The Ozone Productivity of n-Propyl Bromide: Part 2—An Exception to the Maximum Incremental Reactivity Scale

Abstract

In an earlier paper the ozone-forming potential of n-propyl bromide (NPB) was studied with a new methodology designed to address issues associated with a marginal smog-forming compound. However, the U.S. Environmental Protection Agency (EPA) subsequently revised its policy and now recommends using the Maximum Incremental Reactivity (MIR) scale to rank the ozone-forming potential of all volatile organic compounds (VOCs), including those of marginal ozone productivity. Nevertheless, EPA contemplated exceptions to the box-model-derived MIR scale by allowing use of photochemical grid-model simulations for case specific reactivity assessments. The California Air Resources Board (CARB) also uses the MIR scale and CARB has a Reactivity Scientific Advisory Committee that can consider exceptions to the MIR scale. In this study, grid-model simulations that were recommended by EPA are used to evaluate the incremental ozone impacts of NPB using an update to the chemical mechanism developed in an earlier paper. New methods of analysis of the grid-model output are further developed here to quantify the relative reactivities between NPB and ethane over a wide range of conditions. The new grid-model-based analyses show that NPB is significantly different and generally less in ozone-forming potential (i.e., reactivity) than predicted by the box-model-based MIR scale relative to ethane, EPA’s “bright-line” test for non-VOC status. Although NPB has low reactivity compared to typical VOCs on any scale, the new grid-model analyses developed here show that NPB is far less reactive (and even has negative reactivity) compared to the reactivity predicted by the MIR scale.     

Characterization of Sonic Devices Used for Cleaning Fabric Filters

ABSTRACT

Ozone reactivity scales play an important role in selecting which chemical compounds are used in products ranging from gasoline to pesticides to hairspray in California, across the United States and around the world. The California Statewide Air Pollution Research Center (SAPRC) box model that calculates ozone reactivity uses a representative urban atmosphere to predict how much additional ozone forms for each kilogram of compound emission. This representative urban atmosphere has remained constant since 1988, even though more than 25 years of emissions controls have greatly reduced ambient ozone concentrations across the United States during this time period. Here we explore the effects of updating the representative urban atmosphere used for ozone reactivity calculations from 1988 to 2010 conditions by updating the meteorology, emission rates, concentration of initial conditions, concentration of background species, and composition of volatile organic compound (VOC) profiles. Box model scenarios are explored for 39 cities across the United States to calculate the Maximum Incremental Reactivity (MIR) scale for 1,233 individual compounds and compound-mixtures. Median MIR values across the cities decreased by approximately 20.3% when model conditions were updated. The decrease is primarily due to changes in atmospheric composition ultimately attributable to emissions control programs between 1998 and 2010. Further effects were caused by changes in meteorological variables stemming from shifting seasons for peak ozone events (summer versus early fall). Lumped model species with the highest MIR values in 1988 experienced the greatest decrease in MIR values when conditions were updated to 2010. Despite the reduction in the absolute reactivity in the updated 2010 atmosphere, the relative ranking of the VOCs according to their reactivity did not change strongly compared to the original 1988 atmosphere. These findings indicate that past decisions about ozone control programs remain valid today, and the ozone reactivity scale continues to provide relevant guidance for future policy decisions even as new products are developed.

Implications: Updating the representative urban atmosphere used for the Maximum Incremental Reactivity (MIR) scale from 1988 to 2010 conditions caused the reactivity of 1223 individual compounds and combined mixtures to decrease by an average of 20.3% but the relative ranking of the VOCs was not strongly affected. This means that previous guidance about preferred chemical formulations to reduce ozone formation in cities across the United States remain valid today, and the MIR scale continues to provide relevant guidance for future policy decisions even as new products are developed.     

Airshed Model Evaluation of Reactivity Adjustment Factors Calculated with the Maximum Incremental Reactivity Scale for Transitional-Low Emission Vehicles

Abstract

The California Air Resources Board recently adopted regulations for light- and medium-duty vehicles that require reductions in the ozone-forming potential or “reactivity,” rather than the mass, of nonmethane organic gas (NMOG) emissions. The regulations allow sale of all alternatively fueled vehicles (AFVs) that meet NMOG exhaust emission standards equivalent in reactivity to those set for vehicles fueled with conventional gasoline. Reactivity adjustment factors (RAFs), the ratio of the reactivity (per gram) of the AFV exhaust to that of the conventionally fueled vehicle (CFV), are used to correct the stringent exhaust emission standards. Complete chemical speciation of the exhaust and conversion of each NMOG species to an appropriate mass of ozone using the maximum incremental reactivity (MIR) scale of Carter determines the RAF. The MIR approach defines reactivity where NMOG control is the most effective strategy in reducing ozone concentrations, and assumes it is not important to define reactivity at other conditions, i.e., where NO_x is the limiting precursor.

This study used the Carnegie/California Institute of Technology airshed model to evaluate whether the RAF-adjusted AFV emissions result in ozone impacts equivalent to those of CFV emissions. A matrix of two ozone episodes in the South Coast Air Basin (SoCAB) of California, two base emission inventories, and exhaust emissions from three alternative fuels that meet the first level of the low emission vehicle standards bounds the expected range of conditions. Although very good agreement was found previously for individual NMOG species,² this study noted deviations of up to ±15 percent from the equal ozone impacts for any vehicle/fuel combination required by the California regulations. These deviations appear to be attributable to differences in spatial and temporal patterns of emissions between vehicle fleets, rather than a problem with the MIR approach. The first formally adopted RAF, a value of 0.41 for 85 percent methanol/15 percent gasoline-fueled vehicles, includes a 10 percent increase based on the airshed modeling. The correction to the RAF is different for other fuels and may be different for air basins other than the SoCAB.     

Optimized combinations of abatement strategies for urban mobile sources

The maximum incremental reactivity (MIR) scale was chosen as a practical index for quantifying ozone-forming impacts. The integer linear and nonlinear programming techniques were employed as the optimization method to maximize MIR and volatile organic compound (VOC) reductions, and minimize ozone's marginal cost with varied control costs. Mobile vehicles were divided into nine categories according to the demands of decision makers and the distinctive features of local circumstance in metro-Taipei. The emission factor (EF) and vehicle kilometers traveled (VKT) of each kind of vehicle were estimated by MOBILE5B model via native parameters and questionnaires. Compressed natural gas (CNG) and inspection and maintenance (I/M) were the alternative control programs for buses and touring buses; liquefied petroleum gas (LPG), I/M, methanol, electrical vehicle (EV) were for taxis and low duty gasoline vehicles. EV, methanol, and I/M were the possible control methods for two-stroke and four-stroke engine motorcycles; I/M programs for low-duty diesel trucks, heavy-duty diesel trucks, and low-duty gasoline trucks. The results include the emission ratios of specific vehicle to all vehicles, the best combination of abated measures based on different objectives, and the marginal cost for ozone and VOC with varied control costs.     

Estimation of incremental reactivities for multiple day scenarios: an application to ethane and dimethyoxymethane

Single-day scenarios are used to calculate incremental reactivities by definition (Carter, J. Air Waste Management Assoc. 44 (1994) 881–899.) but even unreactive organic compounds may have a non-negligible effect on ozone concentrations if multiple-day scenarios are considered. The concentration of unreactive compounds and their products may build up over a multiple-day period and the oxidation products may be highly reactive or highly unreactive affecting the overall incremental reactivity of the organic compound. We have developed a method for calculating incremental reactivities for multiple days based on a standard scenario for polluted European conditions. This method was used to estimate maximum incremental reactivities (MIR) and maximum ozone incremental reactivities (MOIR) for ethane and dimethyoxymethane for scenarios ranging from 1 to 6 days. It was found that the incremental reactivities increased as the length of the simulation period increased. The MIR of ethane increased faster than the value for dimethyoxymethane as the scenarios became longer. The MOIRs of ethane and dimethyoxymethane increased but the change was more modest for scenarios longer than 3 days. MOIRs of both volatile organic compounds were equal within the uncertainties of their chemical mechanisms by the 5 day scenario. These results show that dimethyoxymethane has an ozone forming potential on a per mass basis that is only somewhat greater than ethane if multiple-day scenarios are considered.     

Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi,Pakistan

Mixing ratios of carbon monoxide (CO), methane (CH₄), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998–1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3 ppmv) and ethane (93 ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH₄ levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3–19 ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2 ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O₃) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O₃ production in Karachi are ethene, CO, propene, m-xylene and toluene.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

Estimating the ozone formation potential of volatile aromatic compounds in vehicle tunnels.

Two vehicle tunnels located in the Taipei area were selected to study the ozone formation potential of volatile aromatic compounds (VACs). Air samples in the two tunnels were collected using canisters. Analysis of VACs was conducted with a gas chromatograph equipped with a mass spectrometer. The total VOCs concentrations in Zefun tunnel ranged from 483.5 to 1032.2 (micrograms/m3) which increased with the increase in traffic volume. In the Lishin tunnel, the total VACs concentration ranged from 356.6 to 1961.3 (micrograms/m3) which was not well correlated with the traffic volume. The most predominant VACs in these vehicle tunnels were toluene and xylenes. Although the traffic volume and types of vehicles were not exactly the same, the characteristic ratios of the VACs concentrations were found to be similar. These results indicated that the existence of a specific characteristic ratio of VAC concentration was affected by the mobile sources. The maximum ozone formation potential resulted from the vehicles in the Lishin motorcycle tunnel which had higher values than the Zefun tunnel and much higher than the SPECIATE databases in the US via weighting the maximum incremental reactivity (MIR) scale.     

Development of the SAPRC-07 chemical mechanism

An updated version of the SAPRC-99 gas-phase atmospheric chemical mechanism, designated SAPRC-07, is described. The rate constants and reactions have been updated based on current data and evaluations, the aromatics mechanisms have been reformulated and are less parameterized, chlorine chemistry has been added, the method used to represent peroxy reactions has been reformulated to be more appropriate for modeling gas-phase secondary organic aerosol precursors, and representations for many types of VOCs have been added or improved. This mechanism was evaluated against the result of ～2400 environmental chamber experiments carried out in 11 different environmental chambers, including experiments to test mechanisms for over 110 types of VOCs. The performance in simulating the chamber data was generally satisfactory for most types of VOCs but some biases were seen in simulations of some types of experiments. The mechanism was used to derive updated MIR and other ozone reactivity scales for almost 1100 types of VOCs, though in most cases the changes in MIR values relative to SAPRC-99 were not large. This mechanism update results in somewhat lower predictions of ozone in one-day ambient model scenarios under low VOC/NO_x conditions. The files needed to implement the mechanism and additional documentation is available at the SAPRC mechanism web site at http://www.cert.ucr.edu/～carter/SAPRC.     

The ozone formation potential of 1-bromo-propane

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photochemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

Scientific Basis of an Improved EPA Policy on Control of Organic Emissions for Ambient Ozone Reduction

ABSTRACT

This article describes an effort to re-examine the scientific bases of the existing, more than two decades-old U.S. Environmental Protection Agency (EPA) policy on volatile organic compound reactivity in light of recent scientific knowledge and understanding. The existing policy allows “negligibly reactive” organic emissions, that is, emissions with ambient ozone production potential lower than that of ethane, to be exempted from all ozone regulations. It relies on use of k_OH and incremental reactivity data for determining whether an organic compound is negligibly reactive. Recent scientific evidence suggests that (1) exempting the negligibly reactive organic emissions from all regulations is unjustifiable, (2) the choice of ethane as the benchmark organic species for distinguishing reactive from negligibly reactive organics may be inappropriate, (3) the assumptions and methods used for classifying organic compounds as “reactive” and “negligibly reactive” should be reconsidered, and (4) the volatility factor should be considered, more appropriately, in much the same way as the reactivity factor.     

Emission,speciation, and evaluation of impacts of non-methane volatile organic compounds from open dump site

Surface emission from Dhapa, the only garbage disposal ground in Kolkata, is a matter of concern to the local environment and also fuels the issues of occupational and environmental health. Surface emission of the Dhapa landfill site was studied using a flux chamber measurement for nonmethane volatile organic compounds (NMVOCs). Eighteen noncarbonyl volatile organic compounds (VOCs) and 14 carbonyl VOCs, including suspected and known carcinogens, were found in appreciable concentrations. The concentrations of the target species in the flux chamber were found to be significantly higher for most of the species in summer than winter. Surface emission rate of landfill gas was estimated by using two different approaches to assess the applicability for an open landfill site. It was found that the emissions predicted using the model Land GEM version 3.02 is one to two orders less than the emission rate calculated from flux chamber measurement for the target species. Tropospheric ozone formation has a serious impact for NMVOC emission. The total ozone-forming potential (OFP) of the Dhapa dumping ground considering all target NMVOCs was estimated to be 4.9E+04 and 1.2E+05 g/day in winter and summer, respectively. Also, it was found that carbonyl VOCs play a more important role than noncarbonyl VOCs for tropospheric ozone formation. Cumulative cancer risk estimated for all the carcinogenic species was found to be 2792 for 1 million population, while the total noncancer hazard index (HI) was estimated to be 246 for the occupational exposure to different compounds from surface emission to the dump-site workers at Dhapa.

Implications:This paper describes the real-time surface emission of NMVOCs from an open municipal solid waste (MSW) dump site studied using a flux chamber. Our study findings indicate that while planning for new landfill site in tropical meteorology, real-time emission data must be considered, rather than relying on modeled data. The formation of tropospheric ozone from emitted NMVOC has also been studied. Our result shows how an open landfill site acts as a source and adds to the tropospheric ozone for the airshed of a metropolitan city.     

Effects of Constant versus Diurnally-Varying Light Intensity on Ozone Formation

Abstract

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photo-chemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

Estimate of initial isoprene contribution to ozone formation potential in Beijing, China

Volatile organic compounds (VOCs) are important precursors of tropospheric ozone formation. Isoprene contributions to ozone formation by using ambient mixing ratios are generally underestimated because of rapid chemical losses. In this study, ambient mixing ratios of major VOC species were continuously measured at Peking university (PKU) and YUFA, urban and sub-urban sites in Beijing, the city that will host 2008 Olympic Games. The observed mixing ratios of methyl vinyl ketone (MVK), methacrolein (MACR) and isoprene were used to derive the mixing ratios of initial isoprene, which means the ambient isoprene level before it undergoes any photochemical reaction with OH radicals. The average mixing ratios of initial isoprene were 3.3±1.6 and 2.9±1.5 ppbv at PKU and YUFA sites, respectively. The percentages of initial isoprene in total initial VOCs were 10.8% at PKU site and 11.4% at YUFA site, in reasonable agreement with the isoprene contribution in total VOC emissions as derived from source inventories. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential (OFP) for major VOC species. The OFP for initial isoprene accounted for 23% of the total OFPs for all measured species, compared to 11% using ambient mixing ratios of isoprene at PKU site. Similarly, at YUFA site, the ambient measured isoprene and initial isoprene contributed 10% and 22%, respectively, to the OFPs for total measured VOCs. It seems that isoprene has similar contribution to ozone formation at both sites in Beijing city.     

Photochemical reactivities of common solvents: comparison between urban and regional domains

Solvents are one of the most abundant sources of anthropogenic VOCs in the atmosphere, and can comprise a large number of organic compounds having different impacts on the rate and amount of ozone formation. A three-dimensional photochemical air quality model has been used to study the relative impacts of eight solvents, acetone, ethane, ethanol, isobutane, m-xylene, tertiary butyl acetate (TBA), para-chlorobenzotrifluoride (PCBTF) and benzotrifluoride (BTF) in three very different domains: Los Angeles, an urban area with high ozone and NO_x levels; the Swiss Plateau, a more regional domain with much lower ozone and NO_x levels: and Mexico City, a very high VOC urban area with high ozone levels. The results show that there can be a wide range of VOC reactivities under variable environmental conditions. Variability also exists between metrics, which are used to quantify reactivity. In most cases, halogenated aromatics were the least reactive and isobutane and m-xylene the most. The results here, finding that normalized reactivities are less variable than the absolute reactivity, support the applicability of relative VOC reactivity scales for use in air quality management.     

Characteristics and source apportionment of VOCs measured in Shanghai,China

Volatile organic compounds (VOCs) were measured from 2007 to 2010 at the center of Shanghai, China. Because VOCs are important precursors for ozone photochemical formation, detailed information of VOC sources needs to be investigated. The results show that the measured VOC concentrations in Shanghai are dominated by alkanes (43%) and aromatics (30%), following by halo-hydrocarbons (14%) and alkenes (6%). Based on the measured VOC concentrations, a receptor model (PMF; positive matrix factorization) coupled with the information related to VOC sources (the distribution of major industrial complex, meteorological conditions, etc.) is applied to identify the major VOC sources in Shanghai. The result shows that seven major VOC sources are identified by the PMF method, including (1) vehicle related source which contributes to 25% of the measured VOC concentrations, (2) solvent based industrial source to 17%, (3) fuel evaporation to 15%, (4) paint solvent usage to 15%, (5) steel related industrial production to 12%, (6) biomass/biofuel burning to 9%, and (7) coal burning to 7%. Furthermore, ozone formation potential related to VOC sources is calculated by the MIR (maximum incremental reactivity) technique. The most significant VOC source for ozone formation potential is solvent based industrial sources (27%), paint solvent usage (24%), vehicle related emissions (17%), steel related industrial productions (14%), fuel evaporations (9%), coal burning (6%), and biomass/biofuel burning (3%). The weekend effect on the VOC concentrations shows that VOC concentrations are generally higher in the weekdays than in the weekends at the sampling site, suggesting that traffic conditions and human activities have important impacts on the VOC emissions in Shanghai.     

Effects of reactive hydrocarbons on ozone formation in southern Taiwan

Ambient air samples were collected at 13 air quality monitoring stations in Kaohsiung city, Kaohsiung county, and Pingtung county (KKP) to investigate the composition and spatial distribution of C₂–C₁₀ non-methane hydrocarbons (NMHCs) in southern Taiwan. Ozone formation potentials (OFPs) of NMHCs were estimated using maximum incremental reactivity (MIR) and k_OH method (reactivity of NMHC with OH radical) to assess the relative effects of hydrocarbons on ozone formation. The measurements showed that mixing ratios of toluene, ethene, ethyne, ethane, isopantane and propane were the highest among all measured species at most of the sampling sites. Nevertheless, considering both the photochemical reactivities and mixing ratios of all the measured species, toluene, xylene, ethene and propene were calculated to have the highest OFPs and reactivities. The OFPs and reactivities assessed by the MIR and k_OH methods for the four compounds accounted for 54.5% and 39.3% of all the measured species. Larger benefit margin of ozone abatement may be obtained by reducing emissions of a group of key species with high OFPs.2,2-dimethylbutane (22DMC4) was used as an indicator of traffic emissions to distinguish traffic from non-traffic contributions of key species in Kaohsiung metropolitan area. It revealed that the contribution of non-traffic source was significant for toluene, whereas xylene was found to be primarily from the traffic source in Kaohsiung metropolitan area during the sampling periods.     

Volatile organic compound emissions from municipal solid waste disposal sites: a case study of Mumbai, India

Improper solid waste management leads to aesthetic and environmental problems. Emission ofvolatile organic compounds (VOCs) is one of the problems from uncontrolled dumpsite. VOCs are well known to be hazardous to human health and many of them are known or potential carcinogens. They also contribute to ozone formation at ground level and climate change as well. The qualitative and quantitative analysis of VOCs emitting from two municipal waste (MSW) disposal sites in Mumbai, India, namely Deonar and Malad, are presented in this paper. Air at dumpsites was sampled and analyzed on gas chromatography-mass spectrometry (GC-MS) in accordance with U.S. Environmental Protection Agency (EPA) TO-17 compendium method for analysis of toxic compounds. As many as 64 VOCs were qualitatively identified, among which 13 are listed under hazardous air pollutants (HAPs). Study of environmental distribution of a few major VOCs indicates that although air is the principal compartment of residence, they also get considerably partitioned in soil and vegetation. The CO2 equivalent of target VOCs from the landfills in Malad and Deonar shows that the total yearly emissions are 7.89E+03 and 8.08E+02 kg, respectively. The total per hour ozone production from major VOCs was found to be 5.34E-01 ppb in Deonar and 9.55E-02 ppb in Malad. The total carcinogenic risk for the workers in the dumpsite considering all target HAPs are calculated to be 275 persons in 1 million in Deonar and 139 persons in 1 million in Malad.