K. C. Aikin

Chemical depletion of Arctic ozone in winter 1999/2000

During Arctic winters with a cold, stable stratospheric circulation, reactions on the surface of polar stratospheric clouds (PSCs) lead to elevated abundances of chlorine monoxide (ClO) that, in the presence of sunlight, destroy ozone. Here we show that PSCs were more widespread during the 1999/2000 Arctic winter than for any other Arctic winter in the past two decades. We have used three fundamentally different approaches to derive the degree of chemical ozone loss from ozonesonde, balloon, aircraft, and satellite instruments. We show that the ozone losses derived from these different instruments and approaches agree very well, resulting in a high level of confidence in the results. Chemical processes led to a 70% reduction of ozone for a region ∼1 km thick of the lower stratosphere, the largest degree of local loss ever reported for the Arctic. The Match analysis of ozonesonde data shows that the accumulated chemical loss of ozone inside the Arctic vortex totaled 117 ± 14 Dobson units (DU) by the end of winter. This loss, combined with dynamical redistribution of air parcels, resulted in a 88 ± 13 DU reduction in total column ozone compared to the amount that would have been present in the absence of any chemical loss. The chemical loss of ozone throughout the winter was nearly balanced by dynamical resupply of ozone to the vortex, resulting in a relatively constant value of total ozone of 340 ± 50 DU between early January and late March. This observation of nearly constant total ozone in the Arctic vortex is in contrast to the increase of total column ozone between January and March that is observed during most years.

Quantifying atmospheric methane emissions from the Haynesville, Fayetteville, and northeastern Marcellus shale gas production regions

We present measurements of methane (CH4) taken aboard a NOAA WP-3D research aircraft in 2013 over the Haynesville shale region in eastern Texas/northwestern Louisiana, the Fayetteville shale region in Arkansas, and the northeastern Pennsylvania portion of the Marcellus shale region, which accounted for the majority of Marcellus shale gas production that year. We calculate emission rates from the horizontal CH4 flux in the planetary boundary layer downwind of each region after subtracting the CH4 flux entering the region upwind. We find 1 day CH4 emissions of (8.0 ± 2.7) × 107 g/h from the Haynesville region, (3.9 ± 1.8) × 107 g/h from the Fayetteville region, and (1.5 ± 0.6) × 107 g/h from the Marcellus region in northeastern Pennsylvania. Finally, we compare the CH4 emissions to the total volume of natural gas extracted from each region to derive a loss rate from production operations of 1.0–2.1% from the Haynesville region, 1.0–2.8% from the Fayetteville region, and 0.18–0.41% from the Marcellus region in northeastern Pennsylvania. The climate impact of CH4 loss from shale gas production depends upon the total leakage from all production regions. The regions investigated in this work represented over half of the U.S. shale gas production in 2013, and we find generally lower loss rates than those reported in earlier studies of regions that made smaller contributions to total production. Hence, the national average CH4 loss rate from shale gas production may be lower than values extrapolated from the earlier studies.

Severe chemical ozone loss inside the Arctic Polar Vortex during winter 1999–2000 Inferred from in situ airborne measurements

Lower stratospheric in situ observations are used to quantify both the accumulated ozone loss and the ozone chemical loss rates in the Arctic polar vortex during the 1999–2000 winter. Multiple long-lived trace gas correlations are used to identify parcels in the inner Arctic vortex whose chemical loss rates are unaffected by extra-vortex intrusions. Ozone-tracer correlations are then used to calculate ozone chemical loss rates. During the late winter the ozone chemical loss rate is found to be −46±6 (1σ) ppbv/day. By mid-March 2000, the accumulated ozone chemical loss is 58±4% in the lower stratosphere near 450 K potential temperature (∼19 km altitude).

Observational evidence for the role of denitrification in Arctic stratospheric ozone loss

Severe and extensive denitrification, chlorine activation, and photochemical ozone loss were observed throughout the lower stratosphere in the 1999–2000 Arctic vortex. A large number of air parcels sampled between late February and mid-March, 2000, were photochemically intercomparable for chemical O3 loss rates. In these air parcels, the temporal evolution of the correlations of O3 with the NOy remaining after denitrification provides strong evidence for the role of NOy in moderating O3 destruction. In 71%-denitrified air parcels, a chemical O3 destruction rate of 63 ppbv/day was calculated, while in 43%-denitrified air parcels the destruction rate was only 43 ppbv/day. These observational results show that representative denitrification models will be required for accurate prediction of future Arctic O3 changes.

Modulation of middle and upper tropospheric ozone at northern midlatitudes by the El Niño/Southern Oscillation

A five-year time series of lidar profiles from a site in Colorado is used to investigate the sources and scales of variability for ozone in the free troposphere. Analysis of 475 daily mean profiles derived from more than 25,000 individual profiles shows that ∼66% of the total variance is due to fluctuations on time scales from 1 day to 1 month, ∼30% on time scales from 1 month to 1 year, and ∼4% on time scales greater than 1 year. The analysis also identifies low-frequency fluctuations correlated with the El Nino/Southern Oscillation (ENSO) (following a ∼6-month lag) that may account for as much as 5% of the total variance in the data. The ENSO-related changes can also lead to apparent ozone trends that range from -0.2 to +0.5 ppbv/yr for different 10-year intervals between 1970 and 1990.

Instrumentation and Measurement Strategy for the NOAA SENEX Aircraft Campaign as Part of the Southeast Atmosphere Study 2013

Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeast of the US. In addition, anthropogenic emissions are significant in the Southeast US and summertime photochemistry is rapid. The NOAA-led SENEX (Southeast Nexus) aircraft campaign was one of the major components of the Southeast Atmosphere Study (SAS) and was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants. During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN. Here we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign. The aircraft, its capabilities and standard measurements are described. The instrument payload is summarized including detection limits, accuracy, precision and time resolutions for all gas-and-aerosol phase instruments. The inter-comparisons of compounds measured with multiple instruments on the NOAA WP-3D are presented and were all within the stated uncertainties, except two of the three NO2 measurements. The SENEX flights included day- and nighttime flights in the Southeast as well as flights over areas with intense shale gas extraction (Marcellus, Fayetteville and Haynesville shale). We present one example flight on 16 June 2013, which was a daytime flight over the Atlanta region, where several crosswind transects of plumes from the city and nearby point sources, such as power plants, paper mills and landfills, were flown. The area around Atlanta has large biogenic isoprene emissions, which provided an excellent case for studying the interactions between biogenic and anthropogenic emissions. In this example flight, chemistry in and outside the Atlanta plumes was observed for several hours after emission. The analysis of this flight showcases the strategies implemented to answer some of the main SENEX science questions.

Observations of methyl nitrate in the lower stratosphere during STRAT: Implications for its gas phase production mechanisms

Methyl nitrate has been measured for the first time in the lower stratosphere at altitudes to 20.5 km during the December 1996 NASA Stratospheric Tracers of Atmospheric Transport (STRAT) deployment. Whole air samples were taken on board the NASA ER2 aircraft and analyzed using gas chromatography/mass spectrometry. Methyl nitrate was present at measurable levels throughout the entire altitude range covered. Taking advantage of the rather simple chemistry in the lower stratosphere compared to the troposphere, and considering the known in-situ photochemical sources for methyl nitrate, the yield of methyl nitrate from the reaction of methyl peroxy radicals with NO was estimated.

Quantifying atmospheric methane emissions from oil and natural gas production in the Bakken shale region of North Dakota

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.

Influence of Oil and Gas Emissions on Summertime Ozone in the Colorado Northern Front Range

Tropospheric O3 has been decreasing across much of the eastern U.S. but has remained steady or even increased in some western regions. Recent increases in VOC and NOx emissions associated with the production of oil and natural gas (O&NG) may contribute to this trend in some areas. The Northern Front Range of Colorado has regularly exceeded O3 air quality standards during summertime in recent years. This region has VOC emissions from a rapidly developing O&NG basin and low concentrations of biogenic VOC in close proximity to urban-Denver NOx emissions. Here VOC OH reactivity (OHR), O3 production efficiency (OPE), and an observationally constrained box model are used to quantify the influence of O&NG emissions on regional summertime O3 production. Analyses are based on measurements acquired over two summers at a central location within the Northern Front Range that lies between major regional O&NG and urban emission sectors. Observational analyses suggest that mixing obscures any OPE differences in air primarily influenced by O&NG or urban emission sector. The box model confirms relatively modest OPE differences that are within the uncertainties of the field observations. Box model results also indicate that maximum O3 at the measurement location is sensitive to changes in NOx mixing ratio but also responsive to O&NG VOC reductions. Combined, these analyses show that O&NG alkanes contribute over 80% to the observed carbon mixing ratio, roughly 50% to the regional VOC OHR, and approximately 20% to regional photochemical O3 production.

Emissions of nitrogen‐containing organic compounds from the burning of herbaceous and arboraceous biomass: Fuel composition dependence and the variability of commonly used nitrile tracers

Volatile organic compounds (VOCs) emitted from residential wood and crop residue burning were measured in Colorado, U.S. When compared to the emissions from crop burning, residential wood burning exhibited markedly lower concentrations of acetonitrile, a commonly used biomass burning tracer. For both herbaceous and arboraceous fuels, the emissions of nitrogen-containing VOCs (NVOCs) strongly depend on the fuel nitrogen content; therefore, low NVOC emissions from residential wood burning result from the combustion of low-nitrogen fuel. Consequently, the emissions of compounds hazardous to human health, such as HNCO and HCN, and the formation of secondary pollutants, such as ozone generated by NOx, are likely to depend on fuel nitrogen. These results also demonstrate that acetonitrile may not be a suitable tracer for domestic burning in urban areas. Wood burning emissions may be best identified through analysis of the emissions profile rather than reliance on a single tracer species.