The details of aerosol processes and size distributions
in the stratosphere are important for both heterogeneous chemistry and
aerosol–radiation interactions. Using in situ, global-scale measurements ...of
the size distribution of particles with diameters > 3 nm from the
NASA Atmospheric Tomography Mission (ATom), we identify a mode of aerosol
smaller than 12 nm in the lowermost stratosphere (LMS) at mid- and high
latitudes. This mode is substantial only in the Northern Hemisphere (NH)
and was observed in all four seasons. We also observe elevated SO2, an
important precursor for new particle formation (NPF) and growth, in the NH
LMS. We use box modelling and thermodynamic calculations to show that NPF
can occur in the LMS conditions observed on ATom. Aircraft emissions are
shown as likely sources of this SO2, as well as a potential source of
nucleation mode particles directly emitted by or formed in the plume of the
engines. These nucleation mode particles have the potential to grow to
larger sizes and to coagulate with larger aerosol, affecting heterogeneous
chemistry and aerosol–radiation interactions. Understanding all sources and
characteristics of stratospheric aerosols is important in the context of
anthropogenic climate change as well as proposals for climate intervention
via stratospheric sulfur injection. This analysis not only adds to the,
currently sparse, observations of the global impact of aviation, but also
introduces another aspect of climate influence, namely a size distribution
shift of the background aerosol distribution in the LMS.
Nitrous oxide (N2O) is a long-lived greenhouse gas that also destroys stratospheric ozone. N2O emissions are uncertain and characterized by high spatiotemporal variability, making individual ...observations difficult to upscale, especially in mixed land use source regions like the San Joaquin Valley (SJV) of California. Here, we calculate spatially integrated N2O emission rates using nocturnal and convective boundary-layer budgeting methods. We utilize vertical profile measurements from the NASA DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality) campaign, which took place January–February, 2013. For empirical constraints on N2O source identity, we analyze N2O enhancement ratios with methane, ammonia, carbon dioxide, and carbon monoxide separately in the nocturnal boundary layer, nocturnal residual layer, and convective boundary layer. We find that an established inventory (EDGAR v4.3.2) underestimates N2O emissions by at least a factor of 2.5, that wintertime emissions from animal agriculture are important to annual totals, and that there is evidence for higher N2O emissions during the daytime than at night.
We present in situ observations of convectively injected water vapor in the lower stratosphere from instruments aboard two aircraft operated during the Deep Convective Clouds and Chemistry ...experiment. Water vapor mixing ratios in the injected air are observed to be 60–225 ppmv at altitudes 1–2 km above the tropopause (350–370 K potential temperature), well above observed background mixing ratios of 5–10 ppmv in the lower stratosphere. Radar observations of the responsible convective systems show deep overshooting at altitudes up to 4 km above the lapse rate tropopause and above the flight ceilings of the aircraft. Backward trajectories from the in situ observations show that convectively injected water vapor is observed from three distinct types of systems: isolated convection, a convective line, and a leading line‐trailing stratiform mesoscale convective system. Significant transport of additional tropospheric or boundary layer trace gases is observed only for the leading line‐trailing stratiform case. In addition, all observations of convective injection are found to occur within large‐scale double‐tropopause events from poleward Rossby wave breaking. Based on this relationship, we present a hypothesis on the role of the large‐scale lower stratosphere during convective overshooting. In particular, the reduced lower stratosphere stability associated with double‐tropopause environments may facilitate deeper levels of overshooting and convective injection.
Key PointsInjected water vapor observed up to 200 ppm above background lower stratosphereConvective overshooting up to 4 km above the tropopauseReduced stability from double tropopause may facilitate deep overshooting
In situ microphysical observations of midlatitude cirrus collected during the Department of Energy Small Particles in Cirrus (SPARTICUS) field campaign are combined with an atmospheric state ...classification for the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) site to understand statistical relationships between cirrus microphysics and the large‐scale meteorology. The atmospheric state classification is informed about the large‐scale meteorology and state of cloudiness at the ARM SGP site by combining ECMWF ERA‐Interim reanalysis data with 14 years of continuous observations from the millimeter‐wavelength cloud radar. Almost half of the cirrus cloud occurrences in the vicinity of the ARM SGP site during SPARTICUS can be explained by three distinct synoptic conditions, namely, upper level ridges, midlatitude cyclones with frontal systems, and subtropical flows. Probability density functions (PDFs) of cirrus microphysical properties such as particle size distributions (PSDs), ice number concentrations, and ice water content (IWC) are examined and exhibit striking differences among the different synoptic regimes. Generally, narrower PSDs with lower IWC but higher ice number concentrations are found in cirrus sampled in upper level ridges, whereas cirrus sampled in subtropical flows, fronts, and aged anvils show broader PSDs with considerably lower ice number concentrations but higher IWC. Despite striking contrasts in the cirrus microphysics for different large‐scale environments, the PDFs of vertical velocity are not different, suggesting that vertical velocity PDFs are a poor predictor for explaining the microphysical variability in cirrus. Instead, cirrus microphysical contrasts may be driven by differences in ice supersaturations or aerosols.
Key Points
About 50% of cirrus occurrences at ARM SGP is explained by three synoptic conditionsCirrus microphysics exhibit striking differences among synoptic regimesVertical velocity is a poor predictor of cirrus microphysical variability
KORUS-AQ was an international cooperative air quality field study in South Korea that measured local and remote sources of air pollution affecting the Korean Peninsula during May–June 2016. Some of ...the largest aerosol mass concentrations were measured during a Chinese haze transport event (24 May). Air quality forecasts using the WRF-Chem model with aerosol optical depth (AOD) data assimilation captured AOD during this pollution episode but overpredicted surface particulate matter concentrations in South Korea, especially PM2.5, often by a factor of 2 or larger. Analysis revealed multiple sources of model deficiency related to the calculation of optical properties from aerosol mass that explain these discrepancies. Using in situ observations of aerosol size and composition as inputs to the optical properties calculations showed that using a low-resolution size bin representation (four bins) underestimates the efficiency with which aerosols scatter and absorb light (mass extinction efficiency). Besides using finer-resolution size bins (8–16 bins), it was also necessary to increase the refractive indices and hygroscopicity of select aerosol species within the range of values reported in the literature to achieve better consistency with measured values of the mass extinction efficiency (6.7 m2 g−1 observed average) and light-scattering enhancement factor (f(RH)) due to aerosol hygroscopic growth (2.2 observed average). Furthermore, an evaluation of the optical properties obtained using modeled aerosol properties revealed the inability of sectional and modal aerosol representations in WRF-Chem to properly reproduce the observed size distribution, with the models displaying a much wider accumulation mode. Other model deficiencies included an underestimate of organic aerosol density (1.0 g cm−3 in the model vs. observed average of 1.5 g cm−3) and an overprediction of the fractional contribution of submicron inorganic aerosols other than sulfate, ammonium, nitrate, chloride, and sodium corresponding to mostly dust (17 %–28 % modeled vs. 12 % estimated from observations). These results illustrate the complexity of achieving an accurate model representation of optical properties and provide potential solutions that are relevant to multiple disciplines and applications such as air quality forecasts, health impact assessments, climate projections, solar power forecasts, and aerosol data assimilation.
Biomass burning particulate matter (BBPM) affects regional air quality and global climate, with impacts expected to continue to grow over the coming years. We show that studies of North American ...fires have a systematic altitude dependence in measured BBPM normalized excess mixing ratio (NEMR; ΔPM/ΔCO), with airborne and high-altitude studies showing a factor of 2 higher NEMR than ground-based measurements. We report direct airborne measurements of BBPM volatility that partially explain the difference in the BBPM NEMR observed across platforms. We find that when heated to 40–45 °C in an airborne thermal denuder, 19% of lofted smoke PM1 evaporates. Thermal denuder measurements are consistent with evaporation observed when a single smoke plume was sampled across a range of temperatures as the plume descended from 4 to 2 km altitude. We also demonstrate that chemical aging of smoke and differences in PM emission factors can not fully explain the platform-dependent differences. When the measured PM volatility is applied to output from the High Resolution Rapid Refresh Smoke regional model, we predict a lower PM NEMR at the surface compared to the lofted smoke measured by aircraft. These results emphasize the significant role that gas-particle partitioning plays in determining the air quality impacts of wildfire smoke.
Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using ...burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements. Here, we present a novel method to estimate fire plume-integrated total carbon and speciated emission rates using a unique combination of lidar remote sensing aerosol extinction profiles and in situ measured carbon constituents. We show strong agreement between these aircraft-derived emission rates of total carbon and a detailed burned area-based inventory that distributes carbon emissions in time using Geostationary Operational Environmental Satellite FRP observations (Fuel2Fire inventory, slope = 1.33 ± 0.04, r 2 = 0.93, and RMSE = 0.27). Other more commonly used inventories strongly correlate with aircraft-derived emissions but have wide-ranging over- and under-predictions. A strong correlation is found between carbon monoxide emissions estimated in situ with those derived from the TROPOspheric Monitoring Instrument (TROPOMI) for five wildfires with coincident sampling windows (slope = 0.99 ± 0.18; bias = 28.5%). Smoke emission coefficients (g MJ–1) enable direct estimations of primary gas and aerosol emissions from satellite FRP observations, and we derive these values for many compounds emitted by temperate forest fuels, including several previously unreported species.
OH and HO2 were measured with the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) as part of a large measurement suite from the NASA DC‐8 aircraft during the Intercontinental Chemical Transport ...Experiment‐A (INTEX‐A). This mission, which was conducted mainly over North America and the western Atlantic Ocean in summer 2004, was an excellent test of atmospheric oxidation chemistry. The HOx results from INTEX‐A are compared to those from previous campaigns and to results for other related measurements from INTEX‐A. Throughout the troposphere, observed OH was generally 0.95 of modeled OH; below 8 km, observed HO2 was generally 1.20 of modeled HO2. This observed‐to‐modeled comparison is similar to that for TRACE‐P, another midlatitude study for which the median observed‐to‐modeled ratio was 1.08 for OH and 1.34 for HO2, and to that for PEM‐TB, a tropical study for which the median observed‐to‐modeled ratio was 1.17 for OH and 0.97 for HO2. HO2 behavior above 8 km was markedly different. The observed‐to‐modeled HO2 ratio increased from ∼1.2 at 8 km to ∼3 at 11 km with the observed‐to‐modeled ratio correlating with NO. Above 8 km, the observed‐to‐modeled HO2 and observed NO were both considerably greater than observations from previous campaigns. In addition, the observed‐to‐modeled HO2/OH, which is sensitive to cycling reactions between OH and HO2, increased from ∼1.5 at 8 km to almost 3.5 at 11 km. These discrepancies suggest a large unknown HOx source and additional reactants that cycle HOx from OH to HO2. In the continental planetary boundary layer, the observed‐to‐modeled OH ratio increased from 1 when isoprene was less than 0.1 ppbv to over 4 when isoprene was greater than 2 ppbv, suggesting that forests throughout the United States are emitting unknown HOx sources. Progress in resolving these discrepancies requires a focused research activity devoted to further examination of possible unknown OH sinks and HOx sources.
Fires emit sufficient sulfur to affect local and regional air quality and climate. This study analyzes SO2 emission factors and variability in smoke plumes from US wildfires and agricultural fires, ...as well as their relationship to sulfate and hydroxymethanesulfonate (HMS) formation. Observed SO2 emission factors for various fuel types show good agreement with the latest reviews of biomass burning emission factors, producing an emission factor range of 0.47–1.2 g SO2 kg^(−1) C. These emission factors vary with geographic location in a way that suggests that deposition of coal burning emissions and application of sulfur-containing fertilizers likely play a role in the larger observed values, which are primarily associated with agricultural burning. A 0-D box model generally reproduces the observed trends of SO2 and total sulfate (inorganic + organic) in aging wildfire plumes. In many cases, modeled HMS is consistent with the observed organosulfur concentrations. However, a comparison of observed organosulfur and modeled HMS suggests that multiple organosulfur compounds are likely responsible for the observations but that the chemistry of these compounds yields similar production and loss rates as that of HMS, resulting in good agreement with the modeled results. We provide suggestions for constraining the organosulfur compounds observed during these flights, and we show that the chemistry of HMS can allow organosulfur to act as an S(IV) reservoir under conditions of pH > 6 and liquid water content >10^(−7) g sm^(−3). This can facilitate long-range transport of sulfur emissions, resulting in increased SO2 and eventually sulfate in transported smoke.
The Korea – United States Air Quality Study (May – June 2016) deployed instrumented aircraft and ground-based measurements to elucidate causes of poor air quality related to high ozone and aerosol ...concentrations in South Korea. This work synthesizes data pertaining to aerosols (specifically, particulate matter with aerodynamic diameters <2.5 micrometers, PM2.5) and conditions leading to violations of South Korean air quality standards (24-hr mean PM2.5 < 35 µg m–3). PM2.5 variability from AirKorea monitors across South Korea is evaluated. Detailed data from the Seoul vicinity are used to interpret factors that contribute to elevated PM2.5. The interplay between meteorology and surface aerosols, contrasting synoptic-scale behavior vs. local influences, is presented. Transboundary transport from upwind sources, vertical mixing and containment of aerosols, and local production of secondary aerosols are discussed. Two meteorological periods are probed for drivers of elevated PM2.5. Clear, dry conditions, with limited transport (Stagnant period), promoted photochemical production of secondary organic aerosol from locally emitted precursors. Cloudy humid conditions fostered rapid heterogeneous secondary inorganic aerosol production from local and transported emissions (Transport/Haze period), likely driven by a positive feedback mechanism where water uptake by aerosols increased gas-to-particle partitioning that increased water uptake. Further, clouds reduced solar insolation, suppressing mixing, exacerbating PM2.5 accumulation in a shallow boundary layer. The combination of factors contributing to enhanced PM2.5 is challenging to model, complicating quantification of contributions to PM2.5 from local versus upwind precursors and production. We recommend co-locating additional continuous measurements at a few AirKorea sites across South Korea to help resolve this and other outstanding questions: carbon monoxide/carbon dioxide (transboundary transport tracer), boundary layer height (surface PM2.5 mixing depth), and aerosol composition with aerosol liquid water (meteorologically-dependent secondary production). These data would aid future research to refine emissions targets to further improve South Korean PM2.5 air quality.
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