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

Relationship between continuous aerosol measurements and firn core chemistry over a 10-year period at the South Pole

Before ice core chemistry can be used to estimate past atmospheric chemistry it is necessary to establish an unambiguous link between concentrations of chemical species in the air and snow. For the first time a continuous long-term record of aerosol properties (aerosol light scattering coefficient, σsp, and Ångström exponent, å) at the South Pole are compared with the chemical record from a high resolution firn core (∼10 samples per year) covering the period from 1981 to 1991. Seasonal signals in å, associated with winter minima due to coarse mode seasalt and summer maxima due to accumulation mode sulfate aerosol, are reflected in the firn core SO42−/Na+ concentration ratio. Summertime ratios of σsp and aerosol optical depth, τ to corresponding firn core sulfur concentrations are determined and the ‘calibrations’ are applied to sulfur concentrations in snowpits from a previous study. Results show that σsp estimates from snowpit sulfur concentrations are in agreement with atmospheric measurements while τ estimates are significantly different, which is likely due to the lack of understanding of the processes that mix surface air with air aloft

A simple model to estimate atmospheric concentrations of aerosol chemical species based on snow core chemistry at Summit, Greenland

A simple model is presented to estimate atmospheric concentrations of chemical species that exist primarily as aerosols based on snow core/ice core chemistry at Summit, Greenland. The model considers the processes of snow, fog, and dry deposition. The deposition parameters for each of the processes are estimated for SO42− and Ca2+ and are based on experiments conducted during the 1993 and 1994 summer field seasons. The seasonal mean atmospheric concentrations are estimated based on the deposition parameters and snow cores obtained during the field seasons. The ratios of the estimated seasonal mean airborne concentration divided by the measured mean concentration ( ) for SO42− over the 1993 and 1994 field seasons are 0.85 and 0.95, respectively. The ratios for Ca2+ are 0.45 and 0.90 for the 1993 and 1994 field seasons. The uncertainties in the estimated atmospheric concentrations range from 30% to 40% and are due to variability in the input parameters. The model estimates the seasonal mean atmospheric SO42− and Ca2+ concentrations to within 15% and 55%, respectively. Although the model is not directly applied to ice cores, the application of the model to ice core chemical signals is briefly discussed

Modeling of the processing and removal of trace gas and aerosol species by Arctic radiation fogs and comparison with measurements

A Lagrangian radiation fog model is applied to a fog event at Summit, Greenland. The model simulates the formation and dissipation of fog. Included in the model are detailed gas and aqueous phase chemistry, and deposition of chemical species with fog droplets. Model predictions of the gas phase concentrations of H2O2, HCOOH, SO2, and HNO3 as well as the fog fluxes of S(VI), N(V), H2O2, and water are compared with measurements. The predicted fluxes of S(VI), N(V), H2O2, and fog water generally agree with measured values. Model results show that heterogeneous SO2 oxidation contributes to approximately 40% of the flux of S(VI) for the modeled fog event, with the other 60% coming from preexisting sulfate aerosol. The deposition of N(V) with fog includes contributions from HNO3 and NO2 initially present in the air mass. HNO3 directly partitions into the aqueous phase to create N(V), and NO2 forms N(V) through reaction with OH and the nighttime chemistry set of reactions which involves N2O5 and water vapor. PAN contributes to N(V) by gas phase decomposition to NO2, and also by direct aqueous phase decomposition. The quantitative contributions from each path are uncertain since direct measurements of PAN and NO2 are not available for the fog event. The relative contributions are discussed based on realistic ranges of atmospheric concentrations. Model results suggest that in addition to the aqueous phase partitioning of the initial HNO3 present in the air mass, the gas phase decomposition of PAN and subsequent reactions of NO2 with OH as well as nighttime nitrate chemistry may play significant roles in depositing N(V) with fog. If a quasi-liquid layer exists on snow crystals, it is possible that the reactions taking place in fog droplets also occur to some extent in clouds as well as at the snow surface

The contributions of snow, fog, and dry deposition to the summer flux of anions and cations at Summit, Greenland

Experiments were performed during the period May–July of 1993 at Summit, Greenland. Aerosol mass size distributions as well as daily average concentrations of several anionic and cationic species were measured. Dry deposition velocities for SO42− were estimated using surrogate surfaces (symmetric airfoils) as well as impactor data. Real-time concentrations of particles greater than 0.5 μm and greater than 0.01 μm were measured. Snow and fog samples from nearly all of the events occurring during the field season were collected. Filter sampler results indicate that SO42− is the dominant aerosol anion species, with Na+, NH4+, and Ca2+being the dominant cations. Impactor results indicate that MSA and SO42− have similar mass size distributions. Furthermore, MSA and SO42− have mass in both the accumulation and coarse modes. A limited number of samples for NH4+ indicate that it exists in the accumulation mode. Na, K, Mg, and Ca exist primarily in the coarse mode. Dry deposition velocities estimated from impactor samples and a theory for dry deposition to snow range from 0.017 cm/s +/− 0.011 cm/s for NH4+ to 0.110 cm/s +/− 0.021 cm/s for Ca. SO42− dry deposition velocity estimates using airfoils are in the range 0.023 cm/s to 0.062 cm/s, as much as 60% greater than values calculated using the airborne size distribution data. The rough agreement between the airfoil and impactor-estimated dry deposition velocities suggests that the airfoils may be used to approximate the dry deposition to the snow surface. Laser particle counter (LPC) results show that particles \u3e 0.5 μm in diameter efficiently serve as nuclei to form fog droplets. Condensation nuclei (CN) measurements indicate that particles \u3c 0.5 μm are not as greatly affected by fog. Furthermore, impactor measurements suggest that from 50% to 80% of the aerosol SO42−serves as nuclei for fog droplets. Snow deposition is the dominant mechanism transporting chemicals to the ice sheet. For NO3−, a species that apparently exists primarily in the gas phase as HNO3(g), 93% of the seasonal inventory (mass of a deposited chemical species per unit area during the season) is due to snow deposition, which suggests efficient scavenging of HNO3(g) by snowflakes. The contribution of snow deposition to the seasonal inventories of aerosols ranges from 45% for MSA to 76% for NH4+. The contribution of fog to the seasonal inventories ranges from 13% for Na+ and Ca2+ to 26% and 32% for SO42− and MSA. The dry deposition contribution to the seasonal inventories of the aerosol species is as low as 5% for NH4+ and as high as 23% for MSA. The seasonal inventory estimations do not take into consideration the spatial variability caused by blowing and drifting snow. Overall, results indicate that snow deposition of chemical species is the dominant flux mechanism during the summer at Summit and that all three deposition processes should be considered when estimating atmospheric concentrations based on ice core chemical signals

Temporal and spatial variability of snow accumulation in central Greenland

Snow accumulation records from central Greenland are explored to improve the understanding of the accumulation signal in Greenland ice core records. Results from a “forest” of 100 bamboo poles and automated accumulation monitors in the vicinity of Summit as well as shallow cores collected in the Summit and Crete areas are presented. Based on these accumulation data, a regression has been calculated to quantify the signal-to-noise variance ratio of ice core accumulation signals on a variety of temporal (1 week to 2 years) and spatial (20 m to 200 km) scales. Results are consistent with data obtained from year-round automated accumulation measurements deployed at Summit which suggest that it is impossible to obtain regional snow accumulation data with seasonal resolution using four accumulation monitors positioned over a length scale of ∼30 km. Given this understanding of the temporal and spatial dependence of noise in the ice core accumulation signal, the accumulation records from 17 shallow cores are revisited. Each core spans the time period from 1964 to 1983. By combining the accumulation records, the regional snow accumulation record has been obtained for this period. The results show that 9 of the 20 years can be identified as having an accumulation different from the 20 year mean with 99% confidence. The signal-to-noise variance ratio for the average accumulation signal sampled at annual intervals is 5.8±0.5. The averaged accumulation time series may be useful to climate modelers attempting to validate their models with accurate regional hydrologic data sets

Relationship between Continuous Aerosol Measurements and Firn Core Chemistry over a 10‐year Period at the South Pole

Before ice core chemistry can be used to estimate past atmospheric chemistry it is necessary to establish an unambiguous link between concentrations of chemical species in the air and snow. For the first time a continuous long‐term record of aerosol properties (aerosol light scattering coefficient, σsp , and Ångström exponent, å) at the South Pole are compared with the chemical record from a high resolution firn core (∼10 samples per year) covering the period from 1981 to 1991. Seasonal signals in å, associated with winter minima due to coarse mode seasalt and summer maxima due to accumulation mode sulfate aerosol, are reflected in the firn core SO42−/Na+ concentration ratio. Summertime ratios of σsp and aerosol optical depth, τ to corresponding firn core sulfur concentrations are determined and the ‘calibrations’ are applied to sulfur concentrations in snowpits from a previous study. Results show that σsp estimates from snowpit sulfur concentrations are in agreement with atmospheric measurements while τ estimates are significantly different, which is likely due to the lack of understanding of the processes that mix surface air with air aloft

Disk Imaging Survey of Chemistry with SMA: II. Southern Sky Protoplanetary Disk Data and Full Sample Statistics

This is the second in a series of papers based on data from DISCS, a Submillimeter Array observing program aimed at spatially and spectrally resolving the chemical composition of 12 protoplanetary disks. We present data on six Southern sky sources - IM Lup, SAO 206462 (HD 135344b), HD 142527, AS 209, AS 205 and V4046 Sgr - which complement the six sources in the Taurus star forming region reported previously. CO 2-1 and HCO+ 3-2 emission are detected and resolved in all disks and show velocity patterns consistent with Keplerian rotation. Where detected, the emission from DCO+ 3-2, N2H+ 3-2, H2CO 3-2 and 4-3,HCN 3-2 and CN 2-1 are also generally spatially resolved. The detection rates are highest toward the M and K stars, while the F star SAO 206462 has only weak CN and HCN emission, and H2CO alone is detected toward HD 142527. These findings together with the statistics from the previous Taurus disks, support the hypothesis that high detection rates of many small molecules depend on the presence of a cold and protected disk midplane, which is less common around F and A stars compared to M and K stars. Disk-averaged variations in the proposed radiation tracer CN/HCN are found to be small, despite two orders of magnitude range of spectral types and accretion rates. In contrast, the resolved images suggest that the CN/HCN emission ratio varies with disk radius in at least two of the systems. There are no clear observational differences in the disk chemistry between the classical/full T Tauri disks and transitional disks. Furthermore, the observed line emission does not depend on measured accretion luminosities or the number of infrared lines detected, which suggests that the chemistry outside of 100 AU is not coupled to the physical processes that drive the chemistry in the innermost few AU.Comment: accepted for publication in ApJ, 41 pages including 7 figure

Local anthropogenic impact on particulate elemental carbon concentrations at Summit, Greenland

Summit, Greenland is a remote Arctic research station allowing for field measurements at the highest point of the Greenland Ice Sheet. Due to the current reliance on diesel generators for electricity at Summit, unavoidable local emissions are a potential contamination threat to the measurement of combustion-related species in the air and snow. The effect of fossil-fuel combustion on particulate elemental carbon (EC) is assessed by a combination of ambient measurements (~1 km from the main camp), a series of snow pits, and Gaussian plume modeling. Ambient measurements indicate that the air directly downwind of the research station generators experiences particulate absorption coefficient (closely related to EC) values that are up to a factor of 200 higher than the summer 2006 non-camp-impacted ambient average. Local anthropogenic influence on snow EC content is also evident. The average EC concentration in 1-m snow pits in the "clean air" sector of Summit Camp are a factor of 1.8–2.4 higher than in snow pits located 10 km and 20 km to the north ("downwind") and south ("upwind") of the research site. Gaussian plume modeling performed using meteorological data from years 2003–2006 suggests a strong angular dependence of anthropogenic impact, with highest risk to the northwest of Summit Camp and lowest to the southeast. Along a transect to the southeast (5 degree angle bin), the modeled frequency of significant camp contribution to atmospheric EC (i.e. camp-produced EC>summer 2006 average EC) at a distance of 0.5 km, 10 km, and 20 km is 1%, 0.2%, and 0.05%, respectively. According to both the snow pit and model results, a distance exceeding 10 km towards the southeast is expected to minimize risk of contamination. These results also suggest that other remote Arctic monitoring stations powered by local fuel combustion may need to account for local air and snow contamination in field sampling design and data interpretation

Evaluating local anthropogenic impact on remote Arctic monitoring stations: a case study at Summit, Greenland

International audienceSummit, Greenland is a remote Arctic research station allowing for field measurements at the highest point of the Greenland Ice Sheet. Due to the current reliance on diesel generators for electricity at Summit, unavoidable local emissions are a potential contamination threat to the measurement of combustion-related species in the air and snow. The effect of fossil-fuel combustion on particulate elemental carbon (EC) is assessed by a combination of ambient measurements (~1 km from the main camp), a series of snow pits (up to 20 km from Summit Camp), and Gaussian plume modeling. Ambient measurements indicate that the air directly downwind of the research station generators experiences particulate absorption coefficient (closely related to EC) values that are up to a factor of 200 higher than the summer 2006 non-camp-impacted ambient average. Local anthropogenic influence on snow EC content is also evident. The average EC concentration in 1-m snow pits in the "clean air" sector of Summit Camp are a factor of 1.8?2.4 higher than in snow pits located 10 km and 20 km to the north ("downwind") and south ("upwind") of the research site. Gaussian plume modeling performed using meteorological data from years 2003?2006 suggests a strong angular dependence of anthropogenic impact, with highest risk to the northwest of Summit Camp and lowest to the southeast. Along a transect to the southeast (5 degree angle bin), the modeled frequency of significant camp contribution to atmospheric EC (i.e. camp-produced EC>2006 summer average EC) at a distance of 0.5 km, 10 km, and 20 km is 1%, 0.2%, and 0.05%, respectively. According to both the snow pit and model results, a distance exceeding 10 km towards the southeast is expected to minimize risk of contamination. These results also suggest that other remote Arctic monitoring stations powered by local fuel combustion may need to account for local air and snow contamination in field sampling design and data interpretation