Composition and distribution of aerosols over the North Atlantic during the Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX)

We report the mixing ratios of aerosol-associated soluble ions (focusing on SO4= and NO3−) and HNO3 over the North Atlantic during NASA\u27s Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX). The SONEX campaign was designed to quantify the impacts of jet emissions in the North Atlantic Flight Corridor (NAFC) by sampling both directly within and far removed from the organized track system. Beryllium-7 activities were also measured to assess the magnitude of stratospheric influence in the SONEX study region. Mixing ratios of aerosol-associated SO4= and NO3− above 8 km during SONEX were lower than recent measurements over the central United States during the Subsonic Aircraft Contrail and Cloud Effects Special Study (SUCCESS) and the same as those over the remote South Pacific during the Pacific Exploratory Mission-Tropics (PEM-Tropics), suggesting that aircraft emissions cannot yet be a major source of these ions. Furthermore, mean SO4= mixing ratios at high altitudes were 65% higher in regions away from the NAFC than they were directly in the track system just a few hours after peak traffic. Nitric acid mixing ratios at the highest DC-8 sampling altitudes were elevated during SONEX compared to PEM-Tropics, but there was no clear signal of enhancement by jet exhaust. Strong correlations with 7Be indicate that a large fraction of HNO3and aerosol-associated SO4= measured at high altitudes during SONEX were derived from a stratospheric source

Tropospheric sulfate distribution during SUCCESS: Contributions from jet exhaust and surface sources

The distribution of SO4= aerosol over the central US during SUCCESS indicates that surface sources of SO4= and SO2 in the western US caused SO4= enhancements up to 10 km altitude. The mean (median) SO4= mixing ratio in the mid- and upper-troposphere increased from 24 (16) pptv over the Pacific ocean to 58 (29) pptv over the central plains. Above 10 km the SO4=mixing ratio was essentially the same in both regions, and also when the geographic classifications were further partitioned into upper tropospheric and lower stratospheric categories (mean near 40 pptv). No obvious enhancements of SO4= could be detected in jet exhaust plumes, but this may reflect the difficulty of keeping a large airborne sampling platform within a turbulent wake for time periods longer than a few seconds. Expected SO4=enhancements (based on observed CO2 enhancements and emission factors for these two species) were generally much smaller than the variability of ambient SO4= mixing ratios, so our null result does not mean that aircraft do not emit H2SO4

Influence of vertical transport on free tropospheric aerosols over the central USA in springtime

Measurements of the atmospheric aerosol chemical composition during the Subsonic Aircraft: Contrail and Cloud Effects Special Study (SUCCESS) indicate substantial vertical transport of boundary layer aerosol to the free troposphere over the south-central United States during springtime. Mixing ratios of water-soluble aerosol Ca 2+ at 6 - 12 km altitude exhibited a median mixing ratio of 20 pptv, with 15% of the measurements \u3e 100 pptv and a maximum of ! 235 pptv. In air parcels with enhanced Ca 2+, the ratios K+/Ca 2+, Mg2+/Ca 2+, and Na+/Ca 2+ in the bulk aerosol were distinctly characteristic of those in limestone and/or cement. Significantly enhanced mixing ratios of aerosol SO42-, NO3-, and NH4 + were also concomitant with the elevated Ca 2+, suggesting transport of both crustal and anthropogenic aerosols to the upper troposphere. The mass concentration of water-soluble aerosol material was in the range 0.1 - 6 pg m -3 STP, and estimated crustal dust levels were 7 - 160 pg m \u273 ST

Beryllium 7 and Lead 210 in the western hemisphere Arctic atmosphere: Observations from three recent aircraft-based sampling programs

Concentrations of the natural radionuclides 7Be and 210Pb were determined in aerosol samples collected in the western hemisphere Arctic during the recent NOAA Arctic Gas and Aerosol Sampling Program (AGASP 3) and NASA Global Tropospheric Experiment/Arctic Boundary Layer Expeditions (GTE/ABLE 3A and ABLE 3B) missions. Beryllium 7 showed a free tropospheric concentration maximum between 4 and 5 km in the summer of 1990. Previous 7Be data obtained in the late 1950s and early 1960s also indicated a similar vertical distribution of 7Be near 70°N. Injection of stratospheric air through tropopause folds associated with the Arctic jet near 70°N appears to explain the presence of a layer of air near 4–5 km in the high Arctic free troposphere with elevated 7Be concentrations. The vertical distribution of 210Pb showed a distinct difference between the high-Arctic and sub-Arctic in the summer of 1988. At latitudes greater than 65°N, 210Pb concentrations at 3–6 km were elevated compared to those below 1 km. The reverse of this trend was observed near 60°N. These same vertical distributions were also apparent in aerosol SO42−, determined in separate aerosol samples collected on the same flights (Talbot et al., this issue). The results for 210Pb suggest that some of the difference between the summer troposphere in the high- and sub-Arctic is also due to enhanced stratosphere-troposphere exchange in the vicinity of the Arctic jet. These observations, and other findings from ABLE 3A presented in this issue, suggest that for some species the stratosphere may be a principal source influencing their distribution in the Arctic summer troposphere. For example, intrusions of stratospheric air constitute the dominant source term for tropospheric budgets of 7Be and ozone, and may be important in the 210Pb, SO42−, and NOybudgets. Further investigation, including determination of detailed 7Be and 210Pb distributions, is needed to quantify the stratospheric impact on the chemistry of the Arctic troposphere during the summer

Soluble acidic species in air and snow at Summit, Greenland

Simultaneous measurements of the concentrations of soluble acidic species in the gas, aerosol and snow phases at Summit, Greenland were made during summer 1993. Mean concentrations of gas phase HCOOH, CH3COOH, and HNO3 (49±28, 32±17 and 0.9±0.6 nmol m−3 STP, respectively) exceeded the concentrations of aerosol-associated HCOO−, CH3COO−, and NO3−by 1–3 orders of magnitude. On average, SO2 concentrations (0.9±0.6 nmol m−3 STP) were approximately 1/3 those of aerosol SO4=, but this ratio varied widely due largely to changes in the concentration of aerosol SO4=. Concentrations of aerosol SO4= plus SO2 consistently exceeded the sum of aerosol NO3− plus HNO3, yet NO3− was 3–20 times as abundant as SO4=in surface snow. Gas phase concentrations of HCOOH and CH3COOH at Summit were unexpectedly as large as those previously reported for several high latitude continental sites. However, carboxylate concentrations in snow were lower than those of SO4=. Our observation of post-depositional loss of these carboxylic acids within hours after a snowfall must partially explain the low concentrations found in snow. The relative abundance of soluble acids in summer snow at Summit was opposite of that in the overlying atmosphere. Our results highlight the need for improved understanding of the processes controlling transfer of soluble atmospheric species between air and snow

Be-10/Be-7 tracer of atmospheric transport and stratosphere-troposphere exchange

The 10Be/7Be ratio is a sensitive tracer of atmospheric transport and stratosphere-troposphere exchange (STE). Data from five NASA aircraft field missions (PEM: West A and B, Tropics A; SONEX; and SUCCESS) have been assembled to produce the largest data set of 10Be,7Be, and their ratio collected to date (\u3e300 samples). Ratios near 0.60 are indicative of tropospheric air with little stratospheric influence, while higher ratios are found in stratospheric air. Samples from the lower stratosphere were all collected within 2.5 km of the tropopause and had ratios \u3e1.27. Of these lower stratosphere samples only 16% had ratios in excess of 3.0, suggesting that higher ratio air resides away from the tropopause. Seasonality observed in the10Be/7Be ratios results from the downwelling of air with elevated ratios from higher in the stratosphere in the spring and summer (midlatitudes) and from the decay of 7Be during descent in the winter polar vortex (high latitudes). Our results illustrate the complexity of STE and some of the mechanisms through which it occurs, including tropopause folding, mixing associated with subtropical jets, and the effect of synoptic systems such as hurricanes and northeasters. The10Be/7Be ratio provides important information beyond that which can be derived from studies that rely on chemical mixing ratios alone

Summertime ozone at Mount Washington: Meteorological controls at the highest peak in the northeast

This study examined the synoptic and regional-scale meteorological controls on summertime O3 at Mount Washington, the highest peak (1910 m) in the northeastern United States. Analysis of air mass transport to Mount Washington was conducted for the summers of 1998–2003 using backward trajectories. Distinct patterns in air mass history were revealed using this approach that helped explain extreme variations in O3 mixing ratios. Most enhanced (≥90th percentile) and depleted (≤10th percentile) O3 events were short-lived and spread out over the summer months. Enhanced O3 events at Mount Washington were generally associated with westerly transport, while depleted events corresponded to northwesterly transport. Periods of O3 greater than 80 ppbv during nighttime periods coincided with westerly (71%) and southwesterly (29%) transport. Periods of elevated O3 commonly occurred during regional warm sector flow or on the western edge of a surface anticyclone. Our analysis also identified a stratospheric contribution to a small percentage (∼5%) of extreme O3 events at the site, but more evidence is required to establish the significance of the contribution to background O3levels in this region

Asian dust storm events of spring 2001 and associated pollutants observed in New England by the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) monitoring network

Between 18 April and 13 May 2001, three statistically extreme dust aerosol events were observed across the entire northeastern United States. High levels of bulk aerosol water-soluble Ca2+ (range = 42–482 pptv) and PM2.5 elemental Ca (range = 19–156 pptv) were observed simultaneously at Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) and Interagency Monitoring of Protected Visual Environments (IMPROVE) stations. On the basis of Ca2+ concentrations, the average bulk dust concentration for all events across all four AIRMAP stations was estimated to be 7.4 μg/m3. There was no evidence of dust outbreaks in North America large enough to explain these events. However, in April 2001, massive dust storms occurred in the Tarim Pendi basin and in the Gobi deserts of southern Mongolia and China. Comparison of elemental ratios of AIRMAP samples to previously reported Asian dust aerosol samples showed that all AIRMAP samples had a chemical composition similar to Asian dust transported over long distances. Within the dust plumes, strong correlations were observed between absorption, scattering, and CO, indicative of an anthropogenic contribution including elemental carbon and SO42− aerosols. Aerosol NO3− was also highly elevated during event days, most likely due to uptake of HNO3 by the dust during transport. A comparison of dust plumes sampled by AIRMAP to those sampled off the Asian coast during the TRACE-P airborne mission and on the U.S. west coast, strongly suggested entrainment of additional pollutants (e.g., CO, aerosol NO3−, and SO42−) as the dust plumes were transported over North America

Airborne sampling of aerosol particles: Comparison between surface sampling at Christmas Island and P-3 sampling during PEM-Tropics B

Bulk aerosol sampling of soluble ionic compounds from the NASA Wallops Island P-3 aircraft and a tower on Christmas Island during PEM-Tropics B provides an opportunity to assess the magnitude of particle losses in the University of New Hampshire airborne bulk aerosol sampling system. We find that most aerosol-associated ions decrease strongly with height above the sea surface, making direct comparisons between mixing ratios at 30 m on the tower and the lowest flight level of the P-3 (150 m) open to interpretation. Theoretical considerations suggest that vertical gradients of sea-salt aerosol particles should show exponential decreases with height. Observed gradients of Na+ and Mg2+, combining the tower observations with P-3 samples collected below 1 km, are well described by exponential decreases (r values of 0.88 and 0.87, respectively), though the curve fit underestimates average mixing ratios at the surface by 25%. Cascade impactor samples collected on the tower show that \u3e99% of the Na+ and Mg2+mass is on supermicron particles, 65% is in the 1–6 micron range, and just 20% resides on particles with diameters larger than 9 microns. These results indicate that our airborne aerosol sampling probes must be passing particles up to at least 6 microns with high efficiency. We also observed that nss SO42− and NH4+, which are dominantly on accumulation mode particles, tended to decrease between 150 and 1000 m, but they were often considerably higher at the lowest P-3 sampling altitudes than at the tower. This finding is presently not well understood

Enhanced secondary organic aerosol formation due to water uptake by fine particles

This study characterizes the partitioning behavior of a significant fraction of the ambient organic aerosol through simultaneous measurements of gas and particle watersoluble organic carbon (WSOC). During the summer in Atlanta, WSOC gas/particle partitioning showed a strong RH dependence that was attributed to particulate liquid water. At elevated RH levels (\u3e70%) a significant increase in WSOC partitioning to the particle phase was observed and followed the predicted water uptake by fine particles. The enhancement in particle-phase partitioning translated to increased median particle WSOC concentrations ranging from 0.3 –0.9 mgCm3 . The results provide a detailed overview of the WSOC partitioning behavior in the summertime in an urban region dominated by biogenic emissions, and indicate that secondary organic aerosol formation involving partitioning to liquid water may be a significant aerosol formation route that is generally not considered. Citation: Hennigan, C. J., M. H. Bergin, J. E. Dibb, and R. J. Weber (2008), Enhanced secondary organic aerosol formation due to water uptake by fine particles, Geophys. Res. Lett., 35, L18801, doi:10.1029/2008GL035046