opacity measurement between the DOCS technology and EPA Reference Method 9 (Method 9) was 1.12%. This opacity difference, which was computed from the evaluation of 241 regulated air sources, was found to be statistically significant at the 99% confidence level. In evaluating only those sources for which a nonzero visible opacity level was recorded, the average difference in opacity measurement between the DOCS technology and Method 9 was 1.20%. These results suggest that the two opacity measurement methods are essentially equivalent when measuring the opacity of visible emissions.

Given the costs and technical limitations associated with use of Method 9, there is a recognized need to develop accurate, reproducible, and scientifically defensible alternatives to the use of human observers. The use of digital imaging/processing brings current technology to bear on this important regulatory issue. Digital technology offers increased accuracy, a permanent record of measurement events, lower costs, and a scientifically defensible approach for opacity determination.     

Particulate matter emission rates from beef cattle feedlots in Kansas-reverse dispersion modeling

Open beef cattle feedlots emit various air pollutants, including particulate matter (PM) with equivalent aerodynamic diameter of 10 microm or less (PM10); however limited research has quantified PM10 emission rates from feedlots. This research was conducted to determine emission rates of PM10 from large cattle feedlots in Kansas. Concentrations of PM10 at the downwind and upwind edges of two large cattle feedlots (KS1 and KS2) in Kansas were measured with tapered element oscillating microbalance (TEOM) PM10 monitors from January 2007 to December 2008. Weather conditions at the feedlots were also monitored. From measured PM10 concentrations and weather conditions, PM10 emission rates were determined using reverse modeling with the American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model (AERMOD). The two feedlots differed significantly in median PM10 emission flux (1.60 g/m2-day for KS1 vs. 1.10 g/m2-day for KS2) but not in PM10 emission factor (27 kg/1000 head-day for KS1 and 30 kg/1000 head-day KS2). These emission factors were smaller than published U.S. Environmental Protection Agency (EPA) emission factor for cattle feedlots.     

Uptake of 14C-atropine and/or its transformation products from soil by wheat (Triticum aestivum var Kronjet) and their translocation to shoots

Plant uptake of toxins and their translocation to edible plant parts are important processes in the transfer of contaminants into the food chain. Atropine, a highly toxic muscarine receptor antagonist produced by Solanacea species, is found in all plant tissues and can enter the soil and hence be available for uptake by crops. The absorption of atropine and/or its transformation products from soil by wheat (Triticum aestivum var Kronjet) and its distribution to shoots was investigated by growing wheat in soil spiked with unlabeled or ¹⁴C-labeled atropine. Radioactivity attributable to ¹⁴C-atropine and its transformation products was measurable in plants sampled at 15 d after sowing (DAS) and thereafter until the end of experiment. The highest accumulation of ¹⁴C-atropine and/or its transformation products by plants was detected in leaves (between 73 and 90% of the total accumulated) with lower amounts in stems, roots, and seeds (approximately 14%, 9%, and 3%, respectively). ¹⁴C-Atropine and/or its transformation products were detected in soil leachate at 30, 60, and 90 DAS and were strongly adsorbed to soil, with 60% of the applied dose adsorbed at 30 DAS, plateauing at 70% from 60 DAS. Unlabeled atropine was detected in shoots 30 DAS at a concentration of 3.9 ± 0.1 μg kg^?1 (mean ± SD). The observed bioconcentration factor was 2.3 ± 0.04. The results suggest a potential risk of atropine toxicity to consumers.