Highly Reactive Volatile Organic Compounds Research Articles

Characterization of the incipient smoke point for steam-/air-assisted and nonassisted flares

ABSTRACTFlares are important safety devices for pressure relief; at the same time, flares are a significant point source for soot and highly reactive volatile organic compounds (HRVOCs). Currently, simple guidelines for flare operations to maintain high combustion efficiency (CE) remain elusive. This paper fills the gap by investigating the characteristics of the incipient smoke point (ISP), which is widely recognized as the condition for good combustion. This study characterizes the ISP in terms of 100–% combustion inefficiency (CE), percent opacity, absorbance, air assist, steam assist, air equivalence ratio, steam equivalence ratio, exit velocity, vent gas net heating value, and combustion zone net heating value. Flame lengths were calculated for buoyant and momentum-dominated plumes under calm and windy conditions at stable and neutral atmosphere. Opacity was calculated using the Beer–Lambert law based on soot concentration, flame diameter, and mass-specific extinction cross section of soot. The calculated opacity and absorbance were found to be lognormally distributed. Linear relations were established for soot yield versus absorptivity with R2 > 0.99 and power-law relations for opacity versus soot emission rate with R2 ≥ 0.97 for steam-assisted, air-assisted, and nonassisted flares. The characterized steam/air assists, combustion zone/vent gas heating values, exit velocity, steam, and air equivalence ratios for the incipient smoke point will serve as a useful guideline for efficient flare operations.Implications: A Recent EPA rule requires an evaluation of visible emissions in terms of opacity in compliance with the standards. In this paper, visible emissions such as soot particles are characterized in terms of opacity at ISP. Since ISP is widely recognized as most efficient flare operation for high combustion efficiency (CE)/destruction efficiency (DE) with initial soot particles formed in the flame, this characterization provides a useful guideline for flare operators in the refinery, oil and gas, and chemical industries to sustain smokeless and high combustion efficiency flaring in compliance with recent EPA regulations, in addition to protecting the environment.

Long-term meteorologically independent trend analysis of ozone air quality at an urban site in the greater Houston area

ABSTRACTThe Houston-Galveston-Brazoria (HGB) area of Texas has a history of ozone exceedances and is currently classified under moderate nonattainment status for the 2008 8-hr ozone standard of 75 ppb. The HGB area is characterized by intense solar radiation, high temperature, and high humidity, which influence day-to-day variations in ozone concentrations. Long-term air quality trends independent of meteorological influence need to be constructed for ascertaining the effectiveness of air quality management in this area. The Kolmogorov-Zurbenko (KZ) filter technique, used to separate different scales of motion in a time series, is applied in the current study for maximum daily 8-hr (MDA8) ozone concentrations at an urban site (U.S. Environmental Protection Agency [EPA] Air Quality System [AQS] Site ID: 48-201-0024, Aldine) in the HGB area. This site, located within 10 miles of downtown Houston and the George Bush Intercontinental Airport, was selected for developing long-term meteorologically independent MDA8 ozone trends for the years 1990–2016. Results from this study indicate a consistent decrease in meteorologically independent MDA8 ozone between 2000 and 2016. This pattern could be partially attributed to a reduction in underlying nitrogen oxide (NOx) emissions, particularly lowering nitrogen dioxide (NO2) levels, and a decrease in the release of highly reactive volatile organic compounds (HRVOCs). Results also suggest solar radiation to be most strongly correlated to ozone, with temperature being the secondary meteorological control variable. Relative humidity and wind speed have tertiary influence at this site. This study observed that meteorological variability accounts for a high of 61% variability in baseline ozone (low-frequency component, sum of long-term and seasonal components), whereas 64% of the change in long-term MDA8 ozone post 2000 could be attributed to NOx emission reduction. Long-term MDA8 ozone trend component was estimated to be decreasing at a linear rate of 0.412 ± 0.007 ppb/yr for the years 2000–2016 and 0.155 ± 0.005 ppb/yr for the overall period of 1990–2016.Implications: The effectiveness of air emission controls can be evaluated by developing long-term air quality trends independent of meteorological influences. The KZ filter technique is a well-established method to separate an air quality time series into short-term, seasonal, and long-term components. This paper applies the KZ filter technique to MDA8 ozone data between 1990 and 2016 at an urban site in the greater Houston area and estimates the variance accounted for by the primary meteorological control variables. Estimates for linear trends of MDA8 ozone are calculated and underlying causes are investigated to provide a guidance for further investigation into air quality management of the greater Houston area.

Retrospective Air Quality Simulations of the TexAQS-II: Focused on Emissions Uncertainty

There are several studies on the effects of emissions of highly reactive volatile organic compounds (HRVOC) from the industrial sources in the Houston-Galveston-Brazoria (HGB) area on the high ozone events during the Texas Air Quality Study (TexAQS) in summer of 2000. They showed that the modeled atmosphere lacked reactivity to produce the observed high ozone event and suggested “imputation” of HRVOC emissions from the base inventory. Byun et al. (2007b) showed the imputed inventory leads to too high ethylene concentrations compared to the measurements at the chemical super sites but still too little aloft compared to the NOAA aircraft. The paper suggested that the lack of reactivity in the modeled Houston atmosphere must be corrected by targeted, and sometimes of episodic, increase of HRV OC emissions from the large sources such as flares in the Houston Ship Channel (HSC) distributed into the deeper level of the boundary layer. We performed retrospective meteorological and air quality modeling to achieve better air quality prediction of ozone by comparison with various chemical and meteorological measurements during the Texas Air Quality Study periods in August-September 2006 (TexA QS-Ⅱ). After identifying several shortcomings of the forecast meteorological simulations and emissions inputs, we prepared new retrospective meteorological simulations and updated emissions inputs. We utilized assimilated MM5 inputs to achieve better meteorological simulations (detailed description of MM5 assimilation can be found in F. Ngan et al., 2012) and used them in this study for air quality simulations. Using the better predicted meteorological results, we focused on the emissions uncertainty in order to capture high peak ozone which occasionally happens in the HGB area. We described how the ozone predictions are affected by emissions uncertainty in the air quality simulations utilizing different emission inventories and adjustments.

Anthropogenic emissions of highly reactive volatile organic compounds in eastern Texas inferred from oversampling of satellite (OMI) measurements of HCHO columns

Satellite observations of formaldehyde (HCHO) columns provide top-down constraints on emissions of highly reactive volatile organic compounds (HRVOCs). This approach has been used previously in the US to estimate isoprene emissions from vegetation, but application to anthropogenic emissions has been stymied by lack of a discernable HCHO signal. Here we show that temporal oversampling of HCHO data from the Ozone Monitoring Instrument (OMI) for 2005–2008 enables detection of urban and industrial plumes in eastern Texas including Houston, Port Arthur, and Dallas/Fort Worth. By spatially integrating the HCHO enhancement in the Houston plume observed by OMI we estimate an anthropogenic HCHO source of 250 ± 140 kmol h−1. This implies that anthropogenic HRVOC emissions in Houston are 4.8 ± 2.7 times higher than reported by the US Environmental Protection Agency inventory, and is consistent with field studies identifying large ethene and propene emissions from petrochemical industrial sources.

Slower ozone production in Houston, Texas following emission reductions: evidence from Texas Air Quality Studies in 2000 and 2006

Abstract. Airborne measurements from two Texas Air Quality Study (TexAQS) field campaigns have been used to investigate changes of ozone production in Houston, Texas, from 2000 to 2006, a period of major emission reduction measures for petrochemical and other sources. Simultaneous declines in nitrogen oxides (NOx = NO + NO2) and highly reactive volatile organic compounds (HRVOCs) were observed between the two periods. We simulate HOx (OH and HO2) and organic radicals with a box model, the Dynamically Simple Model of Atmospheric Chemical Complexity, constrained by available airborne observations. Parameters such as total radical production, total OH reactivity of VOCs and ozone production rate (OPR) are computed to characterize the change of ozone production between 2000 and 2006 in the Houston area. The reduction in HRVOCs led to a decline in total radical production by 20–50%. Ozone production rates in the Houston area declined by 40–50% from 2000 to 2006, to which the reduction in NOx and HRVOCs made large contributions. Despite the significant decline in OPR, ozone production efficiency held steady, and VOC-sensitive conditions dominated during times of most rapid ozone formation, while the slow ozone formation continued to be NOx-limited. Our results highlight the importance of a balanced approach of ongoing HRVOC controls with NOx controls to further reduce O3 levels in the Houston area.

Houston’s rapid ozone increases: preconditions and geographic origins

Many of Houston's highest 8-h ozone (O3) peaks are characterised by increases in concentrations of at least 40 ppb in 1 h, or 60 ppb in 2 h. These rapid increases are called non-typical O3 changes (NTOCs). In 2004, the Texas Commission on Environmental Quality (TCEQ) developed a novel emissions control strategy aimed at eliminating NTOCs. The strategy limited routine and short-term emissions of ethene, propene, 1,3-butadiene and butene isomers, collectively called highly reactive volatile organic compounds (HRVOCs), which are released from petrochemical facilities. HRVOCs have been associated with NTOCs through field campaigns and modelling studies. This study analysed wind measurements and O3, formaldehyde (HCHO) and sulfur dioxide (SO2) concentrations from 2000 to 2011 at 25 ground monitors in Houston. NTOCs almost always occurred when monitors were downwind of petrochemical facilities. Rapid O3 increases were associated with low wind speeds; 75 % of NTOCs occurred when the 3-h average wind speed preceding the event was less than 6.5 km h-1. Statistically significant differences in HCHO concentrations were seen between days with and without NTOCs. Early afternoon HCHO concentrations were greater on NTOC days. In the morning before an observed NTOC event, however, there were no significant differences in HCHO concentrations between days with and without NTOCs. Hourly SO2 concentrations also increased rapidly, exhibiting behaviour similar to NTOCs. Oftentimes, the SO2 increases preceded a NTOC. These findings show that, despite the apparent success of targeted HRVOC emission controls, further restrictions may be needed to eliminate the remaining O3 events.

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.

Primary and secondary sources of formaldehyde in urban atmospheres: Houston Texas region

Abstract. We evaluate the rates of secondary production and primary emission of formaldehyde (CH2O) from petrochemical industrial facilities and on-road vehicles in the Houston Texas region. This evaluation is based upon ambient measurements collected during field studies in 2000, 2006 and 2009. The predominant CH2O source (92 ± 4% of total) is secondary production formed during the atmospheric oxidation of highly reactive volatile organic compounds (HRVOCs) emitted from the petrochemical facilities. Smaller contributions are primary emissions from these facilities (4 ± 2%), and secondary production (~3%) and primary emissions (~1%) from vehicles. The primary emissions from both sectors are well quantified by current emission inventories. Since secondary production dominates, control efforts directed at primary CH2O emissions cannot address the large majority of CH2O sources in the Houston area, although there may still be a role for such efforts. Ongoing efforts to control alkene emissions from the petrochemical facilities, as well as volatile organic compound emissions from the motor vehicle fleet, will effectively reduce the CH2O concentrations in the Houston region. We do not address other emission sectors, such as off-road mobile sources or secondary formation from biogenic hydrocarbons. Previous analyses based on correlations between ambient concentrations of CH2O and various marker species have suggested much larger primary emissions of CH2O, but those results neglect confounding effects of dilution and loss processes, and do not demonstrate the causes of the observed correlations. Similar problems must be suspected in any source apportionment analysis of secondary species based upon correlations of ambient concentrations of pollutants.

Removal of Propylene and Butylene as Individual Compounds with Compost and Wood Chip Biofilters

ABSTRACT Propylene and butylene are highly reactive volatile organic compounds (HRVOCs) in terms of ground-level ozone formation. This study examined the effectiveness of biofiltration in removing propylene and butylene as separate compounds. Specific objectives were (1) to measure maximum removal efficiencies for propylene and butylene and the corresponding microbial acclimation times, which will be useful in the design of future biofilters for removal of these compounds; (2) to compare removal efficiencies of propylene and butylene for different ratios of compost/hard wood-chip media; and (3) to identify the microorganisms responsible for propylene and butylene degradation. Two laboratory-scale polyvinyl chloride biofilter columns were filled with 28 in. of biofilter media (compost/wood-chip mixtures of 80:20 and 50:50 ratios). Close to 100% removal efficiency was obtained for propylene for inlet concentrations ranging from 2.9 × 104 to 6.3 × 104 parts per million (ppm) (232–602 g/m3-hr) and for butylene for inlet concentrations ranging from 91 to 643 ppm (1.7–13.6 g/m3-hr). The microbial acclimation period to attain 100% removal efficiency was 12–13 weeks for both compounds. The lack of similar microbial species in the fresh and used media likely accounts for the long acclimation time required. Both ratios of compost/wood chips (80:20 and 50:50) gave similar results. During the testing, media pH increased slightly from 7.1 to 7.5–7.7. None of the species in the used media that treated butylene were the same as those in the used media that treated propylene, indicating that different microbes are adept at degrading the two compounds. IMPLICATIONS This study is the first, to the authors’ knowledge, to demonstrate the effectiveness of a compost/wood-chip biofilter for propylene and butylene removal. Propylene and butylene are HRVOCs that are very efficient at forming ground-level ozone. This research determined removal efficiency values, microbial acclimation times, and microbial species responsible for compound degradation that will all be useful in the design of future biofilters for the removal of these compounds.

Overview of the Second Texas Air Quality Study (TexAQS II) and the Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS)

The Second Texas Air Quality Study (TexAQS II) was conducted in eastern Texas during 2005 and 2006. This 2‐year study included an intensive field campaign, TexAQS 2006/Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS), conducted in August–October 2006. The results reported in this special journal section are based on observations collected on four aircraft, one research vessel, networks of ground‐based air quality and meteorological (surface and radar wind profiler) sites in eastern Texas, a balloon‐borne ozonesonde‐radiosonde network (part of Intercontinental Transport Experiment Ozonesonde Network Study (IONS‐06)), and satellites. This overview paper provides operational and logistical information for those platforms and sites, summarizes the principal findings and conclusions that have thus far been drawn from the results, and directs readers to appropriate papers for the full analysis. Two of these findings deserve particular emphasis. First, despite decreases in actual emissions of highly reactive volatile organic compounds (HRVOC) and some improvements in inventory estimates since the TexAQS 2000 study, the current Houston area emission inventories still underestimate HRVOC emissions by approximately 1 order of magnitude. Second, the background ozone in eastern Texas, which represents the minimum ozone concentration that is likely achievable through only local controls, can approach or exceed the current National Ambient Air Quality Standard of 75 ppbv for an 8‐h average. These findings have broad implications for air quality control strategies in eastern Texas.

Modeling ozone formation from industrial emission events in Houston, Texas

It is now generally accepted that industrial emission events are occurring from chemical processing facilities in Houston, Texas with daily frequencies and significant temporal variability. These events have been reported to last from hours to days, and a large fraction are made up of four highly reactive volatile organic compounds (HRVOCs): ethene, propene, butenes, and 1,3-butadiene. The Texas Commission on Environmental Quality (TCEQ) has targeted industrial sources of HRVOCs by imposing annual and hourly limits and creating a market-based HRVOC emissions cap and trade (HECT) program. The HECT program uses the Maximum Incremental Reactivity (MIR) scale to calculate the magnitude needed to trade between HRVOCs. The work reported here used the TCEQ regulatory model to evaluate the HECT program's use of the MIR scale by simulating a series of hypothetical but observational-based industrial emission events for different VOC species. The magnitude of each release was adjusted based on the MIR scale under the assumption that this would give the same increase in ozone. The regulatory model, however, predicted that o-xylene caused the largest increase in ozone. In every simulation, ozone production was directly related to the amount of hydroxyl radicals produced from the photolysis of formaldehyde and other aldehydes. The sensitivity of ozone production to these hydroxyl radical sources appeared regardless of whether the industrial emission event plume encountered high sources of NO x . The MIR scale was developed for an average urban atmosphere and its failure in equating ozone reactivity here may be due to the extreme levels of NO x and VOC seen in event emissions in Houston.

Application of high resolution land use and land cover data for atmospheric modeling in the Houston–Galveston Metropolitan area: Part II: Air quality simulation results

In the companion paper, we showed that MM5 simulation using a satellite-derived high resolution Texas Forest Service (TFS) land use and land cover (LULC) data set (M2), compared to the MM5 results with the default USGS-LULC (M1), improved representation of the complicated features of the atmospheric planetary boundary layer (PBL) in the Houston ship channel (HSC) area, where large industrial emission sources are concentrated. In the present paper, the study is extended to investigate these effects on air quality simulations. Two emission inputs, namely E1 and E2, are prepared with the M1 and M2 meteorology data, respectively, to reflect the differences in the point source plume rise estimates while keeping the biogenic and mobile emissions the same. Air quality simulations were performed with CMAQ using the M1E1 and M2E2 inputs. The simulation results demonstrate the importance of utilizing high resolution LULC data. In the default LULC data, the HSC area was classified as grass land cover, and MM5 predicted confined mixing, resulting in over-prediction of ozone (O 3) precursors, such as NO x (NO plus NO 2), and highly reactive volatile organic compounds (HRVOC) species, including ethylene and propylene, over the HSC area. In the TFS data, the area was classified as the impervious “urban” land use and MM5 predicted enhanced mixing of the precursor species, leading to better agreements with measurements. The high resolution LULC also resolves the location of water body near the HSC more accurately, predicting shallower PBL heights than the default LULC during daytime. With favorable wind conditions, the O 3 precursors were transported from the HSC emission source towards the area, trapping the pollutants in a confined shallow mixing layer that occasionally led to a rapid photochemical production of O 3. The above comparison includes the changes in both meteorological and plume-rise emissions inputs. We performed two additional CMAQ simulations using the same meteorological result (M2) but with different emission point sources E1 and E2 to determine the importance of emission changes on the air quality simulations. The sensitivity tests with the different plume-rise emission inputs due to two different meteorological inputs show little impact on the air quality simulations in this case.

Photochemical Modeling of Emissions Trading of Highly Reactive Volatile Organic Compounds in Houston, Texas. 1. Reactivity Based Trading and Potential for Ozone Hot Spot Formation

As part of the State Implementation Plan for attaining the National Ambient Air Quality Standard for ozone, the Texas Commission of Environmental Quality has created a Highly Reactive Volatile Organic Compounds (HRVOC) Emissions Cap and Trade Program for industrial point sources in the Houston/Galveston/Brazoria area. This program has a number of unique features, including its focus on a limited group of ozone precursors and its provisions for trading emissions based on atmospheric reactivity. This series of papers examines the potential air quality impacts of this new emission trading program through photochemical modeling of potential trading scenarios; this first paper in the series describes the air quality modeling methods used to assess potential trades, the potential for localized increases in ozone concentrations (ozone "hot spots") due to HRVOC emission trading, and the use of reactivity scales in the trading. When HRVOC emissions are traded on a mass basis, the simulations indicate that trading of HRVOC allowances between facilities resulted in less than 0.15 ppb (<0.13%) and 0.06 ppb (<0.06%) increases in predicted maximum, area-wide 1-h averaged and 8-h averaged ozone concentrations, respectively. Maximum decreases in ozone concentrations associated with trading, as opposed to across-the-board reductions, were larger than the increases. All of these changes are small compared to the maximum changes in ozone concentrations due to the VOC emissions from these sources (up to 5-10 ppb for 8 h averages; up to 30 ppb for 1-h averages). When emissions of HRVOCs are traded for other, less reactive emissions, on a reactivity weighted basis, air quality simulations indicate that daily maximum ozone concentrations increased by less than 0.3%. Because these relatively small changes (< 1%) are for unlikely trading scenarios designed to produce a maximum change in ozone concentrations (all emissions traded into localized regions), the simulations indicate that the implementation of the trading program, as currently configured and possibly expanded, is unlikely to cause localized increases in ozone concentrations ("hot spots").

Photochemical Modeling of Emissions Trading of Highly Reactive Volatile Organic Compounds in Houston, Texas. 2. Incorporation of Chlorine Emissions

As part of the State Implementation Plan for attaining the National Ambient Air Quality Standard for ozone, the Texas Commission of Environmental Quality has created a Highly Reactive Volatile Organic Compounds (HRVOC) Emissions Cap and Trade Program for industrial point sources in the Houston/Galveston/Brazoria area. This series of papers examines the potential air quality impacts of this new emission trading program through photochemical modeling of potential trading scenarios; this paper examines the air quality impact of allowing facilities to trade chlorine emission reductions for HRVOC allocations on a reactivity weighted basis. The simulations indicate that trading of anthropogenic chlorine emission reductions for HRVOC allowances at a single facility or between facilities, in general, resulted in improvements in air quality. Decreases in peak 1-h averaged and 8-h averaged ozone concentrations associated with trading chlorine emissions for HRVOC allocations on a Maximum Incremental Reactivity (MIR) basis were up to 0.74 ppb (0.63%) and 0.56 ppb (0.61%), respectively. Air quality metrics based on population exposure decreased by up to 3.3% and 4.1% for 1-h and 8-h averaged concentrations. These changes are small compared to the maximum changes in ozone concentrations due to the VOC emissions from these sources (5-10 ppb for 8-h averages; up to 30 ppb for 1-h averages) and the chlorine emissions from the sources (5-10 ppb for maximum concentrations over wide areas and up to 70 ppb in localized areas). The simulations indicate that the inclusion of chlorine emissions in the trading program is likely to be beneficial to air quality and is unlikely to cause localized increases in ozone concentrations ("hot spots").

Evaluation of air quality models for the simulation of a high ozone episode in the Houston metropolitan area

A high ozone event in the Houston–Galveston–Brazoria area was utilized to study the shortcomings of the current air quality models. To improve the baseline simulations with the Comprehensive Air quality Model with Extensions (CAMx) for developing the state implementation plan, the Texas Commission on Environmental Quality (TCEQ) imputed emissions of highly reactive volatile organic compounds (HRVOCs) by scaling the amount of fugitive emissions of olefins to co-emitted NO x from selected point sources, effectively multiplying by 3–12 times over the regular inventory values. In this paper, CAMx and the Community Multiscale Air Quality (CMAQ) model were used to determine if the imputed HRVOC emissions were consistent with the observed atmospheric conditions. With the base emissions, CMAQ and CAMx both with the Carbon-Bond 4 (CB-4) mechanism simulated similar ozone concentrations. But with the imputed HRVOC emissions, CMAQ predicted lower ozone peaks than CAMx in the vicinity and downwind of the Ship Channel and other highly HRVOC-rich areas. Based on analyses of sensitivity simulations of CMAQ with different emission inputs and vertical diffusion algorithms in the model, we found that the modeled atmosphere lacked reactivity to produce the observed high ozone event. Although the imputed HRVOC emissions improved ozone prediction at the surface sites, but the ethylene concentrations were not consistent with the measurements at the super sites (La Porte and Clinton) and by NOAA aircraft. Several sensitivity tests designed to provide additional radicals into the system and other research results suggested that the lack of reactivity may need to be corrected by targeted, and probably of episodic, increase of HRVOC emissions, from the sources in the Houston Ship Channel. Additional investigation of the ozone production efficiency for different chemical mechanisms is necessary to pinpoint the emissions uncertainty issues.

Hydrocarbon emissions from industrial release events in the Houston-Galveston area and their impact on ozone formation

Abstract Ambient measurements have shown that ozone formation in the Houston-Galveston area of Texas is frequently much more rapid than in other urban areas. One of the contributing factors is believed to be short-term episodic or “event” emissions from industrial facilities, particularly releases that contain significant mass fractions of highly reactive volatile organic compounds (HRVOCs). In this work, time series analyses are used to compare average annual flow rates for air pollutant emissions with those released during reported emission events. The results indicate that the magnitude and frequency of HRVOC event emissions are an important element in accurately reflecting ozone precursor emission patterns in the Houston-Galveston area, particularly in Harris, Brazoria, Galveston, and Chambers counties. More than 50% of the reported episodic (event) emissions of HRVOCs are ethene and approximately a third are propene; the remainders are isomers of butene and 1,3-butadiene. Most events last less than 24 h. The mass released in an event can vary from a few hundred to more than 100,000 lb, and the dominant type of industrial source is chemical manufacturers (SIC 2869). Daily emissions from a single facility can vary from annual average emissions by multiple orders of magnitude at a frequency of several times a year. Because there are so many facilities in the Houston-Galveston area, HRVOC emission variability of this magnitude can be expected daily, at some time and some location in the Houston-Galveston area. If the emission variability occurs at times and locations where atmospheric conditions are conducive to ozone formation, both ambient data and photochemical modeling indicate that industrial emission events can lead to elevated concentrations of ozone. Specifically, peak, area-wide ozone concentration can be increased by as much as 100 ppb for large HRVOC emission events.