ALBERT

Beschreibung: The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NOy. The severe model overestimate of NOy during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NOy partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3 % to 9 % and improves model–measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr−1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Beschreibung: Emissions of methane (CH 4 ) and volatile organic compounds (VOCs) from oil and gas production may have large impacts on air quality and climate change. Methane and VOCs were measured over the Haynesville and Marcellus shale gas plays onboard the NCAR C-130 and NOAA WP-3D research aircraft in June-July of 2013. We used an eddy covariance technique to measure in situ fluxes of CH 4 and benzene from both C-130 flights with high-resolution data (10 Hz) and WP-3D flights with low-resolution data (1 Hz). Correlation (R=0.65) between CH 4 and benzene fluxes was observed when flying over shale gas operations and the enhancement ratio of fluxes was consistent with the corresponding concentration observations. Fluxes calculated by the eddy covariance method show agreement with a mass balance approach within their combined uncertainties. In general, CH 4 fluxes in the shale gas regions follow a lognormal distribution, with some deviations for relatively large fluxes (〉10 µg m −2 s −1 ). Statistical analysis of the fluxes shows that a small number of facilities (i.e. ~10%) are responsible for up to ~40% of the total CH 4 emissions in the two regions. We show that the airborne eddy covariance method can also be applied in some circumstances when meteorological conditions do not favor application of the mass balance method. We suggest that the airborne eddy covariance method is a reliable alternative and complementary analysis method to estimate emissions from oil and gas extraction.

Beschreibung: Tropospheric O 3 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 NO x 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 O 3 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 NO x emissions. Here, VOC OH reactivity (OHR), O 3 production efficiency (OPE), and an observationally constrained box model are used to quantify the influence of O&NG emissions on regional summertime O 3 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 emissions sectors. The box model confirms relatively modest OPE differences that are within the uncertainties of the field observations. Box model results also indicate that maximum O 3 at the measurement location is sensitive to changes in NO x 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 O 3 production.

Beschreibung: We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γ glyx of 2 × 10 -3 , and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8 µg m -3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde ( R GF  = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO 2 ). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO 2 . Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

Beschreibung: [1]  A combined field and laboratory study was conducted to improve our understanding of the chemical and hygroscopic properties of organic compounds in aerosols sampled in the background continental atmosphere. PM 2.5 (particles with aerodynamic diameters smaller than 2.5 µm) aerosols were collected from 24 June to 28 July, 2010 at Storm Peak Laboratory in the Park Range of northwestern Colorado. New particle formation was frequent at Storm Peak Laboratory during this campaign, and the samples were not influenced by regional dust storms. Filter samples were analyzed for organic carbon (OC) and elemental carbon (EC), water soluble OC (WSOC), major inorganic ions, and detailed organic speciation. WSOC was isolated from inorganic ions using solid phase absorbents. Hygroscopic growth factors and cloud condensation nucleus (CCN) activity of the WSOC were measured in the laboratory. Organic compounds comprised the majority (average of 64% with a standard deviation of 9%) of the mass of measured species and WSOC accounted for an average of 89% (with a standard deviation of 21%) of OC mass. Daily samples were composited according to back-trajectories. On average, organic acids, sugars, and sugar alcohols accounted for 12.5 ± 6.2% (average ± standard deviation) of WSOC. Based on the composition of these compounds and that of high molecular weight compounds identified using ultra high resolution mass spectrometry, the organic mass to organic carbon ratio of the WSOC is estimated to be 2.04. The average hygroscopic growth factors at RH = 80% (GF 80 ) were 1.10 ± 0.03 for particles derived from isolated WSOC and 1.27 ± 0.03 for particles derived from the total water-soluble material (WSM). CCN activity followed a similar pattern. The critical diameters at a super-saturation of 0.35% were 0.072 ± 0.009 and 0.094 ± 0.006 µm for particles derived from WSM and isolated WSOC, respectively. These growth factor results compare favorably with estimates from thermodynamic models, which explicitly relate the water activity (RH) to concentration for the total soluble material identified in this study.

Beschreibung: [1]  We have measured the bidirectional reflectance of analogs of dry, wet and frozen Martian soils over a wide range of phase angles in the visible spectral range. All samples were produced from two geologic samples: the standard JSC Mars-1 soil simulant and Hawaiian basaltic sand. In a first step, experiments were conducted with the dry samples to investigate the effects of surface texture. Comparisons with results independently obtained by different teams with similar samples showed a satisfying reproducibility of the photometric measurements as well as a noticeable influence of surface textures resulting from different sample preparation procedures. In a second step, water was introduced to produce wet and frozen samples and their photometry investigated. Optical microscope images of the samples provided information about their micro-texture. Liquid water, even in relatively low amount, resulted in the disappearance of the backscattering peak and the appearance of a forward scattering peak whose intensity increases with the amount of water. Specular reflections only appeared when water was present in an amount large enough to allow water to form a film at the surface of the sample. Icy samples showed a wide variability of photometric properties depending on the physical properties of the water ice. We discuss the implications of these measurements in terms of the expected photometric behavior of the Martian surface, from equatorial to circum-polar regions. In particular, we propose some simple photometric criteria to improve the identification of wet and/or icy soils from multiple observations under different geometries.