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Abstract. Glyoxal (CHOCHO), the simplest dicarbonyl in the troposphere, is a potential precursor for secondary organic aerosol (SOA) and brown carbon (BrC) affecting air quality and climate. The airborne measurement of CHOCHO concentrations during the KORUS-AQ (KORea–US Air Quality study) campaign in 2016 enables detailed quantification of loss mechanisms pertaining to SOA formation in the real atmosphere. The production of this molecule was mainly from oxidation of aromatics (59 %) initiated by hydroxyl radical (OH). CHOCHO loss to aerosol was found to be the most important removal path (69 %) and contributed to roughly ∼ 20 % (3.7 µg sm−3 ppmv−1 h−1, normalized with excess CO) of SOAmore » growth in the first 6 h in Seoul Metropolitan Area. A reactive uptake coefficient (γ) of ∼ 0.008 best represents the loss of CHOCHO by surface uptake during the campaign. To our knowledge, we show the first field observation of aerosol surface-area-dependent (Asurf) CHOCHO uptake, which diverges from the simple surface uptake assumption as Asurf increases in ambient condition. Specifically, under the low (high) aerosol loading, the CHOCHO effective uptake rate coefficient, keff,uptake, linearly increases (levels off) with Asurf; thus, the irreversible surface uptake is a reasonable (unreasonable) approximation for simulating CHOCHO loss to aerosol. Dependence on photochemical impact and changes in the chemical and physical aerosol properties “free water”, as well as aerosol viscosity, are discussed as other possible factors influencing CHOCHO uptake rate. Our inferred Henry's law coefficient of CHOCHO, 7.0×108 M atm−1, is ∼ 2 orders of magnitude higher than those estimated from salting-in effects constrained by inorganic salts only consistent with laboratory findings that show similar high partitioning into water-soluble organics, which urges more understanding on CHOCHO solubility under real atmospheric conditions.« less

Airborne observations over the Amazon Basin showed high aerosol particle concentrations in the upper troposphere (UT) between 8 and 15 km altitude, with number densities (normalized to standard temperature and pressure) often exceeding those in the planetary boundary layer (PBL) by 1 or 2 orders of magnitude. The measurements were made during the German–Brazilian cooperative aircraft campaign ACRIDICON–CHUVA, where ACRIDICON stands for Aerosol, Cloud, Precipitation, and Radiation Interactions and Dynamics of Convective Cloud Systems and CHUVA is the acronym for Cloud Processes of the Main Precipitation Systems in Brazil: A Contribution to Cloud Resolving Modeling and to the GPM (globalmore » precipitation measurement), on the German High Altitude and Long Range Research Aircraft (HALO). The campaign took place in September–October 2014, with the objective of studying tropical deep convective clouds over the Amazon rainforest and their interactions with atmospheric trace gases, aerosol particles, and atmospheric radiation. Aerosol enhancements were observed consistently on all flights during which the UT was probed, using several aerosol metrics, including condensation nuclei (CN) and cloud condensation nuclei (CCN) number concentrations and chemical species mass concentrations. The UT particles differed sharply in their chemical composition and size distribution from those in the PBL, ruling out convective transport of combustion-derived particles from the boundary layer (BL) as a source. The air in the immediate outflow of deep convective clouds was depleted of aerosol particles, whereas strongly enhanced number concentrations of small particles (< 90 nm diameter) were found in UT regions that had experienced outflow from deep convection in the preceding 5–72 h. We also found elevated concentrations of larger (> 90 nm) particles in the UT, which consisted mostly of organic matter and nitrate and were very effective CCN. Our findings suggest a conceptual model, where production of new aerosol particles takes place in the continental UT from biogenic volatile organic material brought up by deep convection and converted to condensable species in the UT. Subsequently, downward mixing and transport of upper tropospheric aerosol can be a source of particles to the PBL, where they increase in size by the condensation of biogenic volatile organic compound (BVOC) oxidation products. This may be an important source of aerosol particles for the Amazonian PBL, where aerosol nucleation and new particle formation have not been observed. We propose that this may have been the dominant process supplying secondary aerosol particles in the pristine atmosphere, making clouds the dominant control of both removal and production of atmospheric particles.« less

In this work, the effect of dry and wet deposition of semi-volatile organic compounds (SVOCs) in the gas phase on the concentrations of secondary organic aerosol (SOA) is reassessed using recently derived water solubility information. The water solubility of SVOCs was implemented as a function of their volatility distribution within the WRF-Chem regional chemistry transport model, and simulations were carried out over the continental United States for the year 2010. Results show that including dry and wet removal of gas-phase SVOCs reduces annual average surface concentrations of anthropogenic and biogenic SOA by 48 and 63% respectively over the continental US.more » Dry deposition of gas-phase SVOCs is found to be more effective than wet deposition in reducing SOA concentrations (-40 vs. -8% for anthropogenics, and -52 vs. -11% for biogenics). Reductions for biogenic SOA are found to be higher due to the higher water solubility of biogenic SVOCs. The majority of the total mass of SVOC + SOA is actually deposited via the gas phase (61% for anthropogenics and 76% for biogenics). Results are sensitive to assumptions made in the dry deposition scheme, but gas-phase deposition of SVOCs remains crucial even under conservative estimates. Considering reactivity of gas-phase SVOCs in the dry deposition scheme was found to be negligible. Further sensitivity studies where we reduce the volatility of organic matter show that consideration of gas-phase SVOC removal still reduces average SOA concentrations by 31% on average. We consider this a lower bound for the effect of gas-phase SVOC removal on SOA concentrations. A saturation effect is observed for Henry's law constants above 10⁸ M atm^-1, suggesting an upper bound of reductions in surface level SOA concentrations by 60% through removal of gas-phase SVOCs. Other models that do not consider dry and wet removal of gas-phase SVOCs would hence overestimate SOA concentrations by roughly 50%. Assumptions about the water solubility of SVOCs made in some current modeling systems (H^* = H^* (CH₃COOH); H^* = 10⁵ M atm^-1; H^* = H^* (HNO₃)) still lead to an overestimation of 35%/25%/10% compared to our best estimate.« less

Globally, secondary organic aerosol (SOA) is mostly formed from emissions of biogenic volatile organic compounds (VOCs) by vegetation, but it can be modified by human activities as demonstrated in recent research. Specifically, nitrogen oxides (NO_x = NO + NO₂) have been shown to play a critical role in the chemical formation of low volatility compounds. We have updated the SOA scheme in the global NCAR (National Center for Atmospheric Research) Community Atmospheric Model version 4 with chemistry (CAM4-chem) by implementing a 4-product volatility basis set (VBS) scheme, including NO_x-dependent SOA yields and aging parameterizations. Small differences are found for themore » no-aging VBS and 2-product schemes; large increases in SOA production and the SOA-to-OA ratio are found for the aging scheme. The predicted organic aerosol amounts capture both the magnitude and distribution of US surface annual mean measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network by 50 %, and the simulated vertical profiles are within a factor of 2 compared to aerosol mass spectrometer (AMS) measurements from 13 aircraft-based field campaigns across different regions and seasons. We then perform sensitivity experiments to examine how the SOA loading responds to a 50 % reduction in anthropogenic nitric oxide (NO) emissions in different regions. We find limited SOA reductions of 0.9–5.6, 6.4–12.0 and 0.9–2.8 % for global, southeast US and Amazon NO_x perturbations, respectively. The fact that SOA formation is almost unaffected by changes in NO_x can be largely attributed to a limited shift in chemical regime, to buffering in chemical pathways (low- and high-NO_x pathways, O₃ versus NO₃-initiated oxidation) and to offsetting tendencies in the biogenic versus anthropogenic SOA responses.« less