Direct measurement of fugitive emissions of hydrocarbons from a refinery

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 the fugitive particulate emissions from construction mud/dirt carryout

Although the fugitive dust associated with construction mud/dirt carryout can represent a substantial portion of the particulate matter (PM) emissions inventory in nonattainment areas, it has not been well characterized by direct sampling methods. In this paper, a research program is described that directly determined both PM10 and PM2.5 (particles < or =10 and 2.5 microm in classical aerodynamic diameter, respectively) emission factors for mud/dirt carryout from a major construction project located in metropolitan Kansas City, MO. The program also assessed the contribution of automotive emissions to the total PM2.5 burden and determined the baseline emissions from the test road. As part of the study, both time-integrated and continuous exposure-profiling methods were used to assess the PM emissions, including particle size and elemental composition. This research resulted in overall PM10 and PM2.5 emission factors of 6 and 0.2 g/vehicle, respectively. Although PM10 is within the range of prior U.S. Environmental Protection Agency (EPA) guidance, the PM2.5 emission factor is far lower than previous estimates published by EPA. In addition, based on both the particle size and chemical data obtained in the study, a major portion of the PM2.5 emissions appears to be attributable to automotive exhaust from light-duty, gasoline-powered vehicles and not to the fugitive dust associated with reentrained mud/dirt carryout.     

Wind tunnel simulation of environmental controls on fugitive dust emissions from mine tailings

The development of techniques for determining fugitive dust emissions presents numerous challenges and remains the subject of much investigation. Past approaches have included field based monitoring stations and wind tunnel studies, while more recently, highly portable field units (e.g., PI-SWERL) have been added to our toolkit of instruments and methodologies. In the case of the investigation reported herein, a laboratory wind tunnel study was designed to systematically simulate PM₁₀ emissions from mine tailings for a range of surface treatments. Unique challenges were associated with the project in the sense that the proposed mine and tailings did not exist at the time of the investigation, so that it was impossible to work on-site. Only a small amount of slurry from a milled drill core was available to work with, and there were no established test protocols and few experimental precedents to work from. The slurry formed highly cohesive bricks when dried, similar to crusted playas investigated in field experiments. The PM₁₀ emissions demonstrated strong temporal variation with particle supply limitation. A small amount of vertical dust dispersion was observed, with PM₁₀ concentrations decaying exponentially away from the source. The emission rates obtained are similar in magnitude to those obtained in field analogues. The highly controlled experiment allowed for separation and analysis of several physical controls on PM₁₀ emissions from tailings; namely, the study addressed the degree of disturbance, shrinkage and cracking, and the effects of spigotting, particle settling and re-wetting.     

Localizing gaseous fugitive emission sources by combining real-time optical remote sensing and wind data

This paper presents a new approach to localize point emissions from ground-level fugitive gaseous air pollution sources. We estimate the crosswind plume's ground-level peak location downwind from the source by combining smooth basis functions minimization (SBFM) with pathintegrated optical remote sensing concentration data acquired along the crosswind direction in alternating beam path lengths. Peak location estimates, in conjunction with real-time measured wind direction data, are used to reconstruct the fugitive source location. We conducted a synthetic data study to evaluate the proposed peak location SBFM reconstruction. Furthermore, the methodology was validated with open-path Fourier transform infrared concentration data collected with wind direction data downwind from a controlled point source. This approach was found to provide reasonable estimates of point source location. The field study reconstructed source location was within several meters of the real source location.     

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.     

Innovative approach for estimating fugitive gaseous fluxes using computed tomography and remote optical sensing techniques.

This paper presents a new approach to quantify emissions from fugitive gaseous air pollution sources. The authors combine Computed Tomography (CT) with Path-Integrated Optical Remote Sensing (PI-ORS) concentration data in a new field beam geometry. Path-integrated concentrations are sampled in a vertical plane downwind from the source along several radial beam paths. An innovative CT technique, which applies the Smooth Basis Function Minimization method to the beam data in conjunction with measured wind data, is used to estimate the total flux from the fugitive source. The authors conducted a synthetic data study to evaluate the proposed methodology under different meteorological conditions, beam geometry configurations, and simulated measurement errors. The measurement errors were simulated based on data collected with an Open-Path Fourier Transform Infra-Red system. This approach was found to be robust for the simulated errors and for a wide range of fluctuating wind directions. In the very sparse beam geometry examined (eight beam paths), successful emission rates were retrieved over a 70 degrees range of wind directions under extremely large measurement error conditions.     

Using satellite imagery to locate innovative forest management practices in Nepal

There is a critical need to locate innovative forest management institutions that significantly impact forest cover change. This research presents an initial "proof of concept" methodology which combines deforestation theory with satellite image change analysis to identify forested areas that, theoretically, should probably not be there. Ten such "forest anomalies" are identified using temporal analysis of Landsat TM imagery of the Chitwan district in Nepal, linked with a GIS database on roads and a visual estimation of topography. A rapid field reconnaissance is undertaken to determine which of these anomalies exhibit interesting forest management innovations. Based on this information, one case is selected for detailed field study: this turns out to be a major case of community forestry and a premier ecotourism initiative that we were not aware of until we undertook this analysis. The utility and limitations of the method are described for monitoring trends in forest cover change.     

Field evaluation of digital optical method to quantify the visual opacity of plumes

Visual Determination of the Opacity of Emissions from Stationary Sources (Method 9) is a reference method established by U.S. Environmental Protection Agency (EPA) to quantify plume opacity. However, Method 9 relies on observations from humans, which introduces subjectivity. In addition, it is expensive to teach and certify personnel to evaluate plume opacity on a semiannual basis. In this study, field tests were completed during a "smoke school" and a 4-month monitoring program of plumes emitted from stationary sources with a Method 9 qualified observer to evaluate the use of digital photography and two computer algorithms as an alternative to Method 9. This Digital Optical Method (DOM) improves objectivity, costs less to implement than Method 9, and provides archival photographic records of the plumes. Results from "smoke school" tests indicate that DOM passed six of eight tests when the sun was located in the 140 degrees sector behind one of the three cameras, with the individual opacity errors of 15% or less and average opacity errors of 7.5% or less. DOM also passed seven of the eight tests when the sun was located in the 216 degrees sector behind another camera. However, DOM passed only one of the eight tests when the sun was located in the 116 degrees sector in front of the third camera. Certification to read plume opacity by a "smoke reader" for 6 months requires that the "smoke reader" pass one of the smoke school tests during smoke school. The average opacity errors and percentage of observations with individual opacity errors above 15% for the results obtained with DOM were lower than those obtained by the smoke school trainees with the sun was located behind the camera, whereas they were higher than the smoke school trainee results with the sun located in front of the camera. In addition, the difference between plume opacity values obtained by DOM and a Method 9 qualified observer, as measured in the field for two industrial sources, were 2.2%. These encouraging results demonstrate that DOM is able to meet Method 9 requirements under a wide variety of field conditions and, therefore, has potential to be used as an alternative to Method 9.     

Characterization of fugitive material within a primary lead smelter.

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO4 and PbO to Pb(o) (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl2, Pb4O3Cl2, Na3Pb2(SO4)3Cl, Pb10(SO4)Cl2O8, Pb4SCl6, and Pb7S2Cl10. The presence of Cl-bearing phases in the fume has possible health implications.     

Geologic emissions of methane to the atmosphere

The atmospheric methane budget is commonly defined assuming that major sources derive from the biosphere (wetlands, rice paddies, animals, termites) and that fossil, radiocarbon-free CH4 emission is due to and mediated by anthropogenic activity (natural gas production and distribution, and coal mining). However, the amount of radiocarbon-free CH4 in the atmosphere, estimated at approximately 20% of atmospheric CH4, is higher than the estimates from statistical data of CH4 emission from fossil fuel related anthropogenic sources. This work documents that significant amounts of "old" methane, produced within the Earth crust, can be released naturally into the atmosphere through gas permeable faults and fractured rocks. Major geologic emissions of methane are related to hydrocarbon production in sedimentary basins (biogenic and thermogenic methane) and, subordinately, to inorganic reactions (Fischer-Tropsch type) in geothermal systems. Geologic CH4 emissions include diffuse fluxes over wide areas, or microseepage, on the order of 10(0)-10(2) mg m(-2) day(-1), and localised flows and gas vents, on the order of 10(2) t y(-1), both on land and on the seafloor. Mud volcanoes producing flows of up to 10(3) t y(-1) represent the largest visible expression of geologic methane emission. Several studies have indicated that methanotrophic consumption in soil may be insufficient to consume all leaking geologic CH4 and positive fluxes into the atmosphere can take place in dry or seasonally cold environments. Unsaturated soils have generally been considered a major sink for atmospheric methane, and never a continuous, intermittent, or localised source to the atmosphere. Although geologic CH4 sources need to be quantified more accurately, a preliminary global estimate indicates that there are likely more than enough sources to provide the amount of methane required to account for the suspected missing source of fossil CH4.     

A combined approach for the evaluation of a volatile organic compound emissions inventory

Emissions inventories significantly affect photochemical air quality model performance and the development of effective control strategies. However, there have been very few studies to evaluate their accuracy. Here, to evaluate a volatile organic compound (VOC) emissions inventory, we implemented a combined approach: comparing the ratios of carbon bond (CB)-IV VOC groups to nitrogen oxides (NOx) or carbon monoxide (CO) using an emission preprocessing model, comparing the ratios of VOC source contributions from a source apportionment technique to NOx or CO, and comparing ratios of CB-IV VOC groups to NOx or CO and the absolute concentrations of CB-IV VOC groups using an air quality model, with the corresponding ratios and concentrations observed at three sites (Maryland, Washington, DC, and New Jersey). The comparisons of the ethene/NOx ratio, the xylene group (XYL)/NOx ratio, and ethene and XYL concentrations between estimates and measurements showed some differences, depending on the comparison approach, at the Maryland and Washington, DC sites. On the other hand, consistent results at the New Jersey site were observed, implying a possible overestimation of vehicle exhaust. However, in the case of the toluene group (TOL), which is emitted mainly from surface coating and printing sources in the solvent utilization category, the ratios of TOL/ NOx or CO, as well as the absolute concentrations revealed an overestimate of these solvent sources by a factor of 1.5 to 3 at all three sites. In addition, the overestimate of these solvent sources agreed with the comparisons of surface coating and printing source contributions relative to NOx from a source apportionment technique to the corresponding value of estimates at the Maryland site. Other studies have also suggested an overestimate of solvent sources, implying a possibility of inaccurate emission factors in estimating VOC emissions from surface coating and printing sources. We tested the impact of these overestimates with a chemical transport model and found little change in ozone but substantial changes in calculated secondary organic aerosol concentrations.     

An automatic sampler for measurement of dust-deposition rates around fugitive sources

A wind-directional sampler for determination of dust-deposition rates has been developed, enabling the measurement of dust-deposition caused by a specific source and, at the same time, providing information on the dust-deposition rate for the background area. The sampler is called METDUST. This paper describes the results of a field evaluation of the METDUST sampler. The field evaluation was performed in a village in Southern Jutland, Denmark, where complaints of dust-deposition had occurred close to a power plant with large stockpiles of coal. The results showed that, out of a 9-month period, increased dust-deposition occurred downwind from the stockpiles during 4 months. Episodes were identified by comparison with the background deposition rate. The METDUST sampler offers an opportunity to measure the dust-deposition rate contributed by the source and the background simultaneously. It can, therefore, be used by environmental authorities to identify the "likelihood of complaint" and to define a suitable guideline for the case in question.     

Global sulfur emissions from 1850 to 2000

The ASL database provides continuous time-series of sulfur emissions for most countries in the World from 1850 to 1990, but academic and official estimates for the 1990s either do not cover all years or countries. This paper develops continuous time series of sulfur emissions by country for the period 1850-2000 with a particular focus on developments in the 1990s. Global estimates for 1996-2000 are the first that are based on actual observed data. Raw estimates are obtained in two ways. For countries and years with existing published data I compile and integrate that data. Previously published data covers the majority of emissions and almost all countries have published emissions for at least 1995. For the remaining countries and for missing years for countries with some published data, I interpolate or extrapolate estimates using either an econometric emissions frontier model, an environmental Kuznets curve model, or a simple extrapolation, depending on the availability of data. Finally, I discuss the main movements in global and regional emissions in the 1990s and earlier decades and compare the results to other studies. Global emissions peaked in 1989 and declined rapidly thereafter. The locus of emissions shifted towards East and South Asia, but even this region peaked in 1996. My estimates for the 1990s show a much more rapid decline than other global studies, reflecting the view that technological progress in reducing sulfur based pollution has been rapid and is beginning to diffuse worldwide.     

Agricultural opportunities to mitigate greenhouse gas emissions

Agriculture is a source for three primary greenhouse gases (GHGs): CO(2), CH(4), and N(2)O. It can also be a sink for CO(2) through C sequestration into biomass products and soil organic matter. We summarized the literature on GHG emissions and C sequestration, providing a perspective on how agriculture can reduce its GHG burden and how it can help to mitigate GHG emissions through conservation measures. Impacts of agricultural practices and systems on GHG emission are reviewed and potential trade-offs among potential mitigation options are discussed. Conservation practices that help prevent soil erosion, may also sequester soil C and enhance CH(4) consumption. Managing N to match crop needs can reduce N(2)O emission and avoid adverse impacts on water quality. Manipulating animal diet and manure management can reduce CH(4) and N(2)O emission from animal agriculture. All segments of agriculture have management options that can reduce agriculture's environmental footprint.     

Development and evaluation of a method to determine indicator microorganisms in air emissions and residue from medical waste incinerators.

To allow testing of microbial destruction in medical waste incinerators, methods were developed to determine indicator microorganisms (Bacillus Stearothermophilus spores) in incinerator air emissions and residue. The emission trapping train consisted of a water cooled glass probe and impingers containing a neutral phosphate buffer. In field tests, spores were injected directly into the probe, and results showed that approximately 60 percent of the spores were recovered. Spores were analyzed with adequate precision using a microbial membrane filter unit. Lab experiments indicated that spores were stable in neutral pH phosphate buffer for up to 20 days, and heat shocking samples (heating to 80 degrees C for 20 minutes) reduced spore numbers in acidic or basic buffer. Laboratory tests also showed that 60 to 70 percent of spores initially added to ash were recovered up to 22 days after addition of the spores. In addition, lab tests showed that spores can be effectively recovered from residue test pipes spiked with indicator spores.     

An evaluation of the tapered element oscillating microbalance method for measuring diesel particulate emissions

We determined the usefulness of tapered element oscillating microbalances (TEOMs) for researchers and engineers involved with measuring diesel particulate mass. Two different test facilities were used for generating diesel particulates and comparing the TEOM to the commonly used U.S. Environmental Protection Agency (EPA) manual filter method. The EPA method is very labor-intensive and requires long periods of time to complete. The TEOM is an attractive approach because it has the potential to reduce the amount of time and labor required in diesel testing, as well as to provide real-time particulate-mass data that are not obtainable with the EPA method. It was found that the TEOM was a precise and easy-to-operate instrument that could measure the mass concentration (MC) of diesel particulate emissions in real time. Although the TEOM diesel particulate MC measurements were highly correlated with the manual filter measurements, the two techniques were not equivalent because the TEOM consistently reported MC results that were 20-25% lower than those obtained using the manual filter technique. In conclusion, the TEOM can be used to increase test-cell throughput and to measure transient values of diesel particulate emissions at sites performing diesel-engine testing. However, unless EPA is able to certify the TEOM as an equivalent method, it cannot replace the manual filter method for diesel certification work.     

Correlating emissions with time and temperature to predict worst-case emissions from open liquid area sources

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry's law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H2S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H2S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85-90 degrees F), the constant emission rate underestimated odor impact significantly (by 73%).     

Open-path tunable diode laser absorption spectroscopy for acquisition of fugitive emission flux data

Air pollutant emission from unconfined sources is an increasingly important environmental issue. The U.S. Environmental Protection Agency (EPA) has developed a ground-based optical remote-sensing method that enables direct measurement of fugitive emission flux from large area sources. Open-path Fourier transform infrared spectroscopy (OP-FTIR) has been the primary technique for acquisition of pollutant concentration data used in this emission measurement method. For a number of environmentally important compounds, such as ammonia and methane, open-path tunable diode laser absorption spectroscopy (OP-TDLAS) is shown to be a viable alternative to Fourier transform spectroscopy for pollutant concentration measurements. Near-IR diode laser spectroscopy systems offer significant operational and cost advantages over Fourier transform instruments enabling more efficient implementation of the measurement strategy. This article reviews the EPA's fugitive emission measurement method and describes its multipath tunable diode laser instrument. Validation testing of the system is discussed. OP-TDLAS versus OP-FTIR correlation testing results for ammonia (R2 = 0.980) and methane (R2 = 0.991) are reported. Two example applications of tunable diode laser-based fugitive emission measurements are presented.     

Assessment of influential range and characteristics of fugitive dust in limestone extraction processes

Fugitive dust emission from limestone extraction areas is a significant pollution source. The cracking operation in limestone extraction areas easily causes high total suspended particulate (TSP) concentrations in the atmosphere, occasionally exceeding the 1-hr national emission standard of Taiwan (500 microg/m3). The concentration and size distribution were measured at different distances (0.05-15 km) in the extraction areas. The highest hourly concentrations of TSP, PM10 (suspended particulate matter [PM] smaller than 10 microm), and PM2.5 (suspended PM smaller than 2.5 microm) are 1111, 825, and 236 microg/m3, respectively, during the cracking process. Measurement results obtained from the Micro-Orifice Uniform Deposit Impactor indicated that the mass median aerodynamic diameter is approximately 0.7 microm, with the geometric standard deviation exceeding 7. In addition, the emission factors are 0.143 and 0.211 kg/t for both vertical well and stair extraction operations, respectively. Experimental results demonstrate that the corresponding TSP control efficiencies for spraying water, planting grass, setting short walls, paving gravel roads, and establishing vertical well transportation are approximately 55, 50, 44, 22, and 30%, respectively. Furthermore, the PM10 control efficiencies are approximately 45, 41, 54, 35, and 30%, respectively, whereas the PM2.5 control efficiencies are roughly 23, 31, 15, 11, and 10%, individually.