Chemical modeling of the L1498 and L1517B prestellar cores: CO and HCO+ depletion

Prestellar cores exhibit a strong chemical differentiation, which is mainly caused by the freeze-out of molecules onto the grain surfaces. Understanding this chemical structure is important, because molecular lines are often used as probes to constrain the core physical properties. Here we present new observations and analysis of the C18O (1-0) and H13CO+ (1-0) line emission in the L1498 and L1517B prestellar cores, located in the Taurus-Auriga molecular complex. We model these observations with a detailed chemistry network coupled to a radiative transfer code. Our model successfully reproduces the observed C18O (1-0) emission for a chemical age of a few 10^5 years. On the other hand, the observed H13CO+ (1-0) is reproduced only if cosmic-ray desorption by secondary photons is included, and if the grains have grown to a bigger size than average ISM grains in the core interior. This grain growth is consistent with the infrared scattered light ("coreshine") detected in these two objects, and is found to increase the CO abundance in the core interior by about a factor four. According to our model, CO is depleted by about 2-3 orders of magnitude in the core center.Comment: Accepted for publication in A&

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

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

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 summer time series of particulate carbon in the air and snow at Summit, Greenland

Carbonaceous particulate matter is ubiquitous in the lower atmosphere, produced by natural and anthropogenic sources and transported to distant regions, including the pristine and climate-sensitive Greenland Ice Sheet. During the summer of 2006, ambient particulate carbonaceous compounds were characterized on the Greenland Ice Sheet, including the measurement of particulate organic (OC) and elemental (EC) carbon, particulate water-soluble organic carbon (WSOC), particulate absorption coefficient (σap), and particle size-resolved number concentration (PM0.1–1.0). Additionally, parallel ∼50-day time series of water-soluble organic carbon (WSOC), water-insoluble organic carbon (WIOC), and elemental carbon (EC) were quantified at time increments of 4–24 h in the surface snow. Measurement of atmospheric particulate carbon found WSOC (average of 52 ng m−3) to constitute a major fraction of particulate OC (average of 56 ng m−3), suggesting that atmospheric organic compounds reaching the Greenland Ice Sheet in summer are highly oxidized. Atmospheric EC (average of 7 ng m−3) was well-correlated with σap (r = 0.95) and the calculated mass-absorption cross-section (average of 24 m2 g−1) appears to be similar to that measured using identical techniques in an urban environment in the United States. Comparing surface snow to atmospheric particulate matter concentrations, it appears the snow has a much higher OC (WSOC+WIOC) to EC ratio (205:1) than air (10:1), suggesting that snow is additionally influenced by water-soluble gas-phase compounds. Finally, the higher-frequency (every 4–6 h) sampling of snow-phase WSOC revealed significant loss (40–54%) of related organic compounds in surface snow within 8 h of wet deposition

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

Atomic jet from SMM1 (FIRS1) in Serpens uncovers non-coeval binary companion

We report on the detection of an atomic jet associated with the protostellar source SMM1 (FIRS1) in Serpens. The jet is revealed in [FeII] and [NeII] line maps observed with Spitzer/IRS, and further confirmed in HiRes IRAC and MIPS images. It is traced very close to SMM1 and peaks at ~5 arcsec" from the source at a position angle of $\sim 125 degrees. In contrast, molecular hydrogen emission becomes prominent at distances > 5" from the protostar and extends at a position angle of 160 degrees. The morphological differences suggest that the atomic emission arises from a companion source, lying in the foreground of the envelope surrounding the embedded protostar SMM1. In addition the molecular and atomic Spitzer maps disentangle the large scale CO (3-2) emission observed in the region into two distinct bipolar outflows, giving further support to a proto-binary source setup. Analysis at the peaks of the [FeII] jet show that emission arises from warm and dense gas (T ~1000 K, n(electron) 10^5 - 10^6 cm^-3). The mass flux of the jet derived independently for the [FeII] and [NeII] lines is 10^7 M(sun)/yr, pointing to a more evolved Class~I/II protostar as the driving source. All existing evidence converge to the conclusion that SMM1 is a non-coeval proto-binary source.Comment: 10 pages, 7 figures, 1 table. Accepted for publication in Astronomy \& Astrophysic

Particulate and water-soluble carbon measured in recent snow at Summit, Greenland

Water-soluble organic carbon (WSOC), waterinsoluble particulate organic carbon (WIOC), and particulate elemental carbon (EC) were measured simultaneously for the first time on the Greenland Ice Sheet in surface snow and in a 3-meter snow pit. Snow pit concentrations reveal that, on average, WSOC makes up the majority (89%) of carbonaceous species, followed by WIOC (10%) and EC (1%). The enhancement of OC relative to EC (ratio 99:1) in Greenland snow suggests that, along with atmospheric particulate matter, gaseous organics contribute to snow-phase OC. Comparison of summer surface snow concentrations in 2006 with past summer snow pit layers (2002 – 2005) found a significant depletion in WSOC (20 – 82%) and WIOC (46 – 65%) relative to EC for 3 of the 4 years. The apparent substantial loss of WSOC and WIOC in aged snow suggests that post-depositional processes, such as photochemical reactions, need to be considered in linking ice core records of organics to atmospheric concentrations. Citation: Hagler, G. S. W., M. H. Bergin, E. A. Smith, J. E. Dibb, C. Anderson, and E. J. Steig (2007), Particulate and water-soluble carbon measured in recent snow at Summit, Greenland, Geophys. Res. Lett., 34, L16505, doi:10.1029/2007GL030110