and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state 39 and carbon number (n C ).

Increasing quantities of atmospheric anthropogenic fixed nitrogen entering the open ocean could account for up to about a third of the ocean's external (nonrecycled) nitrogen supply and up to approximately 3% of the annual new marine biological production, approximately 0.3 petagram of carbon per year. This input could account for the production of up to approximately 1.6 teragrams of nitrous oxide (N2O) per year. Although approximately 10% of the ocean's drawdown of atmospheric anthropogenic carbon dioxide may result from this atmospheric nitrogen fertilization, leading to a decrease in radiative forcing, up to about two-thirds of this amount may be offset by the increase in N2O emissions. The effects of increasing atmospheric nitrogen deposition are expected to continue to grow in the future.

No abstract

[1] Aqueous-phase oxidation (in clouds and aerosols) is a potentially important source of organic aerosol and could explain the atmospheric presence of oxalic acid. Methylglyoxal, a water-soluble product of isoprene, oxidizes further in the aqueous phase to pyruvic acid. Discrepancies in the literature regarding the aqueous-phase oxidation of pyruvic acid create large uncertainties in the incloud yields of secondary organic aerosol (SOA) and oxalic acid. Resolving the fate of aqueous-phase pyruvic acid is critical to understanding SOA formation through cloud processing of water-soluble products of isoprene, other alkenes and aromatics. In this work, aqueous-phase photochemical reactions of pyruvic acid and hydrogen peroxide at pH values typical of clouds were conducted and demonstrated that photochemical oxidation of pyruvic acid yields glyoxylic, oxalic, acetic and formic acids. Oxalic and glyoxylic acids remain mostly in the particle phase upon droplet evaporation. Thus isoprene is an important precursor of in-cloud SOA formation. Citation:

No abstract

[1] While there is a growing understanding from laboratory studies of aqueous phase chemical processes that lead to secondary organic aerosol (SOA) formation in cloud droplets (SOA drop ), the contribution of aqueous phase chemistry to atmospheric SOA burden is yet unknown. Using a parcel model including a multiphase chemical mechanism, we show that SOA drop carbon yields (Y c ) from isoprene (1) depend strongly on the initial volatile organic carbon (VOC)/NO x ratio resulting in 42% > Y c > 0.4% over the atmospherically-relevant range of 0.25 < VOC/NO x < 100; (2) increase with increasing cloud-contact time; (3) are less affected by cloud liquid water content, pH, and droplet number. (4) The uncertainty associated with gas/particlepartitioning of semivolatile organics introduces a relative error of À50% DY c < +100 %. The reported yields can be applied to air quality and climate models as is done with SOA formed on/in concentrated aerosol particles (SOA aer ).

Abstract. Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, nitrogen (N) containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter.

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols