Repository for Oil and Gas Energy Research (ROGER)

Abstract:
Enhanced prospects for natural gas production raise questions about the balance of impacts on air quality, as increased emissions from production activities are considered alongside the reductions expected when natural gas is burned in place of other fossil fuels. This study explores how trends in natural gas production over the coming decades might affect emissions of greenhouse gases (GHG), volatile organic compounds (VOCs) and nitrogen oxides (NOx) for the United States and its Rocky Mountain region. The MARKAL (MARKet ALlocation) energy system optimization model is used with the U.S. Environmental Protection Agency's nine-region database to compare scenarios for natural gas supply and demand, constraints on the electricity generation mix, and GHG emissions fees. Through 2050, total energy system GHG emissions show little response to natural gas supply assumptions, due to offsetting changes across sectors. Policy-driven constraints or emissions fees are needed to achieve net reductions. In most scenarios, wind is a less expensive source of new electricity supplies in the Rocky Mountain region than natural gas. U.S. NOx emissions decline in all the scenarios considered. Increased VOC emissions from natural gas production offset part of the anticipated reductions from the transportation sector, especially in the Rocky Mountain region.

Abstract:
The Northern Front Range (NFR) region of Colorado has experienced rapid expansion of oil and gas extraction from shale and tight sands reservoirs in recent years due to advances in hydraulic fracturing technology, with over 25,000 wells currently in operation. This region has also been designated as a federal ozone non-attainment area by the U.S. EPA. High ozone levels are a significant health concern, as are potential health impacts from chronic exposure to primary emissions of non-methane hydrocarbons (NMHC) for residents living near wells. From measurements of ambient atmospheric NMHC present in residential areas located in close proximity to wells in Erie, Colorado, we find that mean mole fractions of the C2–C5 alkanes are enhanced by a factor of 18–77 relative to the regional background, and present at higher levels than typically found in large urban centers. When combined with NMHC observations from downtown Denver and Platteville, it is apparent that these compounds are elevated across the NFR, with highest levels within the Greater Wattenberg Gas Field. This represents a large area source for ozone precursors in the NFR. The BTEX aromatic compounds in Erie were comparable to (e.g., benzene) or lower than (e.g., toluene, ethylbenzene, xylene) in large urban centers, however, benzene was significantly higher in Platteville, and within the range of chronic health-based exposure levels. An initial look at comparisons with data sets from previous years reveal that ambient levels for oil and gas-related NMHC in Erie, as well as further downwind in Boulder, have not decreased, but appear to have been increasing, despite tightening of emissions standards for the oil and gas industries in 2008.

Abstract:
Horizontal drilling, hydraulic fracturing, and other drilling and well stimulation technologies are now used widely in the United States and increasingly in other countries. They enable increases in oil and gas production, but there has been inadequate attention to human health impacts. Air quality near oil and gas operations is an underexplored human health concern for five reasons: (1) prior focus on threats to water quality; (2) an evolving understanding of contributions of certain oil and gas production processes to air quality; (3) limited state air quality monitoring networks; (4) significant variability in air emissions and concentrations; and (5) air quality research that misses impacts important to residents. Preliminary research suggests that volatile compounds, including hazardous air pollutants, are of potential concern. This study differs from prior research in its use of a community-based process to identify sampling locations. Through this approach, we determine concentrations of volatile compounds in air near operations that reflect community concerns and point to the need for more fine-grained and frequent monitoring at points along the production life cycle.

Abstract:
Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H2S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H2S using proton-transfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H2S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H2S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H2S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H2S is only slightly higher than that of water. The H2S sensitivity of PTR-MS ranged between 0.6–1.4 ncps ppbv−1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H2S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H2S measurements using a PTR time-of-flight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H2S / CH4. On average 0.6 ± 0.3 ppbv H2S was present at Horse Pool during UBWOS 2013. The correlation between H2S and methane enhancements suggests that the source of H2S is associated with oil and gas extraction in the basin. Significant H2S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H2S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of H2S at levels below 1 ppbv.

Abstract:
The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

Abstract:
During the past decade, technological advancements in the United States and Canada have led to rapid and intensive development of many unconventional natural gas plays (e.g., shale gas, tight sand gas, coal-bed methane), raising concerns about environmental impacts. Here, we summarize the current understanding of local and regional air quality impacts of natural gas extraction, production, and use. Air emissions from the natural gas life cycle include greenhouse gases, ozone precursors (volatile organic compounds and nitrogen oxides), air toxics, and particulates. National and state regulators primarily use generic emission inventories to assess the climate, air quality, and health impacts of natural gas systems. These inventories rely on limited, incomplete, and sometimes outdated emission factors and activity data, based on few measurements. We discuss case studies for specific air impacts grouped by natural gas life cycle segment, summarize the potential benefits of using natural gas over other fossil fuels, and examine national and state emission regulations pertaining to natural gas systems. Finally, we highlight specific gaps in scientific knowledge and suggest that substantial additional measurements of air emissions from the natural gas life cycle are essential to understanding the impacts and benefits of this resource.

Abstract:
During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River basin (UGRB), Wyoming, during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1 h average up to 166 ppbv – parts per billion by volume). Intensive operational periods (IOPs) of ambient monitoring were performed, which included comprehensive surface and boundary layer measurements. On IOP days, maximum O3 values are restricted to a very shallow surface layer. Low wind speeds in combination with low mixing layer heights (~ 50 m above ground level around noontime) are essential for accumulation of pollutants within the UGRB. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days particularly in the morning hours, reactive nitrogen (up to 69%), aromatics and alkanes (~ 10–15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. Measurements at the Boulder monitoring site during these time periods under SW wind flow conditions show the lowest NMHC / NOx ratios (~ 50), reflecting a relatively low reactive NMHC mixture, and a change from a NOx-limited regime towards a NMHC-limited regime as indicated by photochemical indicators, e.g., O3 /NOy, O3 /NOz, and O3 / HNO3 and the EOR (extent of reaction). OH production on IOP days is mainly due to nitrous acid (HONO). On a 24 h basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~ 83% to OH production on average, followed by alkene ozonolysis (~ 9%). Photolysis by ozone and HCHO photolysis contribute about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1096 pptv – parts per trillion by volume) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO (estimated HONO production: 10.2 ± 40% ppbv h−1) and (ii) combustion-related emission of HONO (estimated HONO production: ~ 0.1 ± 30% ppbv h−1). HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to the high albedo of the snow cover (HONO photolysis rate 10.7 ± 30% ppbv h−1). OH radicals will oxidize NMHCs, mostly aromatics (toluene, xylenes) and alkanes (ethane, propane), eventually leading to an increase in ozone.

Abstract:
The emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uinta Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aromatics, alkanes, cycloalkanes and methanol were observed for extended periods of time and short-term spikes caused by local point sources. The mixing ratios during the time the mobile laboratory spent on the well pads were averaged. High mixing ratios were found close to all point sources, but gas wells using dry-gas collection, which means dehydration happens at the well, were clearly associated with higher mixing ratios than other wells. Another large source was the flowback pond near a recently hydraulically re-fractured gas well. The comparison of the VOC composition of the emissions from the oil and natural gas wells showed that wet gas collection wells compared well with the majority of the data at Horse Pool and that oil wells compared well with the rest of the ground site data. Oil wells on average emit heavier compounds than gas wells. The mobile laboratory measurements confirm the results from an emissions inventory: the main VOC source categories from individual point sources are dehydrators, oil and condensate tank flashing and pneumatic devices and pumps. Raw natural gas is emitted from the pneumatic devices and pumps and heavier VOC mixes from the tank flashings.

Abstract:
Hourly ambient hydrocarbon concentration data were collected, in the Barnett Shale Natural Gas Production Region, using automated gas chromatography (auto-GC), for the period from April 2010 to December 2011. Data for three sites were compared: a site in the geographical center of the natural gas production region (Eagle Mountain Lake (EML)); a rural/suburban site at the periphery of the production region (Flower Mound Shiloh), and an urban site (Hinton). The dominant hydrocarbon species observed in the Barnett Shale region were light alkanes. Analyses of daily, monthly, and hourly patterns showed little variation in relative composition. Observed concentrations were compared to concentrations predicted using a dispersion model (AERMOD) and a spatially resolved inventory of volatile organic compounds (VOC) emissions from natural gas production (Barnett Shale Special Emissions Inventory) prepared by the Texas Commission on Environmental Quality (TCEQ), and other emissions information. The predicted concentrations of VOC due to natural gas production were 0?40% lower than background corrected measurements, after accounting for potential under-estimation of certain emission categories. Hourly and daily variations in observed, background corrected concentrations were primarily explained by variability in meteorology, suggesting that episodic emission events had little impact on hourly averaged concentrations. Total emissions for VOC from natural gas production sources are estimated to be approximately 25?300 tons/yr, when accounting for potential under-estimation of certain emission categories. This region produced, in 2011, approximately 5 bcf/d of natural gas (100 Gg/d) for a VOC to natural gas production ratio (mass basis) of 0.0006.

Abstract:
Emissions of methane (CH4) from oil and natural (O&G) gas operations in the most densely drilled area of the Denver-Julesburg (D-J) Basin in Weld County located in northeastern Colorado are estimated for two days in May 2012 using aircraft-based CH4 observations and planetary boundary layer height and ground-based wind profile measurements. Total top-down CH4 emission estimates are 25.8 ± 8.4 and 26.2 ± 10.7 tonnes CH4/hr for the May 29 and May 31 flights, respectively. Using inventory data, we estimate the total emissions of CH4 from non-O&G gas related sources at 7.1 ± 1.7 and 6.3 ± 1.0 tonnes CH4/hr for these two days. The difference in emissions is attributed to O&G sources in the study region and their total emission is on average 19.3 ± 6.9 tonnes/hr, close to three times higher than an hourly emission estimate based on EPA's Greenhouse Gas Reporting Program data for 2012. We derive top-down emissions estimates for propane, n-butane, i-pentane, n-pentane, and benzene from our total top-down CH4 emission estimate and the relative hydrocarbon abundances in aircraft-based discrete air samples. Emissions for these five non-methane hydrocarbons alone total 25.4 ± 8.2 tonnes/hr. Assuming these emissions are solely originating from O&G related activities in the study region, our results show that the state inventory for total VOC emitted by O&G activities is at least a factor of two too low for May 2012. Our top-down emission estimate of benzene emissions from O&G operations is 173 ± 64 kg/hr, or seven times larger than in the state inventory.

Abstract:
Increased use of hydraulic fracturing (“fracking”) in unconventional oil and natural gas (O & NG) development from coal, sandstone, and shale deposits in the United States (US) has created environmental concerns over water and air quality impacts. In this perspective we focus on how the production of unconventional O & NG affects air quality. We pay particular attention to shale gas as this type of development has transformed natural gas production in the US and is set to become important in the rest of the world. A variety of potential emission sources can be spread over tens of thousands of acres of a production area and this complicates assessment of local and regional air quality impacts. We outline upstream activities including drilling, completion and production. After contrasting the context for development activities in the US and Europe we explore the use of inventories for determining air emissions. Location and scale of analysis is important, as O & NG production emissions in some US basins account for nearly 100% of the pollution burden, whereas in other basins these activities make up less than 10% of total air emissions. While emission inventories are beneficial to quantifying air emissions from a particular source category, they do have limitations when determining air quality impacts from a large area. Air monitoring is essential, not only to validate inventories, but also to measure impacts. We describe the use of measurements, including ground-based mobile monitoring, network stations, airborne, and satellite platforms for measuring air quality impacts. We identify nitrogen oxides, volatile organic compounds (VOC), ozone, hazardous air pollutants (HAP), and methane as pollutants of concern related to O & NG activities. These pollutants can contribute to air quality concerns and they may be regulated in ambient air, due to human health or climate forcing concerns. Close to well pads, emissions are concentrated and exposure to a wide range of pollutants is possible. Public health protection is improved when emissions are controlled and facilities are located away from where people live. Based on lessons learned in the US we outline an approach for future unconventional O & NG development that includes regulation, assessment and monitoring.

Abstract:
Production of natural gas from shale formations is bringing drilling and production operations to regions of the United States that have seen little or no similar activity in the past, which has generated considerable interest in potential environmental impacts. This study focused on the Barnett Shale Fort Worth Basin in Texas, which saw the number of gas-producing wells grow from 726 in 2001 to 15,870 in 2011. This study aimed to measure fence line concentrations of methane and hydrogen sulfide at natural gas production sites (wells, liquid storage tanks, and associated equipment) in the four core counties of the Barnett Shale (Denton, Johnson, Tarrant, and Wise). A mobile measurement survey was conducted in the vicinity of 4788 wells near 401 lease sites, representing 35% of gas production volume, 31% of wells, and 38% of condensate production volume in the four-county core area. Methane and hydrogen sulfide concentrations were measured using a Picarro G2204 cavity ring-down spectrometer (CRDS). Since the research team did not have access to lease site interiors, measurements were made by driving on roads on the exterior of the lease sites. Over 150 hr of data were collected from March to July 2012. During two sets of drive-by measurements, it was found that 66 sites (16.5%) had methane concentrations >3 parts per million (ppm) just beyond the fence line. Thirty-two lease sites (8.0%) had hydrogen sulfide concentrations >4.7 parts per billion (ppb) (odor recognition threshold) just beyond the fence line. Measured concentrations generally did not correlate well with site characteristics (natural gas production volume, number of wells, or condensate production). t tests showed that for two counties, methane concentrations for dry sites were higher than those for wet sites. Follow-up study is recommended to provide more information at sites identified with high levels of methane and hydrogen sulfide. Implications:Information regarding air emissions from shale gas production is important given the recent increase in number of wells in various regions in the United States. Methane, the primary natural gas constituent, is a greenhouse gas; hydrogen sulfide, which can be present in gas condensate, is an odor-causing compound. This study surveyed wells representing one-third of the natural gas production volume in the Texas Barnett Shale and identified the percent of sites that warrant further study due to their fence line methane and hydrogen sulfide concentrations.

Abstract:
Abstract Case study descriptions of acute onset of respiratory, neurologic, dermal, vascular, abdominal, and gastrointestinal sequelae near natural gas facilities contrast with a subset of emissions research, which suggests that there is limited risk posed by unconventional natural gas development (UNGD). An inspection of the pathophysiological effects of acute toxic actions reveals that current environmental monitoring protocols are incompatible with the goal of protecting the health of those living and working near UNGD activities. The intensity, frequency, and duration of exposures to toxic materials in air and water determine the health risks to individuals within a population. Currently, human health risks near UNGD sites are derived from average population risks without adequate attention to the processes of toxicity to the body. The objective of this paper is to illustrate that current methods of collecting emissions data, as well as the analyses of these data, are not sufficient for accurately assessing risks to individuals or protecting the health of those near UNGD sites. Focusing on air pollution impacts, we examined data from public sources and from the published literature. We compared the methods commonly used to evaluate health safety near UNGD sites with the information that would be reasonably needed to determine plausible outcomes of actual exposures. Such outcomes must be based on the pathophysiological effects of the agents present and the susceptibility of residents near these sites. Our study has several findings. First, current protocols used for assessing compliance with ambient air standards do not adequately determine the intensity, frequency or durations of the actual human exposures to the mixtures of toxic materials released regularly at UNGD sites. Second, the typically used periodic 24-h average measures can underestimate actual exposures by an order of magnitude. Third, reference standards are set in a form that inaccurately determines health risk because they do not fully consider the potential synergistic combinations of toxic air emissions. Finally, air dispersion modeling shows that local weather conditions are strong determinates of individual exposures. Appropriate estimation of safety requires nested protocols that measure real time exposures. New protocols are needed to provide 1) continuous measures of a surrogate compound to show periods of extreme exposure; 2) a continuous screening model based on local weather conditions to warn of periodic high exposures; and 3) comprehensive detection of chemical mixtures using canisters or other devices that capture the major components of the mixtures.

Abstract:
Oil and natural gas production in the Western United States has grown rapidly in recent years, and with this industrial expansion, growing environmental concerns have arisen regarding impacts on water supplies and air quality. Recent studies have revealed highly enhanced atmospheric levels of volatile organic compounds (VOCs) from primary emissions in regions of heavy oil and gas development and associated rapid photochemical production of ozone during winter. Here, we present surface and vertical profile observations of VOC from the Uintah Basin Winter Ozone Studies conducted in January?February of 2012 and 2013. These measurements identify highly elevated levels of atmospheric alkane hydrocarbons with enhanced rates of C2?C5 nonmethane hydrocarbon (NMHC) mean mole fractions during temperature inversion events in 2013 at 200?300 times above the regional and seasonal background. Elevated atmospheric NMHC mole fractions coincided with build-up of ambient 1-h ozone to levels exceeding 150 ppbv (parts per billion by volume). The total annual mass flux of C2?C7 VOC was estimated at 194 ± 56 ? 106 kg yr?1, equivalent to the annual VOC emissions of a fleet of ?100 million automobiles. Total annual fugitive emission of the aromatic compounds benzene and toluene, considered air toxics, were estimated at 1.6 ± 0.4 ? 106 and 2.0 ± 0.5 ? 106 kg yr?1, respectively. These observations reveal a strong causal link between oil and gas emissions, accumulation of air toxics, and significant production of ozone in the atmospheric surface layer.

Abstract:
Oil and natural gas exploration and production (E&P) activities generate emissions from diesel engines, compressor stations, condensate tanks, leaks and venting of natural gas, construction of well pads, and well access roads that can negatively impact air quality on both local and regional scales. A mobile, autonomous air quality monitoring laboratory was constructed to collect measurements of ambient concentrations of pollutants associated with oil and natural gas E&P activities. This air-monitoring laboratory was deployed to the Allegheny National Forest (ANF) in northwestern Pennsylvania for a campaign that resulted in the collection of approximately 7 months of data split between three monitoring locations between July 2010 and June 2011. The three monitoring locations were the Kane Experimental Forest (KEF) area in Elk County, which is downwind of the Sackett oilfield; the Bradford Ranger Station (BRS) in McKean County, which is downwind of a large area of historic oil and gas productivity; and the U.S. Forest Service Hearts Content campground (HC) in Warren County, which is in an area relatively unimpacted by oil and gas development and which therefore yielded background pollutant concentrations in the ANF. Concentrations of criteria pollutants ozone and NO2 did not vary significantly from site to site; averages were below National Ambient Air Quality Standards. Concentrations of volatile organic compounds (VOCs) associated with oil and natural gas (ethane, propane, butane, pentane) were highly correlated. Applying the conditional probability function (CPF) to the ethane data yielded most probable directions of the sources that were coincident with known location of existing wells and activity. Differences between the two impacted and one background site were difficult to discern, suggesting the that the monitoring laboratory was a great enough distance downwind of active areas to allow for sufficient dispersion with background air such that the localized plumes were not detected. ImplicationsMonitoring of pollutants associated with oil and natural gas exploration and production activity at three sites within the Allegheny National Forest (ANF) showed only slight site-to-site differences even with one site far removed from these activities. However, the impact was evident not in detection of localized plumes but in regional elevated ethane concentrations, as ethane can be considered a tracer species for oil and natural gas activity. The data presented serve as baseline conditions for evaluation of impacts from future development of Marcellus or Utica shale gas reserves.

Abstract:
Winter maximum daily 8-hour average (MDA8) ozone concentrations in the Upper Green River Basin, Wyoming (UGRBWY) and the Uintah Basin, Utah (UBUT) have frequently exceeded 100 ppb in January, February and March, in the past few years. Such levels are well above the U.S. air quality standard of 75 ppb. In these two remote basins in the Rockies, local ozone precursor emissions result from intense oil and gas extraction activities that release methane, volatile organic compounds (VOCs), and nitrogen oxides (NOx) to the atmosphere. These emissions become trapped beneath a stable and shallow (~50–200 m) boundary layer maintained in low wind conditions. Wintertime surface ozone formation conditions are more likely in the UBUT than in the UGRBWY as the topography of the UBUT is an enclosed basin whereas the UGRBWY is open on its southern perimeter thus allowing for more air turnover. With snow-covered ground, high ozone events regularly begin in mid-December and last into early March in the UBUT whereas they usually do not begin in earnest until about a month later in the UGRBWY and may persist until mid-March. Winters without snow cover and the accompanying cold pool meteorological conditions do not experience high ozone events in either basin. For nine years with ozone observations in the UGRBWY (2005–2013) and four in the UBUT (2010–2013), all years with adequate (≥6 inches) and persistent snow cover, experienced days with ozone values ≥75 ppb except in 2012 in the UGRBWY when persistent high wind (>5 m/s) conditions were prevalent. Year to year differences in the occurrences of high ozone episodes appear to be driven primarily by differing meteorological conditions rather than by variations in ozone precursor levels.

Abstract:
The US Energy Information Administration projects that hydraulic fracturing of shale formations will become a dominant source of domestic natural gas supply over the next several decades, transforming the energy landscape in the United States. However, the environmental impacts associated with fracking for shale gas have made it controversial. This review examines emissions and impacts of air pollutants associated with shale gas production and use. Emissions and impacts of greenhouse gases, photochemically active air pollutants, and toxic air pollutants are described. In addition to the direct atmospheric impacts of expanded natural gas production, indirect effects are also described. Widespread availability of shale gas can drive down natural gas prices, which, in turn, can impact the use patterns for natural gas. Natural gas production and use in electricity generation are used as a case study for examining these indirect consequences of expanded natural gas availability. Expected final online publication date for the Annual Review of Chemical and Biomolecular Engineering Volume 5 is June 07, 2014. Please see http://www.annualreviews.org/catalog/pubdates.aspx for revised estimates.

Abstract:

Abstract:
Shale gas exploration and production (E&P) has experienced substantial growth across the U.S. over the last decade. The Barnett Shale, in north-central Texas, contains one of the largest, most active onshore gas fields in North America, stretching across 5000 square miles and having an estimated 15,870 producing wells as of 2011. Given that these operations may occur in relatively close proximity to populated/urban areas, concerns have been expressed about potential impacts on human health. In response to these concerns, the Texas Commission on Environmental Quality established an extensive air monitoring network in the region. This network provides a unique data set for evaluating the potential impact of shale gas E&P activities on human health. As such, the objective of this study was to evaluate community-wide exposures to volatile organic compounds (VOCs) in the Barnett Shale region. In this current study, more than 4.6 million data points (representing data from seven monitors at six locations, up to 105 VOCs/monitor, and periods of record dating back to 2000) were evaluated. Measured air concentrations were compared to federal and state health-based air comparison values (HBACVs) to assess potential acute and chronic health effects. None of the measured VOC concentrations exceeded applicable acute HBACVs. Only one chemical (1,2-dibromoethane) exceeded its applicable chronic HBACV, but it is not known to be associated with shale gas production activities. Annual average concentrations were also evaluated in deterministic and probabilistic risk assessments and all risks/hazards were below levels of concern. The analyses demonstrate that, for the extensive number of VOCs measured, shale gas production activities have not resulted in community-wide exposures to those VOCs at levels that would pose a health concern. With the high density of active wells in this region, these findings may be useful for understanding potential health risks in other shale play regions.

Abstract:
The Marcellus Shale is one of the largest natural gas reserves in the United States; it has recently been the focus of intense drilling and leasing activity. This paper describes an air emissions inventory for the development, production, and processing of natural gas in the Marcellus Shale region for 2009 and 2020. It includes estimates of the emissions of oxides of nitrogen (NOx), volatile organic compounds (VOCs), and primary fine particulate matter (≤2.5 µm aerodynamic diameter; PM2.5) from major activities such as drilling, hydraulic fracturing, compressor stations, and completion venting. The inventory is constructed using a process-level approach; a Monte Carlo analysis is used to explicitly account for the uncertainty. Emissions were estimated for 2009 and projected to 2020, accounting for the effects of existing and potential additional regulations. In 2020, Marcellus activities are predicted to contribute 6–18% (95% confidence interval) of the NOx emissions in the Marcellus region, with an average contribution of 12% (129 tons/day). In 2020, the predicted contribution of Marcellus activities to the regional anthropogenic VOC emissions ranged between 7% and 28% (95% confidence interval), with an average contribution of 12% (100 tons/day). These estimates account for the implementation of recently promulgated regulations such as the Tier 4 off-road diesel engine regulation and the U.S. Environmental Protection Agency's (EPA) Oil and Gas Rule. These regulations significantly reduce the Marcellus VOC and NOx emissions, but there are significant opportunities for further reduction in these emissions using existing technologies. Implications: The Marcellus Shale is one of the largest natural gas reserves in United States. The development and production of this gas may emit substantial amounts of oxides of nitrogen and volatile organic compounds. These emissions may have special significance because Marcellus development is occurring close to areas that have been designated nonattainment for the ozone standard. Control technologies exist to substantially reduce these impacts. PM2.5 emissions are predicted to be negligible in a regional context, but elemental carbon emissions from diesel powered equipment may be important.

Abstract:
This exploratory study was designed to assess air quality in a rural western Colorado area where residences and gas wells co-exist. Sampling was conducted before, during, and after drilling and hydraulic fracturing of a new natural gas well pad. Weekly air sampling for 1 year revealed that the number of non-methane hydrocarbons (NMHCs) and their concentrations were highest during the initial drilling phase and did not increase during hydraulic fracturing in this closed-loop system. Methylene chloride, a toxic solvent not reported in products used in drilling or hydraulic fracturing, was detected 73% of the time; several times in high concentrations. A literature search of the health effects of the NMHCs revealed that many had multiple health effects, including 30 that affect the endocrine system, which is susceptible to chemical impacts at very low concentrations, far less than government safety standards. Selected polycyclic aromatic hydrocarbons (PAHs) were at concentrations greater than those at which prenatally exposed children in urban studies had lower developmental and IQ scores. The human and environmental health impacts of the NMHCs, which are ozone precursors, should be examined further given that the natural gas industry is now operating in close proximity to human residences and public lands.

Abstract:
Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppmv). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression. Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.

Abstract:
A comprehensive suite of volatile organic compounds (VOCs) was measured at the semirural Boulder Atmospheric Observatory (BAO) in northeast Colorado during the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) campaign during the winter of 2011. A signature of elevated nonmethane hydrocarbon (NMHC) mixing ratios was observed throughout the campaign. The C2-C5 alkane mixing ratios were an order of magnitude greater than the regional background. Light alkane mixing ratios were similar to those at urban sites impacted by petrochemical industry emissions with ethane and propane reaching maximums of over 100 ppbv. The mean (± standard deviation) calculated total OH reactivity (7.0 ± 5.0 s−1) was also similar to urban sites. Analysis of VOC wind direction dependence, emission ratios with tracer compounds, and vertical profiles up to 250 m implicated regional natural gas production activities as the source of the elevated VOCs to the northeast of BAO and urban combustion emissions as the major VOC source to the south of BAO. Elevated acetonitrile and dimethyl sulfide mixing ratios were also associated with natural gas emissions. Fluxes of natural gas associated NMHCs were determined to estimate regional emission rates which ranged from 40 ± 14 Gg yr−1 for propane to 0.03 ± 0.01 Gg yr−1 for n-nonane. These emissions have the potential to impact downwind air quality as natural gas associated NMHCs comprised ≈24% of the calculated OH reactivity. The measurements described here provide a baseline for determining the efficacy of future policies designed to control emissions from natural gas production activities.

Abstract:
Natural gas use in electricity generation in Texas was estimated, for gas prices ranging from $1.89 to $7.74 per MMBTU, using an optimal power flow model. Hourly estimates of electricity generation, for individual electricity generation units, from the model were used to estimate spatially resolved hourly emissions from electricity generation. Emissions from natural gas production activities in the Barnett Shale region were also estimated, with emissions scaled up or down to match demand in electricity generation as natural gas prices changed. As natural gas use increased, emissions decreased from electricity generation and increased from natural gas production. Overall, NOx and SO2 emissions decreased, while VOC emissions increased as natural gas use increased. To assess the effects of these changes in emissions on ozone and particulate matter concentrations, spatially and temporally resolved emissions were used in a month-long photochemical modeling episode. Over the month-long photochemical modeling episode, decreases in natural gas prices typical of those experienced from 2006 to 2012 led to net regional decreases in ozone (0.2-0.7 ppb) and fine particulate matter (PM) (0.1-0.7 μg/m(3)). Changes in PM were predominantly due to changes in regional PM sulfate formation. Changes in regional PM and ozone formation are primarily due to decreases in emissions from electricity generation. Increases in emissions from increased natural gas production were offset by decreasing emissions from electricity generation for all the scenarios considered.

Abstract:
The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) concentrations above levels harmful to human health for multiple days during the winters of 2009-2010 and 2010-2011. These wintertime O3 pollution episodes occur during cold, stable periods when the ground is snowcovered, and have been linked to emissions from the oil and gas extraction process. The Uintah Basin Winter Ozone Study (UBWOS) was a field intensive in early 2012, whose goal was to address current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. Although elevated O3 concentrations were not observed during the winter of 2011-2012, the comprehensive set of observations tests of our understanding of O3 photochemistry in this unusual emissions environment. A box model, constrained to the observations and using the explicit Master Chemical Mechanism (MCM) V3.2 chemistry scheme, has been used to investigate the sensitivities of O3 production during UBWOS 2012. Simulations identify the O3 production photochemistry to be highly radical limited. Production of OH from O3 photolysis (through reaction of O(1D) with water vapor) contributed only 170 pptv day-1, 8% of the total primary radical source on average. Other radical sources, including the photolysis of formaldehyde (HCHO, 52%), nitrous acid (HONO, 26%), and nitryl chloride (ClNO2, 13%) were larger. O3 production was also found to be highly sensitive to aromatic volatile organic compound (VOC) concentrations, due to radical amplification reactions in the oxidation scheme of these species. Radical production was shown to be small in comparison to the emissions of nitrogen oxides (NOx), such that NOx acted as the primary radical sink. Consequently, the system was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons (230 ppbv (2080 ppbC), 6 week average) relative to NOx (5.6 ppbv average). However, the importance of radical sources which are themselves derived from NOx emissions and chemistry, such as ClNO2 and HONO, make the response of the system to changes in NOx emissions uncertain. These box model simulations provide useful insight into the chemistry controlling winter O3 production in regions of oil and gas extraction.

Abstract:
An extensive set of volatile organic compounds (VOCs) was measured at the Boulder Atmospheric Observatory (BAO) in winter 2011 in order to investigate the composition and influence of VOC emissions from oil and natural gas (O&NG) operations in northeastern Colorado. BAO is 30 km north of Denver and is in the southwestern section of Wattenberg Field, one of Colorado?s most productive O&NG fields. We compare VOC concentrations at BAO to those of other U.S. cities and summertime measurements at two additional sites in northeastern Colorado, as well as the composition of raw natural gas from Wattenberg Field. These comparisons show that (i) the VOC source signature associated with O&NG operations can be clearly differentiated from urban sources dominated by vehicular exhaust, and (ii) VOCs emitted from O&NG operations are evident at all three measurement sites in northeastern Colorado. At BAO, the reactivity of VOCs with the hydroxyl radical (OH) was dominated by C2?C6 alkanes due to their remarkably large abundances (e.g., mean propane = 27.2 ppbv). Through statistical regression analysis, we estimate that on average 55 ± 18% of the VOC?OH reactivity was attributable to emissions from O&NG operations indicating that these emissions are a significant source of ozone precursors.

Abstract:
The Comment by Levi (2012) on our paper, Pétron et al. (2012), presents a different interpretation of the atmospheric data and inventory estimates we used to derive our conclusions about methane emissions from oil and natural gas development in the Denver-Julesburg Basin (DJB) in Weld County, Colorado. Levi's (2012) Comment brings up new issues that point to the need for additional information. We maintain the value of the results derived in Pétron et al. (2012), particularly that vented and fugitive methane emissions from Weld County's fossil fuel exploration and production in 2008 were likely larger and more uncertain than values reported by emission inventories. Our findings rely on the interpretation of high-quality atmospheric observations using existing inventory data provided by the industry and regulatory agencies and on reasonable assumptions about the average vented raw gas composition. However, Levi (2012) has caused us to extend our analysis and to better characterize the uncertainties associated with his and with our approaches. In this Reply, we examine some critical limitations of the Pétron et al. (2012) and Levi (2012) interpretations of the atmospheric data using simple, two-source emission models that incorporate inventory data sets of unknown reliability. We present new evidence that the regulatory estimates of flashing emission and regulatory modeled composition profiles for a limited number of condensate tanks, the starting point for the calculations of Pétron et al. (2012) and Levi (2012), probably do not represent the true range of these parameters for the thousands of such sources across the DJB in 2008. The results of Levi (2012) suggest that leakage in Weld County in 2008 was biased toward dry gas wells, which disagrees with current inventories of venting and fugitive emissions in U.S. oil and gas fields, including the DJB. Most importantly, the indirect flux derivations undertaken by Levi (2012) and Pétron et al. (2012) highlight two inherent shortcomings common to most emissions inventories: their reliance on the extrapolation of very limited information and the difficulty in carrying out a full uncertainty analysis of such datasets. We agree with Levi (2012) that there is an urgent need to statistically document the composition profiles and magnitudes of significant sources in oil- and gas-producing fields. Observations-based methods with established uncertainties and that are completely independent of inventory information could directly quantify emission strengths and compositions of both point and aggregated area sources, providing an objective assessment of inventory methodology and estimates.

Abstract:
Pétron et al. (2012) have recently observed and analyzed alkane concentrations in air in Colorado's Weld County and used them to estimate the volume of methane vented from oil and gas operations in the Denver-Julesburg Basin. They conclude that “the emissions of the species we measured are most likely underestimated in current inventories”, often by large factors. However, their estimates of methane venting, and hence of other alkane emissions, rely on unfounded assumptions about the composition of vented natural gas. We show that relaxing those assumptions results in much greater uncertainty. We then exploit previously unused observations reported in Pétron et al. (2012) to constrain methane emissions without making assumptions about the composition of vented gas. This results in a new set of estimates that are consistent with current inventories but inconsistent with the estimates in Pétron et al. (2012). The analysis also demonstrates the value of the mobile air sampling method employed in Pétron et al. (2012).

Abstract:
We use historical and new atmospheric trace gas observations to refine the estimated source of methane (CH4) emitted into California?s South Coast Air Basin (the larger Los Angeles metropolitan region). Referenced to the California Air Resources Board (CARB) CO emissions inventory, total CH4 emissions are 0.44 ± 0.15 Tg each year. To investigate the possible contribution of fossil fuel emissions, we use ambient air observations of methane (CH4), ethane (C2H6), and carbon monoxide (CO), together with measured C2H6 to CH4 enhancement ratios in the Los Angeles natural gas supply. The observed atmospheric C2H6 to CH4 ratio during the ARCTAS (2008) and CalNex (2010) aircraft campaigns is similar to the ratio of these gases in the natural gas supplied to the basin during both these campaigns. Thus, at the upper limit (assuming that the only major source of atmospheric C2H6 is fugitive emissions from the natural gas infrastructure) these data are consistent with the attribution of most (0.39 ± 0.15 Tg yr?1) of the excess CH4 in the basin to uncombusted losses from the natural gas system (approximately 2.5?6% of natural gas delivered to basin customers). However, there are other sources of C2H6 in the region. In particular, emissions of C2H6 (and CH4) from natural gas seeps as well as those associated with petroleum production, both of which are poorly known, will reduce the inferred contribution of the natural gas infrastructure to the total CH4 emissions, potentially significantly. This study highlights both the value and challenges associated with the use of ethane as a tracer for fugitive emissions from the natural gas production and distribution system.

Abstract:
Increased drilling in urban areas overlying shale formations and its potential impact on human health through decreased air quality make it important to estimate the contribution of oil and gas activities to photochemical smog. Flares and compressor engines used in natural gas operations, for example, are large sources not only of NOx but also offormaldehyde, a hazardous air pollutant and powerful ozone precursor We used a neighborhood scale (200 m horizontal resolution) three-dimensional (3D) air dispersion model with an appropriate chemical mechanism to simulate ozone formation in the vicinity ofa hypothetical natural gas processing facility, based on accepted estimates of both regular and nonroutine emissions. The model predicts that, under average midday conditions in June, regular emissions mostly associated with compressor engines may increase ambient ozone in the Barnett Shale by more than 3 ppb beginning at about 2 km downwind of the facility, assuming there are no other major sources of ozone precursors. Flare volumes of 100,000 cubic meters per hour ofnatural gas over a period of 2 hr can also add over 3 ppb to peak 1-hr ozone somewhatfurther (>8 km) downwind, once dilution overcomes ozone titration and inhibition by large flare emissions of NOx. The additional peak ozone from the hypothetical flare can briefly exceed 10 ppb about 16 km downwind. The enhancements of ambient ozone predicted by the model are significant, given that ozone control strategy widths are of the order of a few parts per billion. Degrading the horizontal resolution of the model to 1 km spuriously enhances the simulated ozone increases by reducing the effectiveness of ozone inhibition and titration due to artificial plume dilution.

Abstract:

Abstract:
Technological advances (e.g. directional drilling, hydraulic fracturing), have led to increases in unconventional natural gas development (NGD), raising questions about health impacts. OBJECTIVES: We estimated health risks for exposures to air emissions from a NGD project in Garfield County, Colorado with the objective of supporting risk prevention recommendations in a health impact assessment (HIA). METHODS: We used EPA guidance to estimate chronic and subchronic non-cancer hazard indices and cancer risks from exposure to hydrocarbons for two populations: (1) residents living >½ mile from wells and (2) residents living ≤ ½ mile from wells. RESULTS: Residents living ≤ ½ mile from wells are at greater risk for health effects from NGD than are residents living >½ mile from wells. Subchronic exposures to air pollutants during well completion activities present the greatest potential for health effects. The subchronic non-cancer hazard index (HI) of 5 for residents ≤ ½ mile from wells was driven primarily by exposure to trimethylbenzenes, xylenes, and aliphatic hydrocarbons. Chronic HIs were 1 and 0.4. for residents ≤ ½ mile from wells and >½ mile from wells, respectively. Cumulative cancer risks were 10 in a million and 6 in a million for residents living ≤ ½ mile and >½ mile from wells, respectively, with benzene as the major contributor to the risk. CONCLUSIONS: Risk assessment can be used in HIAs to direct health risk prevention strategies. Risk management approaches should focus on reducing exposures to emissions during well completions. These preliminary results indicate that health effects resulting from air emissions during unconventional NGD warrant further study. Prospective studies should focus on health effects associated with air pollution.

Abstract:
The multispecies analysis of daily air samples collected at the NOAA Boulder Atmospheric Observatory (BAO) in Weld County in northeastern Colorado since 2007 shows highly correlated alkane enhancements caused by a regionally distributed mix of sources in the Denver-Julesburg Basin. To further characterize the emissions of methane and non-methane hydrocarbons (propane, n-butane, i-pentane, n-pentane and benzene) around BAO, a pilot study involving automobile-based surveys was carried out during the summer of 2008. A mix of venting emissions (leaks) of raw natural gas and flashing emissions from condensate storage tanks can explain the alkane ratios we observe in air masses impacted by oil and gas operations in northeastern Colorado. Using the WRAP Phase III inventory of total volatile organic compound (VOC) emissions from oil and gas exploration, production and processing, together with flashing and venting emission speciation profiles provided by State agencies or the oil and gas industry, we derive a range of bottom-up speciated emissions for Weld County in 2008. We use the observed ambient molar ratios and flashing and venting emissions data to calculate top-down scenarios for the amount of natural gas leaked to the atmosphere and the associated methane and non-methane emissions. Our analysis suggests that the emissions of the species we measured are most likely underestimated in current inventories and that the uncertainties attached to these estimates can be as high as a factor of two.

Abstract:
The Haynesville Shale is a subsurface rock formation located beneath the Northeast Texas/Northwest Louisiana border near Shreveport. This formation is estimated to contain very large recoverable reserves of natural gas, and during the two years since the drilling of the first highly productive wells in 2008, has been the focus of intensive leasing and exploration activity. The development of natural gas resources within the Haynesville Shale is likely to be economically important but may also generate significant emissions of ozone precursors. Using well production data from state regulatory agencies and a review of the available literature, projections of future year Haynesville Shale natural gas production were derived for 2009−2020 for three scenarios corresponding to limited, moderate, and aggressive development. These production estimates were then used to develop an emission inventory for each of the three scenarios. Photochemical modeling of the year 2012 showed increases in 2012 8-h ozone design values of up to 5 ppb within Northeast Texas and Northwest Louisiana resulting from development in the Haynesville Shale. Ozone increases due to Haynesville Shale emissions can affect regions outside Northeast Texas and Northwest Louisiana due to ozone transport. This study evaluates only near-term ozone impacts, but the emission inventory projections indicate that Haynesville emissions may be expected to increase through 2020.

Abstract:
The Intermountain West is currently experiencing increased growth in oil and gas production, which has the potential to affect the visibility and air quality of various Class I areas in the region. The following work presents an analysis of these impacts using the Comprehensive Air Quality Model with extensions (CAMx). CAMx is a state-of-the-science, "one-atmosphere" Eulerian photochemical dispersion model that has been widely used in the assessment of gaseous and particulate air pollution (ozone, fine [PM2.5], and coarse [PM10] particulate matter). Meteorology and emissions inventories developed by the Western Regional Air Partnership Regional Modeling Center for regional haze analysis and planning are used to establish an ozone baseline simulation for the year 2002. The predicted range of values for ozone in the national parks and other Class I areas in the western United States is then evaluated with available observations from the Clean Air Status and Trends Network (CASTNET). This evaluation demonstrates the model's suitability for subsequent planning, sensitivity, and emissions control strategy modeling. Once the ozone baseline simulation has been established, an analysis of the model results is performed to investigate the regional impacts of oil and gas development on the ozone concentrations that affect the air quality of Class I areas. Results indicate that the maximum 8-hr ozone enhancement from oil and gas (9.6 parts per billion [ppb]) could affect southwestern Colorado and northwestern New Mexico. Class I areas in this region that are likely to be impacted by increased ozone include Mesa Verde National Park and Weminuche Wilderness Area in Colorado and San Pedro Parks Wilderness Area, Bandelier Wilderness Area, Pecos Wilderness Area, and Wheeler Peak Wilderness Area in New Mexico.

Abstract:
Ozone is an air pollutant that can cause severe respiratory health effects. Photochemical ozone production near the Earth's surface is considered a summertime, urban phenomenon, where hourly average ozone concentrations can exceed 150 p.p.b., compared with background values of about 50 p.p.b., and wintertime ozone concentrations in the US are usually in the range of 35–50 p.p.b. (refs 1, 2, 3). Here we report rapid, diurnal photochemical production of ozone during air temperatures as low as -17 °C, in the rural Upper Green River Basin, Wyoming, in the vicinity of the Jonah–Pinedale Anticline natural gas field. We find that hourly average ozone concentrations rise from 10–30 p.p.b. at night to more than 140 p.p.b. shortly after solar noon, under the influence of a stagnant, high-pressure system that promotes cold temperatures, low wind speeds and limited cloudiness. Under these conditions, an intense, shallow temperature inversion develops in the lowest 100 m of the atmosphere, which traps high concentrations of ozone precursors at night. During daytime, photolytic ozone production then leads to the observed high concentrations. We suggest that similar ozone production during wintertime is probably occurring around the world under comparable industrial and meteorological conditions.