Direct Measurement of Fugitive Emissions of Hydrocarbons from a Refinery

Abstract

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C₂₊ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C₂₊ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C₂₊ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C₂₊ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C₂₊ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

Characterization of emissions from diffusion flare systems

Emissions from flares typical of those found at oil-field battery sites in Alberta, Canada, were investigated to determine the degree to which the flared gases were burned and to characterize the products of combustion in the emissions. The study consisted of laboratory, pilot-scale, and field-scale investigations. Combustion of all hydrocarbon fuels in both laboratory and pilot-scale tests produced a complex variety of hydrocarbon products within the flame, primarily by pyrolytic reactions. Acetylene, ethylene, benzene, styrene, ethynyl benzene, and naphthalene were some of the major constituents produced by conversion of more than 10% of the methane within the flames. The majority of the hydrocarbons produced within the flames of pure gas fuels were effectively destroyed in the outer combustion zone, resulting in combustion efficiencies greater than 98% as measured in the emissions. The addition of liquid hydrocarbon fuels or condensates to pure gas streams had the largest effect on impairing the ability of the resulting flame to destroy the pyrolytically produced hydrocarbons, as well as the original hydrocarbon fuels directed to the flare. Crosswinds were also found to reduce the combustion efficiency (CE) of the co-flowing gas/condensate flames by causing more unburned fuel and the pyrolytically produced hydrocarbons to escape into the emissions. Flaring of solution gas at oil-field battery sites was found to burn with an efficiency of 62-82%, depending on either how much fuel was directed to flare or how much liquid hydrocarbon was in the knockout drum. Benzene, styrene, ethynyl benzene, ethynyl-methyl benzenes, toluene, xylenes, acenaphthalene, biphenyl, and fluorene were, in most cases, the most abundant compounds found in any of the emissions examined in the field flare testing. The emissions from sour solution gas flaring also contained reduced sulfur compounds and thiophenes.     

Source Fingerprints for Volatile Non-Methane Hydrocarbons

Non-methane hydrocarbon (NMHC) source profiles consisting of 35 hydrocarbon species were measured for vehicle and petroleum refinery emissions. Refueling emissions were found to be sensitive to the grade and volatility class of fuel and to be composed mainly of saturated hydrocarbons such as n-butane and 2-methy I butane. Unsaturated and aromatic hydrocarbons, which are released from the tailpipe of vehicles as products of combustion and unburned fuel, were more prevalent in roadway emissions comprising approximately 34 percent of the total NMHCs. Cold-start emissions were nearly indistinguishable from the roadway emission profile. The only significant differences were in toluene, ethylene and acetylene, which may be related to the efficiency of combustion when the vehicle is initially started. Saturated hydrocarbon distributions of the hot-soak profiles were found to be similar to refueling emissions. The only significant difference in the profiles was in the aromatic content, which may be related to the grade of the gasoline and the effectiveness of evaporative emission control devices. The temporal variation in refinery emissions was significant and may be related to variations in refinery activities such as the production and blending of feed stocks to produce different fuels.     

Characterization of Emissions from Diffusion Flare Systems

ABSTRACT

Emissions from flares typical of those found at oil-field battery sites in Alberta, Canada, were investigated to determine the degree to which the flared gases were burned and to characterize the products of combustion in the emissions. The study consisted of laboratory, pilot-scale, and field-scale investigations. Combustion of all hydrocarbon fuels in both laboratory and pilot-scale tests produced a complex variety of hydrocarbon products within the flame, primarily by pyrolytic reactions. Acetylene, eth-ylene, benzene, styrene, ethynyl benzene, and naphthalene were some of the major constituents produced by conversion of more than 10% of the methane within the flames. The majority of the hydrocarbons produced within the flames of pure gas fuels were effectively destroyed in the outer combustion zone, resulting in combustion efficiencies greater than 98% as measured in the emissions.

The addition of liquid hydrocarbon fuels or condensates to pure gas streams had the largest effect on impairing the ability of the resulting flame to destroy the pyrolytically produced hydrocarbons, as well as the original hydrocarbon fuels directed to the flare. Crosswinds were also found to reduce the combustion efficiency (CE) of the co-flowing gas/condensate flames by causing more unburned fuel and the pyrolytically produced hydrocarbons to escape into the emissions.

Flaring of solution gas at oil-field battery sites was found to burn with an efficiency of 62-82%, depending on either how much fuel was directed to flare or how much liquid hydrocarbon was in the knockout drum. Benzene, styrene, ethynyl benzene, ethynyl-methyl benzenes, toluene, xylenes, acenaphthalene, biphenyl, and fluorene were, in most cases, the most abundant compounds found in any of the emissions examined in the field flare testing. The emissions from sour solution gas flaring also contained reduced sulfur compounds and thiophenes.     

Effects of the Motor Vehicle Control Program On Hydrocarbon Concentrations in The Central Los Angeles Atmosphere

The body of information presented in this paper is directed to those individuals concerned with the effect of the motor vehicle control program on ambient hydrocarbon concentrations in a metropolitan area during peak traffic hours. The data used in this study are from gas chromatographic analyses of air samples taken in 1963-65, before implementation of the exhaust control program for new motor vehicles, and in 1971 and 1973, after several years’ application of this program. A brief history of the motor vehicle program in California together with emission standards for hydrocarbons are discussed and certain automobile-related hydrocarbons are identified and characterized. Frequency distributions were constructed for total hydrocarbons, non-methane hydrocarbons, methane, acetylene, and isopentane for 1963-65, 1971, and 1973 and the standard deviation (1 sigma) concentration limits are discussed for each of the subgroups mentioned above. The average concentration and relative percent comparisons for methane, ethane, n-butane, isopentane, C₃+ paraffin, eth-ene, propene, C₄ +olefin, acetylene, benzene, and toluene are shown and discussed in detail. These studies: 1) show hydrocarbon emissions from motor vehicles were reduced 47.6% during this time period; 2) indicate selective reduction of compounds; and 3) reveal a 51.8% reduction in the 1973 ambient total hydrocarbon concentration since 1963-65.     

Derivation of new emission factors for quantification of mass emissions when using optical gas imaging for detecting leaks

This paper describes the development of new "leak/no-leak" emission factors that are suitable for estimating facilities' fugitive emissions when using an alternative work practice (AWP) that is based on optical gas imaging technology for detecting leaking piping system components. These emission factors were derived for valves, pumps, and connectors/flanges for instrument leak detection thresholds ranging from 3 to 60 g/hr using a combination of field data and Monte Carlo statistical simulation techniques. These newly derived leak/no-leak emission factors are designed to replace the U.S. Environment Protection Agency (EPA) 1995 Protocol factors, which were based on Method 21 monitoring of leaks at "uncontrolled" facilities. The emission factors published in the 1995 Protocol have not been updated since the 1970s. This derivation is based on results where the authors document the use of a Monte Carlo simulation technique to quantify the required leak detection thresholds that provide equal--or better--environmental benefits for an AWP. The use of these newly derived emission factors is demonstrated for different methods of computing fugitive emissions from a hypothetical model refinery. The resulting facility emissions calculated by using these new emission factors is compared with the existing emission estimation methods provided in the EPA 1995 Protocol. The results demonstrate that the new emission factors provide an emission estimate that is the closest to that obtained from the direct determination of total emissions by Monte Carlo simulations.     

Concentrations of volatile organic compounds in an industrial area of Korea

We measured and analyzed daily mean concentrations of volatile organic compounds (VOC) at Ulsan industrial and downtown sites from 3 to 8 June 1997. The industrial site is situated at the boundary of a petrochemical complex and the other is at downtown area in Ulsan. At each site, we collected ambient air samples in passivated stainless-steel containers by using constant flow samplers and analyzed them by a GC-FID. At Ulsan industrial site, the concentrations and their daily variations of total VOC were higher than those at the downtown site. The concentrations of oxygenated hydrocarbons were the highest among seven hydrocarbon groups at both sites. The fraction of C₂–C₅ light hydrocarbon concentrations to C₂–C₉ hydrocarbons at Ulsan industrial site was higher than that in other industrial areas. It suggests that fugitive emissions of light hydrocarbons in Ulsan industrial areas might be higher than those of other industrial areas. Under favorable wind conditions, the influence of industrial emissions of VOC on the downtown hydrocarbon levels was observed.     

Ambient Air Measurements of Petroleum Refinery Emissions

An ambient air monitoring program to characterize airborne emissions from the Exxon petroleum refinery at Benicia, California was conducted during September 8–22, 1975. Ground level sampling facilities and an instrumented aircraft provided an integrated, three-dimensional monitoring network. Measurements made during the study included ozone, oxides of nitrogen, methane, carbon monoxide, individual C₂-C₆ hydrocarbons, halocarbons, condensation nuclei, visual distance and various meteorological parameters. The study focused on three major areas: (1) the characterization of gaseous components within the refinery effluent, especially non-methane hydrocarbons and ozone, (2) natural sunlight bag irradiation experiments to determine the ozone forming potential of refinery emissions, and (3) an investigation of changes in plume chemistry as refinery emissions were transported downwind.     

Concentrations of C2–C5 hydrocarbons in atmospheric air at Deonar,Bombay, in relation to possible sources

Atmospheric C₂–C₅ hydrocarbons were determined at Deonar, an industrial suburb north of Bombay, India, during 1985. Samples were pre-concentrated on silica gel at −78°C and subsequently desorbed on to a gaschromatographic column for separation and flame ionization detection. The seasonal pattern of the monthly geometric mean hydrocarbon concentrations are used to show that refinery emissions in addition to auto exhaust are a major source of hydrocarbons at Deonar.     

The impact of natural and anthropogenic hydrocarbons on the tropospheric budget of carbon monoxide

A method to quantify the relative contributions of surface sources and photochemical production of atmospheric carbon monoxide has been implemented in a three-dimensional chemical-transport model. The impact of biogenic and anthropogenic hydrocarbons has been calculated. The oxidation of isoprene contributes to about 10% of the global tropospheric burden of carbon monoxide, with a maximum contribution over southern America and Africa. Oxidation of methane and terpenes contribute to 28 and 2%, respectively, of the tropospheric burden of CO. The oxidation of the other hydrocarbons, which include ethane, propane, ethylene, propylene and the surrogate hydrocarbon representing other hydrocarbons results in 12% of the CO tropospheric burden, among which 69% results from the oxidation of hydrocarbons of biologic origin. The overall global CO yield from the oxidation of isoprene is estimated to be 23% on a carbon basis. Comparisons between model results and the few available observations of isoprene, terpenes and their oxidation products show that there is no evidence that the current global isoprene emissions proposed in the IGAC/GEIA emissions data base are substantially overestimated, as suggested by previous studies.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Speciated hydrocarbon and carbon monoxide emissions from an internal combustion engine operating on methyl tertiary butyl ether-containing fuels

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel. The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane, and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst, while acetaldehyde and methane were quite resistant to oxidation.     

Careers in Air Pollution Control Plant Pathology

ABSTRACT

Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas [LPG], and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C₅ and C₆ saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in the vehicle emission profile. High levels of the C₂-C₄ saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.     

Speciated Hydrocarbon and Carbon Monoxide Emissions from an Internal Combustion Engine Operating on Methyl Tertiary Butyl Ether-Containing Fuels

ABSTRACT

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel.

The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane,and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst,while acetaldehyde and methane were quite resistant to oxidation.     

Comparing estimates of fugitive landfill methane emissions using inverse plume modeling obtained with Surface Emission Monitoring (SEM), Drone Emission Monitoring (DEM), and Downwind Plume Emission Monitoring (DWPEM)

ABSTRACT

As part of the global effort to quantify and manage anthropogenic greenhouse gas emissions, there is considerable interest in quantifying methane emissions in municipal solid waste landfills. A variety of analytical and experimental methods are currently in use for this task. In this paper, an optimization-based estimation method is employed to assess fugitive landfill methane emissions. The method combines inverse plume modeling with ambient air methane concentration measurements. Three different measurement approaches are tested and compared. The method is combined with surface emission monitoring (SEM), above ground drone emission monitoring (DEM), and downwind plume emission monitoring (DWPEM). The methodology is first trialed and validated using synthetic datasets in a hand-generated case study. A field study is also presented where SEM, DEM and DWPEM are tested and compared. Methane flux during two-days measurement campaign was estimated to be between 228 and 350 g/s depending on the type of measurements used. Compared to SEM, using unmanned aerial systems (UAS) allows for a rapid and comprehensive coverage of the site. However, as showed through this work, advancement of DEM-based methane sampling is governed by the advances that could be made in UAS-compatible measurement instrumentations. Downwind plume emission monitoring led to a smaller estimated flux compared with SEM and DEM without information about positions of major leak points in the landfill. Even though, the method is simple and rapid for landfill methane screening. Finally, the optimization-based methodology originally developed for SEM, shows promising results when it is combined with the drone-based collected data and downwind concentration measurements. The studied cases also discovered the limitations of the studied sampling strategies which is exploited to identify improvement strategies and recommendations for a more efficient assessment of fugitive landfill methane emissions.

Implications: Fugitive landfill methane emission estimation is tackled in the present study. An optimization-based method combined with inverse plume modeling is employed to treat data from surface emission monitoring, drone-based emission monitoring and downwind plume emission monitoring. The study helped revealing the advantages and the limitations of the studied sampling strategies. Recommendations for an efficient assessment of landfill methane emissions are formulated. The method trialed in this study for fugitive landfill methane emission could also be appropriate for rapid screening of analogous greenhouse gas emission hotspots.     

South Philadelphia passive sampler and sensor study

From June 2013 to March 2015, in total 41 passive sampler deployments of 2 wk duration each were conducted at 17 sites in South Philadelphia, PA, with results for benzene discussed here. Complementary time-resolved measurements with lower cost prototype fenceline sensors and an open-path ultraviolet differential optical absorption spectrometer were also conducted. Minimum passive sampler benzene concentrations for each sampling period ranged from 0.08 ppbv to 0.65 ppbv, with a mean of 0.25 ppbv, and were negatively correlated with ambient temperature (–0.01 ppbv/°C, R² = 0.68). Co-deployed duplicate passive sampler pairs (N = 609) demonstrated good precision with an average and maximum percent difference of 1.5% and 34%, respectively. A group of passive samplers located within 50 m of a refinery fenceline had a study mean benzene concentration of 1.22 ppbv, whereas a group of samplers located in communities >1 km distant from facilities had a mean of 0.29 ppbv. The difference in the means of these groups was statistically significant at the 95% confidence level (p < 0.001). A decreasing gradient in benzene concentrations moving away from the facilities was observed, as was a significant period-to-period variation. The highest recorded 2-wk average benzene concentration for the fenceline group was 3.11 ppbv. During this period, time-resolved data from the prototype sensors and the open-path spectrometer detected a benzene signal from the west on one day in particular, with the highest 5-min path-averaged benzene concentration measured at 24 ppbv.

Implications: Using a variation of EPA’s passive sampler refinery fenceline monitoring method, coupled with time-resolved measurements, a multiyear study in South Philadelphia informed benzene concentrations near facilities and in communities. The combination of measurement strategies can assist facilities in identification and mitigation of emissions from fugitive sources and improve information on air quality complex air sheds.     

Thermal destruction of benzene

The thermal destruction of benzene in methane/air flue gas is studied experimentally using an atmospheric laminar flow reactor in laboratory scale. The reactor is operated at four different fuel equivalent ratios (phi = 0.06, 0.1,0.5, 3.7), and temperatures in the range from 850 to 973 K and realises a residence time of 5 s. Stable-species concentrations are measured by gas chromatography (GC) and high-pressure liquid chromatography (HPLC), where phenol, acetylene, formaldehyde, acrolein, methane and acetaldehyde are the major hydrocarbon products besides CO and CO2. The augmentation of the temperature from 850 to 973 K increases the benzene conversion rate from 55% to 99%. The experimental results for one fuel equivalent ratio (phi = 0.5) are compared to the benzene model proposed by Emdee et al. (J. Phys. Chem. 92 (1992) 2151-2161). A fair agreement is observed for the benzene consumption and the CO production throughout the temperature range considered here. The small hydrocarbons are not very well matched, which requires further research on the sub-models. Our experimental results on laboratory scale provide a database for the modelling of benzene oxidation in waste incinerators.     

Fast and quantitative measurement of benzene,toluene and C2-benzenes in automotive exhaust during transient engine operation with and without catalytic exhaust gas treatment

Time-Resolved Chemical Ionization Mass Spectrometry (CIMS) has been used to investigate the emission profiles of benzene, toluene and the C₂-benzenes (xylenes and ethyl benzene) in automotive exhaust during transient engine operation. On-line emission measurements with a frequency of 1–5 Hz clearly identified the critical driving conditions that are mainly responsible for the overall aromatic hydrocarbon emissions. The passenger car, equipped with a catalytic converter showed significant BTXE-emissions only in the first part of the New European Driving Cycle (NEDC) due to sub-optimal catalyst temperature. On the same car without a catalytic converter, emissions of aromatic hydrocarbons were detected over the entire test run and the benzene–toluene mixing ratios of the exhaust gas were rather constant. With catalytic exhaust gas treatment the observed benzene–toluene mixing ratios varied to a greater extent reflecting predominantly different catalytic converter conditions. The average molar ratio of benzene over toluene rose from 0.33 to 0.53 upon exhaust gas treatment. With catalytic converter the emissions during extra urban (EUDC) driving repeatedly showed benzene–toluene mixing ratios >1 and an average molar benzene/toluene ratio of 0.74 was detected during the EUDC part of the driving cycle. Whereas the total hydrocarbon (T.HC) emissions were decreased by 83% upon exhaust gas treatment the overall reduction of the benzene emissions was only 70%.     

Characterization of methane emissions from five cold heavy oil production with sands (CHOPS) facilities

Cold heavy oil production with sands (CHOPS) is a common oil extraction method in the Canadian provinces of Alberta and Saskatchewan that can result in significant methane emissions due to annular venting. Little is known about the magnitude of these emissions, nor their contributions to the regional methane budget. Here the authors present the results of field measurements of methane emissions from CHOPS wells and compare them with self-reported venting rates. The tracer ratio method was used not only to analyze total site emissions but at one site it was also used to locate primary emission sources and quantify their contributions to the facility-wide emission rate, revealing the annular vent to be a dominant source. Emissions measured from five different CHOPS sites in Alberta showed large discrepancies between the measured and reported rates, with emissions being mainly underreported. These methane emission rates are placed in the context of current reporting procedures and the role that gas-oil ratio (GOR) measurements play in vented volume estimates. In addition to methane, emissions of higher hydrocarbons were also measured; a chemical “fingerprint” associated with CHOPS wells in this region reveals very low emission ratios of ethane, propane, and aromatics versus methane. The results of this study may inform future studies of CHOPS sites and aid in developing policy to mitigate regional methane emissions.

Implications: Methane measurements from cold heavy oil production with sand (CHOPS) sites identify annular venting to be a potentially major source of emissions at these facilities. The measured emission rates are generally larger than reported by operators, with uncertainty in the gas-oil ratio (GOR) possibly playing a large role in this discrepancy. These results have potential policy implications for reducing methane emissions in Alberta in order to achieve the Canadian government’s goal of reducing methane emissions by 40–45% below 2012 levels within 8 yr.     

Composition of Automobile Evaporative and Tailpipe Hydrocarbon Emissions

Mathematical modeling of ambient air photochemistry requires comprehensive mobile source hydrocarbon emission speciation. Passenger car tailpipe and evaporative hydrocarbon emissions have been examined using procedures described in the Federal Register for emissions certification. Hydrocarbon emission rates and compositions were determined for four passenger cars: a 1963 Chevrolet, a 1977 Ford Mustang II, a 1978 Mercury Monarch, and a 1979 Ford LTD-II. These vehicles are representative of a wide range of exhaust and evaporative emissions control configurations. Both emission rates and compositions were dependent on the emissions control devices used with the vehicles, and the fuel composition and vapor pressure. In agreement with the literature, tailpipe catalyst control systems removed unsaturated olefinic, aromatic, and acetylenic hydrocarbons to a greater extent than saturated paraffinic hydrocarbons. The impact of evaporative control devices on composition was not well defined, however the limited data suggested a sensitivity to fuel aromatic content. The emission rate of benzene, emphasized because of its potential carcinogenicity, was sensitive to both fuel benzene and total aromatic content.