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Greenhouse gas emissions mitigation requires understanding the dominant processes controlling fluxes of these trace gases at increasingly finer spatial and temporal scales. Trace gas fluxes can be estimated using a variety of approaches that translate observed atmospheric species mole fractions into fluxes or emission rates, often identifying the spatial and temporal characteristics of the emission sources as well. Meteorological models are commonly combined with tracer dispersion models to estimate fluxes using an inverse approach that optimizes emissions to best fit the trace gas mole fraction observations. One way to evaluate the accuracy of atmospheric flux estimation methods is to compare results from independent methods, including approaches in which different meteorological and tracer dispersion models are used. In this work, we use a rich data set of atmospheric methane observations collected during an intensive airborne campaign to compare different methane emissions estimates from the Barnett Shale oil and natural gas production basin in Texas, USA. We estimate emissions based on a variety of different meteorological and dispersion models. Previous estimates of methane emissions from this region relied on a simple model (a mass balance analysis) as well as on ground-based measurements and statistical data analysis (an inventory). We find that in addition to meteorological model choice, the choice of tracer dispersion model also has a significant impact on the predicted downwind methane concentrations given the same emissions field. The dispersion models tested often underpredicted the observed methane enhancements with significant variability (up to a factor of 3) between different models and between different days. We examine possible causes for this result and find that the models differ in their simulation of vertical dispersion, indicating that additional work is needed to evaluate and improve vertical mixing in the tracer dispersion models commonly used in regional trace gas flux inversions.

In the past decade, there has been a scientific focus on improving the accuracy and precision of methane (CH4) emission estimates in the United States, with much effort targeting oil and natural gas producing basins. Yet, regional CH4 emissions and their attribution to specific sources continue to have significant associated uncertainties. Recent urban work using aircraft observations have suggested that CH4 emissions are not well characterized in major cities along the U.S. East Coast; discrepancies have been attributed to an under-estimation of fugitive emissions from the distribution of natural gas. However, much of regional and urban research has involved the use of aircraft campaigns that can only provide a spatio-temporal snapshot of the CH4 emission landscape. As such, the annual representation and the seasonal variability of emissions remain largely unknown. To further investigate CH4 emissions, we present preliminary CH4 emissions estimates in the Northeastern US as part of NIST’s Northeast Corridor (NEC) testbed project using a regional inversion framework. This area encompasses over 20% of the US and contains many of the dominant CH4 emissions sources important at both regional and local scales. The atmospheric inversion can estimate sub-monthly 0.1-degree emissions using observations from a regional network of up to 37 in-situ towers; some towers are in non-urban areas while others are in cities or suburban areas. The inversion uses different emission products to help provide a prior constraint within the inversion including anthropogenic emissions from both the EDGAR v42 for the year 2008 and the US EPA for the year 2012, and natural wetland CH4 emissions from the WetCHARTs ensemble mean for the year 2010. Results include the comparison of synthetic model simulated CH4 concentrations (i.e., convolutions of the emission products with WRF-STILT footprints + background) to mole-fractions measured at the regional in-situ sites. The comparison provides an indication as to how well our prior understanding of emissions and incoming air flow matches the atmospheric signatures due to the underlying CH4 sources. We also present a preliminary set of CH4 fluxes for a selected number of urban centers and discuss challenges estimating highly-resolved methane emissions using high-frequency in-situ observations for a regional domain (e.g. few constraints, skewness in underlying fluxes, representing incoming background, etc.). Overall, this work provides the basis for a year-long inversion that will yields regional CH4 emissions over the Northeast US with a focus on Eastern urban areas.

Advances in natural gas extraction technology have led to increased activity in the production and transport sectors in the United States and, as a consequence, an increased need for reliable monitoring of methane leaks to the atmosphere. We present a statistical methodology in combination with an observing system for the detection and attribution of fugitive emissions of methane from distributed potential source location landscapes such as natural gas production sites. We measure long (> 500 m), integrated open-path concentrations of atmospheric methane using a dual frequency comb spectrometer and combine measurements with an atmospheric transport model to infer leak locations and strengths using a novel statistical method, the non-zero minimum bootstrap (NZMB). The new statistical method allows us to determine whether the empirical distribution of possible source strengths for a given location excludes zero. Using this information, we identify leaking source locations (i.e., natural gas wells) through rejection of the null hypothesis that the source is not leaking. The method is tested with a series of synthetic data inversions with varying measurement density and varying levels of model–data mismatch. It is also tested with field observations of (1) a non-leaking source location and (2) a source location where a controlled emission of 3.1 × 10−5 kg s−1 of methane gas is released over a period of several hours. This series of synthetic data tests and outdoor field observations using a controlled methane release demonstrates the viability of the approach for the detection and sizing of very small leaks of methane across large distances (4+ km2 in synthetic tests). The field tests demonstrate the ability to attribute small atmospheric enhancements of 17 ppb to the emitting source location against a background of combined atmospheric (e.g., background methane variability) and measurement uncertainty of 5 ppb (1σ), when measurements are averaged over 2 min. The results of the synthetic and field data testing show that the new observing system and statistical approach greatly decreases the incidence of false alarms (that is, wrongly identifying a well site to be leaking) compared with the same tests that do not use the NZMB approach and therefore offers increased leak detection and sizing capabilities.

Natural gas infrastructure releases methane (CH4), a potent greenhouse gas, into the atmosphere. The estimated emission rate associated with the production and transportation of natural gas is uncertain, hindering our understanding of its greenhouse footprint. This study presents a new application of inverse methodology for estimating regional emission rates from natural gas production and gathering facilities in north-eastern Pennsylvania. An inventory of CH4 emissions was compiled for major sources in Pennsylvania. This inventory served as input emission data for the Weather Research and Forecasting model with chemistry enabled (WRF-Chem), and atmospheric CH4 mole fraction fields were generated at 3 km resolution. Simulated atmospheric CH4 enhancements from WRF-Chem were compared to observations obtained from a 3-week flight campaign in May 2015. Modelled enhancements from sources not associated with upstream natural gas processes were assumed constant and known and therefore removed from the optimization procedure, creating a set of observed enhancements from natural gas only. Simulated emission rates from unconventional production were then adjusted to minimize the mismatch between aircraft observations and model-simulated mole fractions for 10 flights. To evaluate the method, an aircraft mass balance calculation was performed for four flights where conditions permitted its use. Using the model optimization approach, the weighted mean emission rate from unconventional natural gas production and gathering facilities in north-eastern Pennsylvania approach is found to be 0.36 % of total gas production, with a 2σ confidence interval between 0.27 and 0.45 % of production. Similarly, the mean emission estimates using the aircraft mass balance approach are calculated to be 0.40 % of regional natural gas production, with a 2σ confidence interval between 0.08 and 0.72 % of production. These emission rates as a percent of production are lower than rates found in any other basin using a top-down methodology, and may be indicative of some characteristics of the basin that make sources from the north-eastern Marcellus region unique.

Non-dispersive infrared (NDIR) sensors are a low-cost way to observe carbon dioxide concentrations in air, but their specified accuracy and precision are not sufficient for some scientific applications. An initial evaluation of six SenseAir K30 carbon dioxide NDIR sensors in a lab setting showed that without any calibration or correction, the sensors have an individual root mean square error (RMSE) between ∼ 5 and 21 parts per million (ppm) compared to a research-grade greenhouse gas analyzer using cavity enhanced laser absorption spectroscopy. Through further evaluation, after correcting for environmental variables with coefficients determined through a multivariate linear regression analysis, the calculated difference between the each of six individual K30 NDIR sensors and the higher-precision instrument had an RMSE of between 1.7 and 4.3 ppm for 1 min data. The median RMSE improved from 9.6 for off-the-shelf sensors to 1.9 ppm after correction and calibration, demonstrating the potential to provide useful information for ambient air monitoring.

Urban areas are increasingly recognized as an important source of methane (CH4), but we have limited seasonally resolved observations of these regions. In this study, we quantify seasonal and annual urban CH4 emissions over the Baltimore, Maryland, and Washington, DC metropolitan regions. We use CH4 atmospheric observations from four tall tower stations and a Lagrangian particle dispersion model to simulate CH4 concentrations at these stations. We directly compare these simulations with observations and use a geostatistical inversion method to determine optimal emissions to match our observations. We use observations spanning four seasons and employ an ensemble approach considering multiple meteorological representations, emission inventories, and upwind CH4 values. Forward simulations in winter, spring, and fall underestimate observed atmospheric CH4 while in summer, simulations overestimate observations because of excess modeled wetland emissions. With ensemble geostatistical inversions, the optimized annual emissions in DC/Baltimore are 39 ± 9 Gg/month (1 δ), 2.0 ± 0.4 times higher than the ensemble mean of bottom-up emission inventories. We find a modest seasonal variability of urban CH4 emissions not captured in current inventories, with optimized summer emissions ∼41% lower than winter, broadly consistent with expectations if emissions are dominated by fugitive natural gas sources that correlate with natural gas usage.

Continuous measurements of atmospheric methane (CH4) mole fractions measured by NOAA's Global Greenhouse Gas Reference Network in Barrow, AK (BRW), show strong enhancements above background values when winds come from the land sector from July to December from 1986 to 2015, indicating that emissions from arctic tundra continue through autumn and into early winter. Twenty-nine years of measurements show little change in seasonal mean land sector CH4 enhancements, despite an increase in annual mean temperatures of 1.2 ± 0.8°C/decade (2σ). The record does reveal small increases in CH4 enhancements in November and December after 2010 due to increased late-season emissions. The lack of significant long-term trends suggests that more complex biogeochemical processes are counteracting the observed short-term (monthly) temperature sensitivity of 5.0 ± 3.6 ppb CH4/°C. Our results suggest that even the observed short-term temperature sensitivity from the Arctic will have little impact on the global atmospheric CH4 budget in the long term if future trajectories evolve with the same temperature sensitivity.

We present in situ airborne measurements of methane (CH4) and ethane (C2H6) taken aboard a NOAA DHC-6 Twin Otter research aircraft in May 2014 over the Williston Basin in northwestern North Dakota, a region of rapidly growing oil and natural gas production. The Williston Basin is best known for the Bakken shale formation, from which a significant increase in oil and gas extraction has occurred since 2009. We derive a CH4 emission rate from this region using airborne data by calculating the CH4 enhancement flux through the planetary boundary layer downwind of the region. We calculate CH4 emissions of (36 ± 13), (27 ± 13), (27 ± 12), (27 ± 12), and (25 ± 10) × 103 kg/h from five transects on 3 days in May 2014 downwind of the Bakken shale region of North Dakota. The average emission, (28 ± 5) × 103 kg/h, extrapolates to 0.25 ± 0.05 Tg/yr, which is significantly lower than a previous estimate of CH4 emissions from northwestern North Dakota and southeastern Saskatchewan using satellite remote sensing data. We attribute the majority of CH4 emissions in the region to oil and gas operations in the Bakken based on the similarity between atmospheric C2H6 to CH4 enhancement ratios and the composition of raw natural gas withdrawn from the region.

We present estimates of regional methane (CH4) emissions from oil and natural gas operations in the Barnett Shale, Texas, using airborne atmospheric measurements. Using a mass balance approach on eight different flight days in March and October 2013, the total CH4 emissions for the region are estimated to be 76 ± 13 × 10(3) kg hr(-1) (equivalent to 0.66 ± 0.11 Tg CH4 yr(-1); 95% confidence interval (CI)). We estimate that 60 ± 11 × 10(3) kg CH4 hr(-1) (95% CI) are emitted by natural gas and oil operations, including production, processing, and distribution in the urban areas of Dallas and Fort Worth. This estimate agrees with the U.S. Environmental Protection Agency (EPA) estimate for nationwide CH4 emissions from the natural gas sector when scaled by natural gas production, but it is higher than emissions reported by the EDGAR inventory or by industry to EPA's Greenhouse Gas Reporting Program. This study is the first to show consistency between mass balance results on so many different days and in two different seasons, enabling better quantification of the related uncertainty. The Barnett is one of the largest production basins in the United States, with 8% of total U.S. natural gas production, and thus, our results represent a crucial step toward determining the greenhouse gas footprint of U.S. onshore natural gas production.

We present high time resolution airborne ethane (C2H6) and methane (CH4) measurements made in March and October 2013 as part of the Barnett Coordinated Campaign over the Barnett Shale formation in Texas. Ethane fluxes are quantified using a downwind flight strategy, a first demonstration of this approach for C2H6. Additionally, ethane-to-methane emissions ratios (C2H6:CH4) of point sources were observationally determined from simultaneous airborne C2H6 and CH4 measurements during a survey flight over the source region. Distinct C2H6:CH4 × 100% molar ratios of 0.0%, 1.8%, and 9.6%, indicative of microbial, low-C2H6 fossil, and high-C2H6 fossil sources, respectively, emerged in observations over the emissions source region of the Barnett Shale. Ethane-to-methane correlations were used in conjunction with C2H6 and CH4 fluxes to quantify the fraction of CH4 emissions derived from fossil and microbial sources. On the basis of two analyses, we find 71-85% of the observed methane emissions quantified in the Barnett Shale are derived from fossil sources. The average ethane flux observed from the studied region of the Barnett Shale was 6.6 ± 0.2 × 10(3) kg hr(-1) and consistent across six days in spring and fall of 2013.

Recent increases in oil and natural gas (NG) production throughout the western US have come with scientific and public interest in emission rates, air quality and climate impacts related to this industry. This study uses a regional scale air quality model WRF-Chem to simulate high ozone (O3) episodes during the winter of 2013 over the Uinta Basin (UB) in northeastern Utah, which is densely populated by thousands of oil and NG wells. The high resolution meteorological simulations are able to qualitatively reproduce the wintertime cold pool conditions that occurred in 2013, allowing the model to reproduce the observed multi-day buildup of atmospheric pollutants and accompanying rapid photochemical ozone formation in the UB. Two different emission scenarios for the oil and NG sector were employed in this study. The first emission scenario (bottom-up) was based on the US EPA National Emission Inventory (NEI) (2011, version 1) for the oil and NG sector for the UB. The second emission scenario (top-down) was based on the previously derived estimates of methane (CH4) emissions and a regression analysis for multiple species relative to CH4 concentration measurements in the UB. WRF-Chem simulations using the two emission data sets resulted in significant differences for concentrations of most gas-phase species. Evaluation of the model results shows greater underestimates of CH4 and other volatile organic compounds (VOCs) in the simulation with the NEI-2011 inventory than the case when the top-down emission scenario was used. Unlike VOCs, the NEI-2011 inventory significantly overestimates the emissions of nitrogen oxides (NOx), while the top-down emission scenario results in a moderate negative bias. Comparison of simulations using the two emission data sets reveals that the top-down case captures the high O3 episodes. In contrast, the simulation case using the bottom-up inventory is not able to reproduce any of the observed high O3 concentrations in the UB. A sensitivity analysis reveals that the major factors driving high wintertime O3 in the UB are shallow boundary layers with light winds, high emissions of VOCs from oil and NG operations compared to NOx emissions, enhancement of photolysis fluxes and reduction of O3 loss from deposition due to snow cover. Simple emission reduction scenarios show that the UB O3 production is VOC sensitive and NOx insensitive. The model results show a disproportionate contribution of aromatic VOCs to O3 formation relative to all other VOC emissions. We also present modeling results for winter of 2012, when high O3 levels were not observed in the UB. The air quality model together with the top-down emission framework presented here may help to address the emerging science and policy related questions surrounding the environmental impact of oil and NG drilling in western US.

We determined methane (CH4) emissions from Alaska using airborne measurements from the Carbon Arctic Reservoirs Vulnerability Experiment (CARVE). Atmospheric sampling was conducted between May and September 2012 and analyzed using a customized version of the polar weather research and forecast model linked to a Lagrangian particle dispersion model (stochastic time-inverted Lagrangian transport model). We estimated growing season CH4 fluxes of 8 ± 2 mg CH4⋅m−2⋅d−1 averaged over all of Alaska, corresponding to fluxes from wetlands of 56 − 13 + 22 56−13+22 mg CH4⋅m−2⋅d−1 if we assumed that wetlands are the only source from the land surface (all uncertainties are 95% confidence intervals from a bootstrapping analysis). Fluxes roughly doubled from May to July, then decreased gradually in August and September. Integrated emissions totaled 2.1 ± 0.5 Tg CH4 for Alaska from May to September 2012, close to the average (2.3; a range of 0.7 to 6 Tg CH4) predicted by various land surface models and inversion analyses for the growing season. Methane emissions from boreal Alaska were larger than from the North Slope; the monthly regional flux estimates showed no evidence of enhanced emissions during early spring or late fall, although these bursts may be more localized in time and space than can be detected by our analysis. These results provide an important baseline to which future studies can be compared.

To effectively address climate change, aggressive mitigation policies need to be implemented to reduce greenhouse gas emissions. Anthropogenic carbon emissions are mostly generated from urban environments, where human activities are spatially concentrated. Improvements in uncertainty determinations and precision of measurement techniques are critical to permit accurate and precise tracking of emissions changes relative to the reduction targets. As part of the INFLUX project, we quantified carbon dioxide (CO 2 ), carbon monoxide (CO) and methane (CH 4 ) emission rates for the city of Indianapolis by averaging results from nine aircraft-based mass balance experiments performed in November-December 2014. Our goal was to assess the achievable precision of the aircraft-based mass balance method through averaging, assuming constant CO 2 , CH 4 and CO emissions during a three-week field campaign in late fall. The averaging method leads to an emission rate of 14,600 mol/s for CO 2 , assumed to be largely fossil-derived for this period of the year, and 108 mol/s for CO. The relative standard error of the mean is 17% and 16%, for CO 2 and CO, respectively, at the 95% confidence level (CL), i.e. a more than 2-fold improvement from the previous estimate of ~40% for single-flight measurements for Indianapolis. For CH 4 , the averaged emission rate is 67 mol/s, while the standard error of the mean at 95% CL is large, i.e. ±60%. Given the results for CO 2 and CO for the same flight data, we conclude that this much larger scatter in the observed CH 4 emission rate is most likely due to variability of CH 4 emissions, suggesting that the assumption of constant daily emissions is not correct for CH 4 sources. This work shows that repeated measurements using aircraft-based mass balance methods can yield sufficient precision of the mean to inform emissions reduction efforts by detecting changes over time in urban emissions.

High-latitude ecosystems have the capacity to release large amounts of carbon dioxide (CO2) to the atmosphere in response to increasing temperatures, representing a potentially significant positive feedback within the climate system. Here, we combine aircraft and tower observations of atmospheric CO2 with remote sensing data and meteorological products to derive temporally and spatially resolved year-round CO2 fluxes across Alaska during 2012-2014. We find that tundra ecosystems were a net source of CO2 to the atmosphere annually, with especially high rates of respiration during early winter (October through December). Long-term records at Barrow, AK, suggest that CO2 emission rates from North Slope tundra have increased during the October through December period by 73% ± 11% since 1975, and are correlated with rising summer temperatures. Together, these results imply increasing early winter respiration and net annual emission of CO2 in Alaska, in response to climate warming. Our results provide evidence that the decadalscale increase in the amplitude of the CO2 seasonal cycle may be linked with increasing biogenic emissions in the Arctic, following the growing season. Early winter respirationwas not well simulated by the Earth System Models used to forecast future carbon fluxes in recent climate assessments. Therefore, these assessments may underestimate the carbon release from Arctic soils in response to a warming climate.

Non-dispersive infrared (NDIR) sensors are a low-cost way to observe carbon dioxide concentrations in air, but their specified accuracy and precision are not sufficient for some scientific applications. An initial evaluation of six SenseAir K30 carbon dioxide NDIR sensors in a lab setting showed that without any calibration or correction, the sensors have an individual root mean square (RMS) error between ~ 5 to 21 parts per million (ppm) compared to a research-grade greenhouse gas analyzer using cavity enhanced laser absorption spectroscopy. Through further evaluation, after correcting for environmental variables with coefficients determined through a multivariate linear regression analysis, the calculated difference between the each of six individual K30 NDIR sensors and the higher-precision instrument had for one minute data a standard deviation of between 1.6 ppm and 4.4 ppm. The median standard deviation improved from 8.08 for off the shelf sensors to 1.89 ppm after correction and calibration, demonstrating the potential to provide useful information for ambient air monitoring.

We present measurements of CO mole fraction and CO stable isotopes (δ13CO and δC18O) in air during the winters of 2013–14 and 2014–15 at tall tower sampling sites in and around Indianapolis, USA. A tower located upwind of the city was used to quantitatively remove the background CO signal, allowing for the first unambiguous isotopic characterization of the urban CO source and yielding 13CO of –27.7 ± 0.5‰ VPDB and C18O of 17.7 ± 1.1‰ VSMOW for this source. We use the tower isotope measurements, results from a limited traffic study, as well as atmospheric reaction rates to examine contributions from different sources to the Indianapolis CO budget. Our results are consistent with earlier findings that traffic emissions are the dominant source, suggesting a contribution of 96% or more to the overall Indianapolis wintertime CO emissions. Our results are also consistent with the hypothesis that emissions from a small fraction of vehicles without functional catalytic systems dominate the Indianapolis CO budget.

Emissions of methane (CH4) from oil and natural gas (O&G) operations in the most densely drilled area of the Denver-Julesburg Basin in Weld County located in northeastern Colorado are estimated for 2 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 t CH4/h for the 29 and 31 May 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 t CH4/h for these 2 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 t/h, close to 3 times higher than an hourly emission estimate based on Environmental Protection Agency'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 nonmethane hydrocarbons alone total 25.4 ± 8.2 t/h. Assuming that these emissions are solely originating from O&G-related activities in the study region, our results show that the state inventory for total volatile organic compounds emitted by O&G activities is at least a factor of 2 too low for May 2012. Our top-down emission estimate of benzene emissions from O&G operations is 173 ± 64 kg/h, or 7 times larger than in the state inventory.

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-km(2) 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.

[1] Methane (CH4) emissions from natural gas production are not well quantified and have the potential to offset the climate benefits of natural gas over other fossil fuels. We use atmospheric measurements in a mass balance approach to estimate CH4 emissions of 55 ± 15 × 103 kg h−1 from a natural gas and oil production field in Uintah County, Utah, on 1 day: 3 February 2012. This emission rate corresponds to 6.2%–11.7% (1σ) of average hourly natural gas production in Uintah County in the month of February. This study demonstrates the mass balance technique as a valuable tool for estimating emissions from oil and gas production regions and illustrates the need for further atmospheric measurements to determine the representativeness of our single-day estimate and to better assess inventories of CH4 emissions.

[1] Atmospheric methane (CH4) concentration in the mid-to-upper troposphere has been retrieved using atmospheric infrared sounder (AIRS) data on NASA EOS/AQUA. By selecting the AIRS strong CH4 absorption channels near 1306 cm−1, severe CH4 depletion was mapped during a stratospheric intrusion event on 27 March 2010. The areas with depleted CH4 mixing ratio are collocated with enhanced ozone (O3) and low tropopause height. Aircraft measurements observed the depleted CH4 and enhanced O3 down to 550 hPa. An estimate of the depleted CH4 amount which resulted from stratospheric intrusion is −54 to −67 Tg yr−1. This study suggests that the AIRS and/or other thermal infrared sounders can provide an observation of CH4 variation associated with stratospheric intrusion, a key unknown in CH4 budget, and this data set will be also useful for studying the stratosphere-troposphere exchange (STE).

Traditional techniques for measuring the mole fractions of greenhouse gases in the well-mixed atmosphere have required dry sample gas streams (dew point < −25 °C) to achieve the inter-laboratory compatibility goals set forth by the Global Atmosphere Watch programme of the World Meteorological Organisation (WMO/GAW) for carbon dioxide (±0.1 ppm in the Northern Hemisphere and ±0.05 ppm in the Southern Hemisphere) and methane (±2 ppb). Drying the sample gas to low levels of water vapour can be expensive, time-consuming, and/or problematic, especially at remote sites where access is difficult. Recent advances in optical measurement techniques, in particular cavity ring down spectroscopy, have led to the development of greenhouse gas analysers capable of simultaneous measurements of carbon dioxide, methane and water vapour. Unlike many older technologies, which can suffer from significant uncorrected interference from water vapour, these instruments permit accurate and precise greenhouse gas measurements that can meet the WMO/GAW inter-laboratory compatibility goals (WMO, 2011a) without drying the sample gas. In this paper, we present laboratory methodology for empirically deriving the water vapour correction factors, and we summarise a series of in-situ validation experiments comparing the measurements in humid gas streams to well-characterised dry-gas measurements. By using the manufacturer-supplied correction factors, the dry-mole fraction measurements have been demonstrated to be well within the GAW compatibility goals up to a water vapour concentration of at least 1%. By determining the correction factors for individual instruments once at the start of life, this water vapour concentration range can be extended to at least 2% over the life of the instrument, and if the correction factors are determined periodically over time, the evidence suggests that this range can be extended up to and even above 4% water vapour concentrations.

Instrumented aircraft measuring air composition in the Uinta Basin, Utah, during February 2012 and January-February 2013 documented dramatically different atmospheric ozone (O3) mole fractions. In 2012 O3 remained near levels of ∼40 ppb in a well-mixed 500–1000 m deep boundary layer while in 2013, O3 mole fractions >140 ppb were measured in a shallow (∼200 m) boundary layer. In contrast to 2012 when mole fractions of emissions from oil and gas production such as methane (CH4), non-methane hydrocarbons (NMHCs) and combustion products such as carbon dioxide (CO2) were moderately elevated, in winter 2013 very high mole fractions were observed. Snow cover in 2013 helped produce and maintain strong temperature inversions that capped a shallow cold pool layer. In 2012, O3 and CH4 and associated NMHCs mole fractions were not closely related. In 2013, O3 mole fractions were correlated with CH4 and a suite of NMHCs identifying the gas field as the primary source of the O3 precursor NMHC emissions. In 2013 there was a strong positive correlation between CH4 and CO2 suggesting combustion from oil and natural gas processing activities. The presence of O3 precursor NMHCs through the depth of the boundary layer in 2013 led to O3 production throughout the layer. In 2013, O3 mole fractions increased over the course of the week-long episodes indicating O3 photochemical production was larger than dilution and deposition rates, while CH4 mole fractions began to level off after 3 days indicative of some air being mixed out of the boundary layer. The plume of a coal-fired power plant located east of the main gas field was not an important contributor to O3 or O3 precursors in the boundary layer in 2013.

Northern high-latitude carbon sources and sinks, including those resulting from degrading permafrost, are thought to be sensitive to the rapidly warming climate. Because the near-surface atmosphere integrates surface fluxes over large ( ∼ 500–1000 km) scales, atmospheric monitoring of carbon dioxide (CO2) and methane (CH4) mole fractions in the daytime mixed layer is a promising method for detecting change in the carbon cycle throughout boreal Alaska. Here we use CO2 and CH4 measurements from a NOAA tower 17 km north of Fairbanks, AK, established as part of NASA's Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE), to investigate regional fluxes of CO2 and CH4 for 2012–2014. CARVE was designed to use aircraft and surface observations to better understand and quantify the sensitivity of Alaskan carbon fluxes to climate variability. We use high-resolution meteorological fields from the Polar Weather Research and Forecasting (WRF) model coupled with the Stochastic Time-Inverted Lagrangian Transport model (hereafter, WRF-STILT), along with the Polar Vegetation Photosynthesis and Respiration Model (PolarVPRM), to investigate fluxes of CO2 in boreal Alaska using the tower observations, which are sensitive to large areas of central Alaska. We show that simulated PolarVPRM–WRF-STILT CO2 mole fractions show remarkably good agreement with tower observations, suggesting that the WRF-STILT model represents the meteorology of the region quite well, and that the PolarVPRM flux magnitudes and spatial distribution are generally consistent with CO2 mole fractions observed at the CARVE tower. One exception to this good agreement is that during the fall of all 3 years, PolarVPRM cannot reproduce the observed CO2 respiration. Using the WRF-STILT model, we find that average CH4 fluxes in boreal Alaska are somewhat lower than flux estimates by Chang et al. (2014) over all of Alaska for May–September 2012; we also find that enhancements appear to persist during some wintertime periods, augmenting those observed during the summer and fall. The possibility of significant fall and winter CO2 and CH4 fluxes underscores the need for year-round in situ observations to quantify changes in boreal Alaskan annual carbon balance.

Published estimates of methane emissions from atmospheric data (top-down approaches) exceed those from source-based inventories (bottom-up approaches), leading to conflicting claims about the climate implications of fuel switching from coal or petroleum to natural gas. Based on data from a coordinated campaign in the Barnett Shale oil and gas-producing region of Texas, we find that top-down and bottom-up estimates of both total and fossil methane emissions agree within statistical confidence intervals (relative differences are 10% for fossil methane and 0.1% for total methane). We reduced uncertainty in top-down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution. Similarly, our bottom-up estimate incorporates a more complete count of facilities than past inventories, which omitted a significant number of major sources, and more effectively accounts for the influence of large emission sources using a statistical estimator that integrates observations from multiple ground-based measurement datasets. Two percent of oil and gas facilities in the Barnett accounts for half of methane emissions at any given time, and high-emitting facilities appear to be spatiotemporally variable. Measured oil and gas methane emissions are 90% larger than estimates based on the US Environmental Protection Agency’s Greenhouse Gas Inventory and correspond to 1.5% of natural gas production. This rate of methane loss increases the 20-y climate impacts of natural gas consumed in the region by roughly 50%.

Direct quantification of fossil fuel CO2 (CO2ff) in atmospheric samples can be used to examine several carbon cycle and air quality questions. We collected in situ CO2, CO, and CH4 measurements and flask samples in the boundary layer and free troposphere over Sacramento, California, USA, during two aircraft flights over and downwind of this urban area during spring of 2009. The flask samples were analyzed for Δ14CO2 and CO2 to determine the recently added CO2ff mole fraction. A suite of greenhouse and other trace gases, including hydrocarbons and halocarbons, were measured in the same samples. Strong correlations were observed between CO2ff and numerous trace gases associated with urban emissions. From these correlations we estimate emission ratios between CO2ff and these species, and compare these with bottom-up inventory-derived estimates. Recent county level inventory estimates for carbon monoxide (CO) and benzene from the California Air Resources Board CEPAM database are in good agreement with our measured emission ratios, whereas older emissions inventories appear to overestimate emissions of these gases by a factor of two. For most other trace species, there are substantial differences (200–500%) between our measured emission ratios and those derived from available emission inventories. For the first flight, we combine in situ CO measurements with the measured CO:CO2ff emission ratio of 14 ± 2 ppbCO/ppmCO2 to derive an estimate of CO2ff mole fraction throughout this flight, and also estimate the biospheric CO2 mixing ratio (CO2bio) from the difference of total and fossil CO2. The resulting CO2bio varies dramatically from up to 8 ± 2 ppm in the urban plume to −6 ± 1 ppm in the surrounding boundary layer air. Finally, we use the in situ estimates of CO2ff mole fraction to infer total fossil fuel CO2 emissions from the Sacramento region, using a mass balance approach. The resulting emissions are uncertain to within a factor of two due to uncertainties in wind speed and boundary layer height. Nevertheless, this first attempt to estimate urban-scale CO2ff from atmospheric radiocarbon measurements shows that CO2ff can be used to verify and improve emission inventories for many poorly known anthropogenic species, separate biospheric CO2, and indicates the potential to constrain CO2ff emissions if transport uncertainties are reduced.

We report measurements of methane (CH4) emission rates observed at eight different high-emitting point sources in the Barnett Shale, Texas, using aircraft-based methods performed as part of the Barnett Coordinated Campaign. We quantified CH4 emission rates from four gas processing plants, one compressor station, and three landfills during five flights conducted in October 2013. Results are compared to other aircraft- and surface-based measurements of the same facilities, and to estimates based on a national study of gathering and processing facilities emissions and 2013 annual average emissions reported to the U.S. EPA Greenhouse Gas Reporting Program (GHGRP). For the eight sources, CH4 emission measurements from the aircraft-based mass balance approach were a factor of 3.2-5.8 greater than the GHGRP-based estimates. Summed emissions totaled 7022 ± 2000 kg hr(-1), roughly 9% of the entire basin-wide CH4 emissions estimated from regional mass balance flights during the campaign. Emission measurements from five natural gas management facilities were 1.2-4.6 times larger than emissions based on the national study. Results from this study were used to represent "super-emitters" in a newly formulated Barnett Shale Inventory, demonstrating the importance of targeted sampling of "super-emitters" that may be missed by random sampling of a subset of the total.

We report the CH4 emission flux from the city of Indianapolis, IN, the site of the Indianapolis Flux Experiment (INFLUX) project for developing, assessing, and improving top-down and bottom-up approaches for quantifying urban greenhouse gas emissions. Using an aircraft-based mass balance approach, we find that the average CH4 emission rate from five flight experiments in 2011 is 135 ± 58 (1σ) moles s-1 (7800 ± 3300 kg hr-1). The effective per capita CH4 emission rate for Indianapolis is 77 kg CH4 person-1 yr-1, a figure that is less than the national anthropogenic CH4 emission (∼91 kg CH4 person-1 yr-1) but considerably larger than the global figure (∼48 kg CH4 person-1 yr-1). We consistently observed elevated CH4 concentrations at specific coordinates along our flight transects downwind of the city. Inflight investigations as well as back trajectories using measured wind directions showed that the elevated concentrations originated from the southwest side of the city where a landfill and a natural gas transmission regulating station (TRS) are located. Street level mobile measurements downwind of the landfill and the TRS supported the results of aircraft-based data, and were used to quantify the relative contributions from the two sources. We find that the CH4 emission from the TRS was negligible relative to the landfill, which was responsible for 33 ± 10% of the citywide emission flux. A regression of propane versus methane from aircraft flask samples suggests that the remaining citywide CH4 emissions (∼67%) derive from the natural gas distribution system. We discuss the combination of surface mobile observations and aircraft city-wide flux measurements to determine the total flux and apportionment to important sources.

During the winter of 2012–2013 atmospheric surface ozone mole fractions exceeded the US 8 h standard of 75 ppb on 39 days in the Uinta Basin of Utah. As part of the Uinta Basin Winter Ozone Study (UBWOS) aircraft flights were conducted throughout the basin with continuous measurements of ozone (O3), methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), nitrogen dioxide (NO2), and discrete whole air flask samples for determination of ∼50 trace gases including a number of non-methane hydrocarbons (NMHCs). During the course of seven flights conducted between 31 January and 7 February 2013, coinciding with strong, multi-day temperature inversions, O3 levels gradually built up in the shallow boundary layer from ∼45 ppb to ∼140 ppb. Near-surface CH4 mole fractions increased during the episode from near background levels of ∼2 ppm to over 10 ppm. Based on elevated levels of CH4 across the basin and high correlations of CH4 with NMHCs from the discrete air samples, O3 precursor NMHCs were also inferred to be elevated throughout the basin. Discrete plumes of high NO2 were observed in the gas production region of the basin suggesting that gas processing plants and compressor facilities were important point sources of reactive nitrogen oxides (NOx). Vertical profiles obtained during the flights showed that the high O3 mole fractions (as well as other elevated constituents) were confined to a shallow layer from near the ground to 300–400 m above ground level (m a.g.l.) capped by a strong temperature inversion. The highest mole fractions of the measured constituents during the study period were in an isothermal cold layer that varied from ∼300 m depth on 4 February to ∼150 m on 5 February. A gradient layer with declining mole fractions with altitude extended above the isothermal layer to ∼1900 m a.s.l. (300–400 m a.g.l.) indicative of some mixing of air out of the boundary layer. O3 mole fractions continued to increase within the basin as the high O3 episode developed over the course of a week. CH4 mole fractions, on the other hand, leveled off after several days. On several flights, the aircraft sampled the plume of a coal-fired power plant (located east of the main gas field) flowing above the inversion layer. These measurements ruled out the effluents of the power plant as a significant source of NOx for O3 production beneath the temperature inversion in the basin. The presence of elevated O3 precursors within the basin and the rapid daytime production of O3 in the atmosphere beneath the temperature inversion both indicated that O3 was being produced from precursors emitted within the basin beneath the temperature inversion. Although observations show that horizontal winds in the surface layer were relatively light during the high ozone event, they were sufficient to disperse precursors up to 80 km from primary sources in the main gas field in the southeast quadrant to the balance of the Uinta Basin.

Methane is an important greenhouse gas and tropospheric ozone precursor. Simultaneous observation of ethane with methane can help identify specific methane source types. Aerodyne Ethane-Mini spectrometers, employing recently available mid-infrared distributed feedback tunable diode lasers (DFB-TDL), provide 1 s ethane measurements with sub-ppb precision. In this work, an Ethane-Mini spectrometer has been integrated into two mobile sampling platforms, a ground vehicle and a small airplane, and used to measure ethane/methane enhancement ratios downwind of methane sources. Methane emissions with precisely known sources are shown to have ethane/methane enhancement ratios that differ greatly depending on the source type. Large differences between biogenic and thermogenic sources are observed. Variation within thermogenic sources are detected and tabulated. Methane emitters are classified by their expected ethane content. Categories include the following: biogenic (0.2%), dry gas (1-6%), wet gas (6%), pipeline grade natural gas (15%), and processed natural gas liquids (30%). Regional scale observations in the Dallas/Fort Worth area of Texas show two distinct ethane/methane enhancement ratios bridged by a transitional region. These results demonstrate the usefulness of continuous and fast ethane measurements in experimental studies of methane emissions, particularly in the oil and natural gas sector.

In March 2009 the NOAA/ESRL/GMD Carbon Cycle and Greenhouse Gases Group collaborated with the US Coast Guard (USCG) to establish the Alaska Coast Guard (ACG) sampling site, a unique addition to NOAA's atmospheric monitoring network. This collaboration takes advantage of USCG bi-weekly Arctic Domain Awareness (ADA) flights, conducted with Hercules C-130 aircraft from March to November each year. Flights typically last 8 h and cover a large area, traveling from Kodiak up to Barrow, Alaska, with altitude profiles near the coast and in the interior. NOAA instrumentation on each flight includes a flask sampling system, a continuous cavity ring-down spectroscopy (CRDS) carbon dioxide (CO2)/methane (CH4)/carbon monoxide (CO)/water vapor (H2O) analyzer, a continuous ozone analyzer, and an ambient temperature and humidity sensor. Air samples collected in flight are analyzed at NOAA/ESRL for the major greenhouse gases and a variety of halocarbons and hydrocarbons that influence climate, stratospheric ozone, and air quality. We describe the overall system for making accurate greenhouse gas measurements using a CRDS analyzer on an aircraft with minimal operator interaction and present an assessment of analyzer performance over a three-year period. Overall analytical uncertainty of CRDS measurements in 2011 is estimated to be 0.15 ppm, 1.4 ppb, and 5 ppb for CO2, CH4, and CO, respectively, considering short-term precision, calibration uncertainties, and water vapor correction uncertainty. The stability of the CRDS analyzer over a seven-month deployment period is better than 0.15 ppm, 2 ppb, and 4 ppb for CO2, CH4, and CO, respectively, based on differences of on-board reference tank measurements from a laboratory calibration performed prior to deployment. This stability is not affected by variation in pressure or temperature during flight. We conclude that the uncertainty reported for our measurements would not be significantly affected if the measurements were made without in-flight calibrations, provided ground calibrations and testing were performed regularly. Comparisons between in situ CRDS measurements and flask measurements are consistent with expected measurement uncertainties for CH4 and CO, but differences are larger than expected for CO2. Biases and standard deviations of comparisons with flask samples suggest that atmospheric variability, flask-to-flask variability, and possible flask sampling biases may be driving the observed flask versus in situ CO2 differences rather than the CRDS measurements.

[1] Atmospheric CO2 gradients are usually dominated by the signal from net terrestrial biological fluxes, despite the fact that fossil fuel combustion fluxes are larger in the annual mean. Here, we use a six year long series of 14CO2 and CO2 measurements obtained from vertical profiles at two northeast U.S. aircraft sampling sites to partition lower troposphere CO2 enhancements (and depletions) into terrestrial biological and fossil fuel components (Cbio and Cff). Mean Cff is 1.5 ppm, and 2.4 ppm when we consider only planetary boundary layer samples. However, we find that the contribution of Cbio to CO2 enhancements is large throughout the year, and averages 60% in winter. Paired observations of Cff and the lower troposphere enhancements (Δgas) of 22 other anthropogenic gases (CH4, CO, halo- and hydrocarbons and others) measured in the same samples are used to determine apparent emission ratios for each gas. We then scale these ratios by the well known U.S. fossil fuel CO2 emissions to provide observationally based estimates of national emissions for each gas and compare these to “bottom up” estimates from inventories. Correlations of Δgas with Cff for almost all gases are statistically significant with median r2for winter, summer and the entire year of 0.59, 0.45, and 0.42, respectively. Many gases exhibit statistically significant winter:summer differences in ratios that indicate seasonality of emissions or chemical destruction. The variability of ratios in a given season is not readily attributable to meteorological or geographic variables and instead most likely reflects real, short-term spatiotemporal variability of emissions.

[1] 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.

Previous work has shown that unlike YBa2 Cu3 O7-δ (Y123), the Nd-Ba-Cu-O system exhibits a solid solution Nd1+xBa2-x Cu3O7+δ (Nd123ss) for 0.04≤ × ≤0.6.1–3) An earlier paper showed that although the superconducting properties decrease nonlinearly for increasing x, Tc can be varied by increasing the annealing temperature without changing the low temperature oxygen soak.2 The changes in microstructure and Tc with increasing x are analogous with Y123 with increasing δ except that the total hole concentration remained constant. Tc was modeled in terms of oxygen disorder resulting from Nd3+ atoms on the Ba sites relocating chain oxygens to anti-chain sites. The variability in Tc as a function of x and processing conditions can be explained by the number of fourfold coordinated coppers on the chain sites. In this paper, the model has been further substantiated by processing in 1% O2. The annealing in a reduced oxygen partial pressure followed by a 450°C oxygen soak resulted in a marked increase in Tc compared to the 100% PO2 anneal. The low PO2 anneal favors pairing of Nd3+ substituting for Ba2+ to conserve oxygen ions, resulting in fewer disrupted fourfold-coordinated coppers thus increasing charge transfer from the planes to the chains.

The quantification of greenhouse gas emissions requires high precision measurements made with high spatial resolution. Here we describe measurements of carbon dioxide (CO2) and methane (CH4) conducted using Purdue University's Airborne Laboratory for Atmospheric Research (ALAR), aimed at the quantification of the "footprints" for these greenhouse gases for Indianapolis, IN. A cavity ring-down spectrometer measured atmospheric concentrations, and flask samples were obtained at various points for comparison. Coupled with pressure, temperature, and model-derived horizontal winds, these measurements allow for flux estimation. Long horizontal transects were flown perpendicular to the wind downwind of the city. Emissions were calculated using the wind speed and the difference between the concentration in the plume and the background concentration. A kriging method is applied to interpolate the measured values to a vertical plane traced out by the flight pattern within the mixed layer. Results show the urban plume is clearly distinguishable in the downwind concentrations for most flights. Additionally, there is large variability in the measured day-to-day emissions fluxes as well as in the relative CH4 and CO2 fluxes. Uncertainties in the method are discussed, and its potential utilityin determining sector-based emission factors is shown.