Exceedances of the National Ambient Air Quality Standard for Ozone Occurring at a “Pristine” Area Site

Abstract

This paper presents a comparative study of the biodegradation of three aromatic volatile compounds in a compost-based biofilter: toluene, xylene, and 1,2,4-trimethyl-benzene, used in the course of this work for the first time in the field of biofiltration. Hence, three identical biofiltration units have been operated at the laboratory scale. During the experiments, nitrogen (as urea) was supplied at various concentrations to each reactor, via irrigated nutrient solutions. A comparative analysis of the results showed that the biodegradability scale followed the degree of substitution around the aromatic ring: toluene > xylene > trimethylbenzene, with 95, 80, and 70% maximum conversions, respectively. In addition, and despite the different removal levels achieved in the three biore-actors, it was established that from a reaction viewpoint, the degradation of the three compounds seemed to follow similar metabolic pathways involving methylcatechol isomers. Finally, by varying the nitrogen input concentrations in the three reactors, three degradation regimes have been highlighted: an N-limitation regime and an N-optimum regime, common to the three solvents, and an N-excess regime, favorable to the colonization of the filter beds by nitrifying species, which particularly affected the xylene and trimethylbenzene biodegradation.     

Assessment of Needs for Technical Information in EPA’s Hazardous and Solid Waste Programs

Headquarters managers and Regional staff in the U.S. Environmental Protection Agency’s hazardous and solid waste programs were surveyed to determine priorities for technical information and guidance among EPA Regional staff, state hazardous waste management staff, EPA contractors, and the regulated community. The survey also examined delivery systems effective for EPA Regional staff. The fifteen highest ranked technical needs for RCRA, Superfund, and UST reflect a pervasive interest in hazardous waste remediation. Top priority technical needs focus on establishing cleanup levels, subsurface fate and transport, field monitoring and quality assurance, remedy selection, and most importantly, which remedies work and which do not in specific situations. Technical needs of non- EPA audiences are quite similar to those for EPA field staff. Preferences for technology transfer delivery systems are generally for conventional distribution methods (such as print materials and workshops) rather than electronic or video media. Regional staff report serious problems in utilizing technology transfer because of time constraints, insufficient knowledge of available products, insufficient travel funds, and limited access to and training on computers.     

The OTC Challenge: Adding VOC Controls in the Northeast

The 1990 Clean Air Act Amendments create an ozone transport region made up of the northeastern and mid-Atlantic states. These new provisions call for VOC and NOx controls even in clean areas of the region in order to reduce ozone transport to downwind areas. The stationary and mobile source requirements will subject many air pollution sources to controls for the first time.

The provisions also create an Ozone Transport Commission, which can recommend that additional control measures be adopted in all or part of the region. So far, the commission has focused primarily on region-wide mobile source controls, such as California low emission vehicle standards and reformulated gasoline. But lately it has been paying increasing attention to stationary source measures, including NOx controls.     

Measurement of Volatile Organics at Part per Billion Concentrations Using a Cold Trap Inlet and High Speed Gas Chromatography

Direct inlet gas chromatography (GC) is becoming one of the most frequently used techniques for measurement of volatile organics in air. Although GC is an effective tool, its usefulness as a field method can be limited by retention times of several minutes or more, and by the limits of detection. In order to address these issues, a high speed GC system featuring a capillary cold trap inlet and variable speed electrometeramplifier was developed and tested.

The gas cooled inlet was used to collect and focus organic vapors from injection volumes of up to 1 ml. Resistance heating of the metal cold trap produced a narrow injection band that allowed simple separations to be completed in 5 to 20 seconds. Use of a variable speed electrometer-amplifier allowed the response time and noise suppression characteristics to be adjusted to the needs of the specific analysis.

Simple mixtures of organics including aromatics, alkanes and chlorinated hydrocarbons were separated in 20 seconds or less. The limits of detection for 13 test compounds ranged from less than 1 part per billion by volume (ppbv) to about 50 ppbv. Data presented here indicate that high speed GC using a cold trap inlet may be a feasible approach for near real-time measurement of volatile organics in ambient air.     

An Analysis of Biomedical Waste Incineration

The California Air Resources Board (ARB) completed a series of source tests of eight operating biomedical waste incinerators (BMWI) under conditions of typical operation. The emissions of certain metals, and chlorinated dioxins and furans in the flue gases of BMWI are relatively high in comparison to emissions from other combustion sources, such as hazardous waste or municipal waste incinerators of modern design. This study reports on an analysis of the status of the existing regulatory framework and the California data base. Clarification of definitional issues at the federal level is needed to effectively treat BMWI management issues. Although few relationships among combustion parameters and emissions were uncovered, patterns of emissions were evident, suggesting commonality and relationships among the waste stream constituents and emissions. Potential implications for future research, operation of BMWI, controls and source reduction and waste segregation strategies are also discussed.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

Development of Emission Factors for Polycarbonate Processing

Abstract

Emission factors for selected volatile organic compounds (VOCs) and particulate emissions were developed while processing eight commercial grades of polycarbonate (PC) and one grade of a PC/acrylonitrile-butadiene-styrene (ABS) blend. A small commercial-type extruder was used, and the extrusion temperature was held constant at 304 °C. An emission factor was calculated for each substance measured and is reported as pounds released to the atmosphere/million pounds of polymer resin processed [ppm (wt/wt)]. Scaled to production volumes, these emission factors can be used by processors to estimate emission quantities from similar PC processing operations.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Near-source air quality impacts of large olefin flares

Large petrochemical flares, common in the Houston Ship Channel (the Ship Channel) and other industrialized areas in the Gulf of Mexico region, emit hundreds to thousands of pounds per hour of highly reactive volatile organic compounds (HRVOCs). We employed fine horizontal resolution (200 m?×?200 m) in a three-dimensional (3D) Eulerian chemical transport model to simulate two historical Ship Channel flares. The model reasonably reproduced the observed ozone rise at the nearest monitoring stations downwind of the flares. The larger of the two flares had an olefin emission rate exceeding 1400 lb/hr. In this case, the model simulated a rate of increase in peak ozone greater than 40 ppb/hr over a 12 km?×?12 km horizontal domain without any unusual meteorological conditions. In this larger flare, formaldehyde emissions typically neglected in official inventories enhanced peak ozone by as much as 16 ppb and contributed over 10 ppb to ambient formaldehyde up to ～8 km downwind of the flare. The intense horizontal gradients in large flare plumes cannot be simulated by coarse models typically used to demonstrate ozone attainment. Moreover, even the relatively dense monitoring network in the Ship Channel may not be able to detect many transient high ozone events (THOEs) caused by industrial flare emissions in the absence of stagnant air recirculation or stalled sea breeze fronts, even though such conditions are unnecessary for the occurrence of THOEs.

Implications: Flare minimization may be an important strategy to attain the U.S. federal ozone standard in industrialized areas, and to avoid inordinate exposure to formaldehyde in neighborhoods surrounding petrochemical facilities. Moreover, air quality monitoring networks, emission inventories, and chemical transport models with higher spatial and temporal resolution and more refined speciation of HRVOCs are needed to better account for the near-source air quality impacts of large olefin flares.     

A Monte-Carlo Simulation of the Ozone Attainment Process

A Monte-Carlo simulation of the approach to attainment of the National Ambient Air Quality Standard for ozone has been performed for the California Bay Area Air Quality Management District. Four compliance tests together with different design values are used in the simulation. The results show that the present compliance test requiring a zero-percent chance of violation and the design value represented by the fourth highest value in three years makes both the standard and the control requirement much more stringent than generally assumed. In fact, to attain the standard on a long-term basis would require annual means and annual second-highest values that are close to those of the rural background ozone. The simulation also shows that by taking into account the fluctuation of ozone concentrations in the compliance test, such as a t test, and by using a design value consistent with the test, a standard defined in terms of the three-year mean of the annual second-highest values not only is more consistent with the currently- perceived stringency of the present standard, but may also be attainable with a more reasonable control requirement.