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.

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.

Emissions of methane (CH 4 ) 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 CH 4 observations and planetary boundary layer height and ground-based wind profile measurements. Total top-down CH 4 emission estimates are 25.8 ± 8.4 and 26.2 ± 10.7 t CH 4 /h for the 29 and 31 May flights, respectively. Using inventory data, we estimate the total emissions of CH 4 from non-O&G gas-related sources at 7.1 ± 1.7 and 6.3 ± 1.0 t CH 4 /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 CH 4 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.

[1] Methane (CH 4 ), carbon dioxide (CO 2 ), carbon monoxide (CO), and C 2 -C 5 alkanes were measured throughout the Los Angeles (L.A.) basin in May and June 2010. We use these data to show that the emission ratios of CH 4 /CO and CH 4 /CO 2 in the L.A. basin are larger than expected from population-apportioned bottom-up state inventories, consistent with previously published work. We use experimentally determined CH 4 /CO and CH 4 /CO 2 emission ratios in combination with annual State of California CO and CO 2 inventories to derive a yearly emission rate of CH 4 to the L.A. basin. We further use the airborne measurements to directly derive CH 4 emission rates from dairy operations in Chino, and from the two largest landfills in the L.A. basin, and show these sources are accurately represented in the California Air Resources Board greenhouse gas inventory for CH 4 . We then use measurements of C 2 -C 5 alkanes to quantify the relative contribution of other CH 4 sources in the L.A. basin, with results differing from those of previous studies. The atmospheric data are consistent with the majority of CH 4 emissions in the region coming from fugitive losses from natural gas in pipelines and urban distribution systems and/or geologic seeps, as well as landfills and dairies. The local oil and gas industry also provides a significant source of CH 4 in the area. The addition of CH 4 emissions from natural gas pipelines and urban distribution systems and/or geologic seeps and from the local oil and gas industry is sufficient to account for the differences between the top-down and bottom-up CH 4 inventories identified in previously published work.

Abstract. A reliable and precise in situ CO2 and CO analysis system has been developed and deployed at eight sites in the NOAA Earth System Research Laboratory's (ESRL) Global Greenhouse Gas Reference Network. The network uses very tall (> 300 m) television and radio transmitter towers that provide a convenient platform for mid-boundary-layer trace-gas sampling. Each analyzer has three sample inlets for profile sampling, and a complete vertical profile is obtained every 15 min. The instrument suite at one site has been augmented with a cavity ring-down spectrometer for measuring CO2 and CH4. The long-term stability of the systems in the field is typically better than 0.1 ppm for CO2, 6 ppb for CO, and 0.5 ppb for CH4, as determined from repeated standard gas measurements. The instrumentation is fully automated and includes sensors for measuring a variety of status parameters, such as temperatures, pressures, and flow rates, that are inputs for automated alerts and quality control algorithms. Detailed and time-dependent uncertainty estimates have been constructed for all of the gases, and the uncertainty framework could be readily adapted to other species or analysis systems. The design emphasizes use of off-the-shelf parts and modularity to facilitate network operations and ease of maintenance. The systems report high-quality data with > 93% uptime. Recurrent problems and limitations of the current system are discussed along with general recommendations for high-accuracy trace-gas monitoring. The network is a key component of the North American Carbon Program and a useful model for future research-grade operational greenhouse gas monitoring efforts.

We demonstrate coherent dual frequency-comb spectroscopy for detecting variations in greenhouse gases. High signal-to-noise spectra are acquired spanning 5990 to 6260 cm -1 (1600 to 1670 nm) covering ~700 absorption features from CO 2 , CH 4 , H 2 O, HDO, and 13 CO 2 , across a 2-km open-air path. The transmission of each frequency comb tooth is resolved, leading to spectra with <1 kHz frequency accuracy, no instrument lineshape, and a 0.0033-cm -1 point spacing. The fitted path-averaged concentrations and temperature yield dry-air mole fractions. These are compared with a point sensor under well-mixed conditions to evaluate current absorption models for real atmospheres. In heterogeneous conditions, timeresolved data demonstrate tracking of strong variations in mole fractions. A precision of <1 ppm for CO 2 and <3 ppb for CH 4 is achieved in 5 minutes in this initial demonstration. Future portable systems could support regional emissions monitoring and validation of the spectral databases critical to global satellitebased trace gas monitoring.

[1] Airborne and ground-based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well-known and much-studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NO x = NO + NO 2 ) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non-methane volatile organic compounds (VOCs) to NO x . In accord with previous assessments, the 2010 airborne and ground-based data show an average decrease in NO x of 46 AE 11% and 34 AE 4%, respectively, and an average increase in VOC/NO x ratio of 48 AE 8% and 43 AE 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC-NO x oxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday-to-weekend differences in the products of NO x oxidation show 45 AE 13% and 42 AE 12% more extensive photochemical processing and, when compared with odd oxygen (O x = O 3 + NO 2 ), 51 AE 14% and 22 AE 17% greater ozone production efficiency on weekends in the airborne and ground-based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.

Results of mobile ground-based atmospheric measurements conducted during the Barnett Shale Coordinated Campaign in spring and fall of 2013 are presented. Methane and ethane are continuously measured downwind of facilities such as natural gas processing plants, compressor stations, and production well pads. Gaussian dispersion simulations of these methane plumes, using an iterative forward plume dispersion algorithm, are used to estimate both the source location and the emission magnitude. The distribution of emitters is peaked in the 0-5 kg/h range, with a significant tail. The ethane/methane molar enhancement ratio for this same distribution is investigated, showing a peak at ∼1.5% and a broad distribution between ∼4% and ∼17%. The regional distributions of source emissions and ethane/methane enhancement ratios are examined: the largest methane emissions appear between Fort Worth and Dallas, while the highest ethane/methane enhancement ratios occur for plumes observed in the northwestern potion of the region. Individual facilities, focusing on large emitters, are further analyzed by constraining the source location.