Relationships between surface and column aerosol radiative properties and air mass transport at a rural New England site

Chemical, physical, and radiative properties of surface and vertical column aerosols were measured at a rural site in southern New Hampshire from July 2000 to September 2001. The primary objective was to determine how intensive and extensive aerosol properties vary in air masses originating in different upwind regions. The data set also allows for an investigation of some of the relationships between surface and column aerosol properties at the site, and provides an estimate of direct radiative forcing by aerosols during the study period. Extensive properties (e.g., optical depth and chemical concentration) were at maximum values during times of south-southwest (S-SW) transport, while minimum values were seen during north-northeast (N-NE) transport. Certain intensive properties such as fine particle mass scattering efficiency did not vary significantly between times of transport from different source regions. Mean optical depth (wavelength = 500 nm) was 0.24 during S-SW transport, compared to 0.10 during N-NE transport. The study period average scattering efficiency for (NH4)2SO4 was 6.54 ± 0.26 m2 g−1 (± standard error) and 3.36 ± 0.49 m2 g−1 for organic carbon, while the absorption efficiency of elemental carbon was 12.85 ± 0.80 m2 g−1. Top of the atmosphere aerosol direct radiative forcing was −0.35 ± 0.83 Wm−2 (±1 standard deviation) in winter 2000–2001 and −9.06 ± 3.77 Wm−2 in summer 2001, differences that can be primarily attributed to seasonal changes in surface reflectance (high in winter, low in summer) and the relatively low values of single scatter albedo observed in winter. The annual average direct radiative forcing was −5.14 ± 4.32 Wm−2. We generally observed a moderate correlation between surface and column aerosol light extinction, suggesting that vertical column aerosol radiative properties measured by surface-based radiometers should be supplemented by boundary layer measurements of aerosol chemical, physical, and radiative properties to help understand the mechanisms contributing to global aerosol variability

Air-snow exchange investigations at Summit, Greenland: An overview

The Greenland Ice Sheet Project 2 (GISP2) and Greenland Ice Core Project (GRIP) deep drilling programs at Summit, Greenland included support (both logistical and scientific) of extensive investigation of atmospheric transport and air-snow exchange processes of gases and particles relevant to the interpretation of the ice-core records. Much of the sampling for the air-snow exchange investigations was conducted at a unique solar-powered camp 30 km southwest of the GISP2 drill camp (even further from the GRIP camp) and was characterized by a high degree of international collaboration and cooperation. The wide range of expertise and analytical capabilities of the 20-plus investigators participating in these studies has provided important insight into the meteorological, physical, and chemical processes which interact to determine the composition of snow and firn at Summit. Evolving understanding of this system will allow improved reconstruction of the composition of the atmosphere over Greenland in the past from the detailed Summit ice-core records. This paper provides an overview of air-snow exchange investigations at Summit, including their development through the course of the drilling programs (1989–1993), significant findings related to both air-snow exchange issues and the present state of the Arctic free troposphere, as well as the major outstanding questions which are being addressed in ongoing experiments at Summit

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

Simultaneous measurements of particulate and gas-phase water-soluble organic carbon concentrations at remote and urban-influenced locations

The sources, sinks, and overall importance of watersoluble organic carbon (WSOC) in the atmosphere are not well understood. Although the primary historical focus has been on particulate WSOC (WSOCP), here we also present results obtained using a newly developed technique that additionally measures gas-phase water-soluble organic carbon (WSOCG). These first-of-their-kind measurements show that WSOCG can often be more than ten times larger than WSOCP at both urban and remote locations. The average fraction of WSOC residing in the gas phase (fg = WSOCG/(WSOCG + WSOCP)) at five various field sites ranged from 0.64 to 0.93, implying significant differences in WSOC phase partitioning between locations. At Houston, TX, and Summit, Greenland, a repeatable diurnal pattern was observed, with minimum values for fg occurring at night. These trends likely are due, at least in part, to temperature and/or relative humidity related gas-to-particle partitioning. These coincident measurements of WSOC in both the gas and particle phases indicate that a relatively large reservoir of water-soluble organic mass is not taken into account by measurements focused only on WSOCP. In addition, a significant amount of WSOCG is available to form WSOCP or enter cloud droplets depending on the chemical and physical properties of the droplets and/or aerosols present. Citation: Anderson, C., J. E. Dibb, R. J. Griffin, and M. H. Bergin (2008), Simultaneous measurements of particulate and gas-phase water-soluble organic carbon concentrations at remote and urban-influenced locations, Geophys. Res. Lett., 35, L13706, doi:10.1029/2008GL033966

Sulfate and MSA in the air and snow on the Greenland Ice Sheet

Sulfate and methanesulfonic acid (MSA) concentrations in aerosol, surface snow, and snowpit samples have been measured at two sites on the Greenland Ice Sheet. Seasonal variations of the concentrations observed for these chemical species in the atmosphere are reproduced in the surface snow and preserved in the snowpit sequence. The amplitude of the variations over a year are smaller in the snow than in the air, but the ratios of the concentrations are comparable. The seasonal variations for sulfate are different at the altitude of the Ice Sheet compared to those observed at sea level, with low concentrations in winter and short episodes of elevated concentrations in spring. In contrast, the variations in concentrations of MSA are similar to those measured at sea level, with a first sequence of elevated concentrations in spring and another one during summer, and a winter low resulting from low biogenic production. The ratio MSA/sulfate clearly indicates the influence of high-latitude sources for the summer maximum of MSA, but the large impact of anthropogenic sulfate precludes any conclusion for the spring maximum. The seasonal pattern observed for these species in a snowpit sampled according to stratigraphy indicates a deficit in the accumulation of winter snow at the summit of the Greenland Ice Sheet, in agreement with some direct observations. A deeper snowpit covering the years 1985–1992 indicates the consistency of the seasonal pattern for MSA over the years, which may be linked to transport and deposition processes

Bromide and other ions in the snow, firn air, and atmospheric boundary layer at Summit during GSHOX

Measurements of gas phase soluble bromide in the boundary layer and in firn air, and Br− in aerosol and snow, were made at Summit, Greenland (72.5° N, 38.4° W, 3200 m a.s.l.) as part of a larger investigation into the influence of Br chemistry on HOx cycling. The soluble bromide measurements confirm that photochemical activation of Br− in the snow causes release of active Br to the overlying air despite trace concentrations of Br− in the snow (means 15 and 8 nmol Br− kg−1 of snow in 2007 and 2008, respectively). Mixing ratios of soluble bromide above the snow were also found to be very small (mean \u3c1 ppt both years, with maxima of 3 and 4 ppt in 2007 and 2008, respectively), but these levels clearly oxidize and deposit long-lived gaseous elemental mercury and may perturb HOx partitioning. Concentrations of Br− in surface snow tended to increase/decrease in parallel with the specific activities of the aerosol-associated radionuclides 7Be and 210Pb. Earlier work has shown that ventilation of the boundary layer causes simultaneous increases in 7Be and 210Pb at Summit, suggesting there is a pool of Br in the free troposphere above Summit in summer time. Speciation and the source of this free tropospheric Br− are not well constrained, but we suggest it may be linked to extensive regions of active Br chemistry in the Arctic basin which are known to cause ozone and mercury depletion events shortly after polar sunrise. If this hypothesis is correct, it implies persistence of the free troposphere Br− for several months after peak Br activation in March/April. Alternatively, there may be a ubiquitous pool of Br− in the free troposphere, sustained by currently unknown sources and processes

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

An estimate of the stratospheric contribution to springtime tropospheric ozone maxima using TOPSE measurements and beryllium-7 simulations

Measurements of tropospheric ozone (O3) between 30°N and 70°N show springtime maxima at remote locations. The contribution of seasonal changes in stratosphere–troposphere exchange (STE) to these maxima was investigated using measurements from the Tropospheric Ozone Production about the Spring Equinox Experiment (TOPSE) campaign and the beryllium-7 (7Be) distribution from a calculation driven by fields from the Goddard Earth Observing System Data Assimilation System (GEOS DAS). Comparison with TOPSE measurements revealed that upper tropospheric model-calculated 7Be mixing ratios were reasonable (a change from previous calculations) but that lower tropospheric mixing ratios were too low most likely due to an overestimation of scavenging. Temporal fluctuations were well captured although their amplitudes were often underestimated. Analysis of O3measurements indicated that O3 mixing ratios increased by 5–10% month−1 for θ \u3c 300 K (the underworld) and by 10–15% month−1 for θ \u3e 300 K (the tropospheric middleworld). 7Be mixing ratios decreased with time for θ \u3c 290 K and increased with time for θ \u3e 300 K. Model-calculated middleworld increases of 7Be were a factor of 2 less than measured increases. 7Be with a stratospheric source (strat-7Be) increased by 4.6–8.8% month−1 along TOPSE flight paths within the tropospheric middleworld. Increases in strat-7Be were not seen along TOPSE flight paths in the underworld. Assuming changes in tropospheric O3 with a stratospheric source are the same as changes in strat-7Be and that 50% of O3 in the region of interest is produced in the stratosphere, changes in STE explain 20–60% of O3 increases in the tropospheric middleworld and less than 33% of O3 increases in the underworld

Observations of HONO by laser-induced fluorescence at the South Pole during ANTCI 2003

Observations of nitrous acid (HONO) by laser-induced fluorescence (LIF) at the South Pole taken during the Antarctic Troposphere Chemistry Investigation (ANTCI), which took place over the time period of Nov. 15, 2003 to Jan. 4, 2004, are presented here. The median observed mixing ratio of HONO 10 m above the snow was 5.8 pptv (mean value 6.3 pptv) with a maximum of 18.2 pptv on Nov 30th, Dec 1st, 3rd, 15th, 17th, 21st, 22nd, 25th, 27th and 28th. The measurement uncertainty is ±35%. The LIF HONO observations are compared to concurrent HONO observations performed by mist chamber/ion chromatography (MC/IC). The HONO levels reported by MC/IC are about 7.2 ± 2.3 times higher than those reported by LIF. Citation: Liao, W., A. T. Case, J. Mastromarino, D. Tan, and J. E. Dibb (2006), Observations of HONO by laser-induced fluorescence at the South Pole during ANTCI 2003, Geophys. Res. Lett., 33, L09810, doi:10.1029/2005GL025470

Relationships between synoptic-scale transport and interannual variability of inorganic cations in surface snow at Summit, Greenland: 1992-1996

To fully utilize the long-term chemical records retrieved from central Greenland ice cores, specific relationships between atmospheric circulation and the variability of chemical species in the records need to be better understood. This research examines associations between the variability of surface snow inorganic cation chemistry at Summit, Greenland (collected during 1992–1996 summer field seasons) and changes in air mass transport pathways and source regions, as well as variations in aerosol source strength. Transport patterns and source regions are determined through 10-day isentropic backward air mass trajectories during a 1 month (late May to late June) common season over the 5 years. Changes in the extent of exposed continental surfaces in source regions are evaluated to estimate aerosol-associated calcium and magnesium ion source strength, while forest fire activity in the circumpolar north is investigated to estimate aerosol ammonium ion source strength. During the 1995 common season, 3 times more calcium and magnesium accumulated in the snowpack than the other study years. Also, an increasing trend of ammonium concentration was noted throughout the 5 years. Anomalous transport pathways and velocities were observed during 1995, which likely contributed to the high levels of calcium and magnesium. Increased forest fire activity in North America was concurrent with increased levels of ammonium and potassium, except for 1996, when ion levels were above average and forest fire activity was below average. Because of the ubiquitous nature of soluble ions, we conclude that it is very difficult to establish a quantitative link between the ion content of snow and firn at Summit and changes in aerosol source regions and source strength