Brian H. Stirm

Toward a better understanding and quantification of methane emissions from shale gas development

Significance We identified a significant regional flux of methane over a large area of shale gas wells in southwestern Pennsylvania in the Marcellus formation and further identified several pads with high methane emissions. These shale gas pads were identified as in the drilling process, a preproduction stage not previously associated with high methane emissions. This work emphasizes the need for top-down identification and component level and event driven measurements of methane leaks to properly inventory the combined methane emissions of natural gas extraction and combustion to better define the impacts of our nation’s increasing reliance on natural gas to meet our energy needs. The identification and quantification of methane emissions from natural gas production has become increasingly important owing to the increase in the natural gas component of the energy sector. An instrumented aircraft platform was used to identify large sources of methane and quantify emission rates in southwestern PA in June 2012. A large regional flux, 2.0–14 g CH4 s−1 km−2, was quantified for a ∼2,800-km2 area, which did not differ statistically from a bottom-up inventory, 2.3–4.6 g CH4 s−1 km−2. Large emissions averaging 34 g CH4/s per well were observed from seven well pads determined to be in the drilling phase, 2 to 3 orders of magnitude greater than US Environmental Protection Agency estimates for this operational phase. The emissions from these well pads, representing ∼1% of the total number of wells, account for 4–30% of the observed regional flux. More work is needed to determine all of the sources of methane emissions from natural gas production, to ascertain why these emissions occur and to evaluate their climate and atmospheric chemistry impacts.

An Airborne and Wind Tunnel Evaluation of a Wind Turbulence Measurement System for Aircraft-Based Flux Measurements*

Abstract Although the ability to measure vertical eddy fluxes of gases from aircraft platforms represents an important capability to obtain spatially resolved data, accurate and reliable determination of the turbulent vertical velocity presents a great challenge. A nine-hole hemispherical probe known as the “Best Air Turbulence Probe” (often abbreviated as the “BAT Probe”) is frequently used in aircraft-based flux studies to sense the airflow angles and velocity relative to the aircraft. Instruments such as inertial navigation and global positioning systems allow the measured airflow to be converted into the three-dimensional wind velocity relative to the earth’s surface by taking into account the aircraft’s velocity and orientation. Calibration of the aircraft system has previously been performed primarily through in-flight experiments, where calibration coefficients were determined by performing various flight maneuvers. However, a rigorous test of the BAT Probe in a wind tunnel has not been previously ...

Methane destruction efficiency of natural gas flares associated with shale formation wells.

Flaring to dispose of natural gas has increased in the United States and is typically assumed to be 98% efficient, accounting for both incomplete combustion and venting during unintentional flame termination. However, no in situ measurements of flare emissions have been reported. We used an aircraft platform to sample 10 flares in North Dakota and 1 flare in Pennsylvania, measuring CO2, CH4, and meteorological data. Destruction removal efficiency (DRE) was calculated by assuming a flare natural gas input composition of 60-100% CH4. In all cases flares were >99.80 efficient at the 25% quartile. Crosswinds up to 15 m/s were observed, but did not significantly adversely affect efficiency. During analysis unidentified peaks of CH4, most likely from unknown venting practices, appeared much larger in magnitude than emissions from flaring practices. Our analysis suggests 98% efficiency for nonsputtering flares is a conservative estimate for incomplete combustion and that the unidentified venting is a greater contributor to CH4 emissions.

Direct and Indirect Measurements and Modeling of Methane Emissions in Indianapolis, Indiana

This paper describes process-based estimation of CH4 emissions from sources in Indianapolis, IN and compares these with atmospheric inferences of whole city emissions. Emissions from the natural gas distribution system were estimated from measurements at metering and regulating stations and from pipeline leaks. Tracer methods and inverse plume modeling were used to estimate emissions from the major landfill and wastewater treatment plant. These direct source measurements informed the compilation of a methane emission inventory for the city equal to 29 Gg/yr (5% to 95% confidence limits, 15 to 54 Gg/yr). Emission estimates for the whole city based on an aircraft mass balance method and from inverse modeling of CH4 tower observations were 41 ± 12 Gg/yr and 81 ± 11 Gg/yr, respectively. Footprint modeling using 11 days of ethane/methane tower data indicated that landfills, wastewater treatment, wetlands, and other biological sources contribute 48% while natural gas usage and other fossil fuel sources contribute 52% of the city total. With the biogenic CH4 emissions omitted, the top-down estimates are 3.5-6.9 times the nonbiogenic city inventory. Mobile mapping of CH4 concentrations showed low level enhancement of CH4 throughout the city reflecting diffuse natural gas leakage and downstream usage as possible sources for the missing residual in the inventory.

Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling.

Cloudwater and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry (HRMS) with nanospray desorption electrospray ionization (nano-DESI) and direct infusion electrospray ionization (ESI) were utilized to compare the organic composition of the particle and cloudwater samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloudwater, showing the significant influence of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloudwater samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloudwater when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.

Black Carbon Emissions from Associated Natural Gas Flaring

Approximately 150 billion cubic meters (BCM) of natural gas is flared and vented in the world annually, emitting greenhouse gases and other pollutants with no energy benefit. About 7 BCM per year is flared in the United States, and half is from North Dakota alone. There are few emission measurements from associated gas flares and limited black carbon (BC) emission factors have been previously reported from the field. Emission plumes from 26 individual flares in the Bakken formation in North Dakota were sampled. Methane, carbon dioxide, and BC were measured simultaneously, allowing the calculation of BC mass emission factors using the carbon balance method. Particle optical absorption was measured using a three-wavelength particle soot absorption photometer (PSAP) and BC particle number and mass concentrations were measured with a single particle soot photometer. The BC emission factors varied over 2 orders of magnitude, with an average and uncertainty range of 0.14 ± 0.12 g/kg hydrocarbons in associated gas and a median of 0.07 g/kg which represents a lower bound on these measurements. An estimation of the BC emission factor derived from PSAP absorption provides an upper bound at 3.1 g/kg. These results are lower than previous estimations and laboratory measurements. The BC mass absorption cross section was 16 ± 12 m(2)/g BC at 530 nm. The average absorption Ångström exponent was 1.2 ± 0.8, suggesting that most of the light absorbing aerosol measured was black carbon and the contribution of light absorbing organic carbon was small.

Assessing the Methane Emissions from Natural Gas-Fired Power Plants and Oil Refineries

Presently, there is high uncertainty in estimates of methane (CH4) emissions from natural gas-fired power plants (NGPP) and oil refineries, two major end users of natural gas. Therefore, we measured CH4 and CO2 emissions at three NGPPs and three refineries using an aircraft-based mass balance technique. Average CH4 emission rates (NGPPs: 140 ± 70 kg/h; refineries: 580 ± 220 kg/h, 95% CL) were larger than facility-reported estimates by factors of 21-120 (NGPPs) and 11-90 (refineries). At NGPPs, the percentage of unburned CH4 emitted from stacks (0.01-0.08%) was much lower than respective facility-scale losses (0.09-0.34%), and CH4 emissions from both NGPPs and refineries were more strongly correlated with enhanced H2O concentrations (R2avg = 0.65) than with CO2 (R2avg = 0.21), suggesting noncombustion-related equipment as potential CH4 sources. Additionally, calculated throughput-based emission factors (EF) derived from the NGPP measurements made in this study were, on average, a factor of 4.4 (stacks) and 37 (facility-scale) larger than industry-used EFs. Subsequently, throughput-based EFs for both the NGPPs and refineries were used to estimate total U.S. emissions from these facility-types. Results indicate that NGPPs and oil refineries may be large sources of CH4 emissions and could contribute significantly (0.61 ± 0.18 Tg CH4/yr, 95% CL) to U.S. emissions.

Urban Emissions of Water Vapor in Winter

Elevated water vapor (H2Ov) mole fractions were occassionally observed downwind of Indianapolis, IN, and the Washington, D.C.-Baltimore, MD, area during airborne mass balance experiments conducted during winter months between 2012 and 2015. On days when an urban H2Ov excess signal was observed, H2Ov emissions estimates range between 1.6 × 104 and 1.7 × 105 kg s-1, and account for up to 8.4% of the total (background + urban excess) advected flow of atmospheric boundary layer H2Ov from the urban study sites. Estimates of H2Ov emissions from combustion sources and electricity generation facility cooling towers are 1-2 orders of magnitude smaller than the urban H2Ov emission rates estimated from observations. Instances of urban H2Ov enhancement could be a result of differences in snowmelt and evaporation rates within the urban area, due in part to larger wintertime anthropogenic heat flux and land cover differences, relative to surrounding rural areas. More study is needed to understand why the urban H2Ov excess signal is observed on some days, and not others. Radiative transfer modeling indicates that the observed urban enhancements in H2Ov and other greenhouse gas mole fractions contribute only 0.1°C day-1 to the urban heat island at the surface. This integrated warming through the boundary layer is offset by longwave cooling by H2Ov at the top of the boundary layer. While the radiative impacts of urban H2Ov emissions do not meaningfully influence urban heat island intensity, urban H2Ov emissions may have the potential to alter downwind aerosol and cloud properties.

Top‐Down Estimates of NOx and CO Emissions From Washington, D.C.‐Baltimore During the WINTER Campaign

Airborne mass balance experiments were conducted around the Washington, D.C.-Baltimore area using research aircraft from Purdue University and the University of Maryland to quantify emissions of nitrogen oxides (NOx = NO + NO2) and carbon monoxide (CO). The airborne mass balance experiments supported the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign, an intensive airborne study of anthropogenic emissions along the Northeastern United States in February–March 2015, and the Fluxes of Atmospheric Greenhouse Gases in Maryland project which seeks to provide best estimates of anthropogenic emissions from the Washington, D.C.-Baltimore area. Top-down emission rates of NOx and CO estimated from the mass balance flights are compared with the Environmental Protection Agency’s 2011 and 2014 National Emissions Inventory (NEI-11 and NEI-14). Inventory and observation-derived NOx emission rates are consistent within the measurement uncertainty. Observed CO emission rates are a factor of 2 lower than reported by the NEI. The NEI’s accuracy has been evaluated for decades by studies of anthropogenic emissions, yet despite continuous inventory updates, observation-inventory discrepancies persist. WINTER NOx/CO2 enhancement ratios are consistent with inventories, but WINTER CO/NOx and CO/CO2 enhancement ratios are lower than those reported by other urban summertime studies, suggesting a strong influence of CO seasonal trends and/or nationwide CO reductions. There is a need for reliable observation-based criterion pollutant emission rate measurements independent of the NEI. Such determinations could be supplied by the community’s reporting of sector-specific criteria pollutant/CO2 enhancement ratios and subsequent multiplication with currently available and forthcoming high-resolution CO2 inventories.

Correction to Assessing the Methane Emissions from Natural Gas-Fired Power Plants and Oil Refineries

In our article, the throughput estimate for the three natural gasfired power plants, P1−3, was calculated incorrectly. The throughput estimate in Table 3 of the main article incorrectly shows the methane (CH4) throughput for the duration of the experiment (kg CH4/experiment), not the hourly throughput estimate (kg CH4/h), as intended. Correcting this error changed the CH4 loss rates for these three power plants, shown in Table 3. Please note that, except in one case (e.g., P2, 9/19, stack loss rate), the corrected CH4 loss rates are not statistically different from the numbers reported in the original article (at a 95% confidence level, note that numbers in Table 3 are reported ±1σ). This also results in adjustment of several in-text references to the corrected values, described here. Within the Abstract and the Results and Discussion section, the reported range of CH4 loss rates for stacks changes from 0.01−0.14% to 0.01−0.08%, and the range of CH4 loss rates for the entire facilities changes from 0.10−0.42% to 0.09−0.34%. Within the Results and Discussion section, the description of the factor difference between the stack and facility-scale losses should be updated to reflect the new numbers in Table 3. The original sentence “The percentage of unburned CH4 emitted from stacks at the three NGPPs (0.01−0.14%) was lower than respective facility-scale losses (0.10−0.42%) in all cases, by factors of 3 (P1, 9/20), 15 (P1, 9/21), 10 (P2, 9/21), and 13 (P3, 9/25), again suggesting that more CH4 is lost from noncombustion-related equipment than from combustion processes (Table 3)”., should be updated to “The percentage of unburned CH4 emitted from stacks at the three NGPPs (0.01−0.08%) was lower than respective facility-scale losses (0.09−0.34%) in all cases, by factors of 4 (P1, 9/20), 12 (P1, 9/21), 9 (P2, 9/21), and 17 (P3, 9/25)...”. Additionally, in the original Abstract we note that the calculated throughput-based emission factor (EF) derived from the NGPP measurements made in this study were, on average, a factor of 4.4 (stacks) and 42 (facility-scale) larger than industry-used EFs. This sentence should be changed to read “a factor of 4.4 (stacks) and 37 (facility-scale) larger than industry-used EFs”. Note that this change is not related to the corrected calculation of throughput estimation described above, but due to an unrelated miscalculation of the average factor difference, as the error did not carry through to the throughputbased EF calculation shown in the last two columns of Table 3. To reflect the correction of this calculation, an updated version of eq S4 from the Supporting Information is provided below, which applies a correction factor to eq S4 ((60 min/50 min) in this example) to obtain an hourly heat input, instead of the total heat input per length of the experiment as used previously. Please refer to the original Supporting Information text for a description of the example used in eq S4 below. The hourly average heat inputs obtained using eq S4 are then used to calculate the corrected CH4 throughputs reported here, using eq 3 in the main text, with corrected version shown below.