Particle Formation and Growth From Ozonolysis of α-pinene

Observations of particle nucleation and growth during ozonolysis of α-pinene were carried out in Calspan\u27s 600 m3 environmental chamber utilizing relatively low concentrations of α-pinene (15 ppb) and ozone (100 ppb). Model simulations with a comprehensive sectional aerosol model which incorporated the relevant gas-phase chemistry show that the observed evolution of the size distribution could be simulated within the accuracy of the experiment by assuming only one condensable product produced with a molar yield of 5% to 6% and a saturation vapor pressure (SVP) of about 0.01 ppb or less. While only one component was required to simulate the data, more than one product may have been involved, in which case the one component must be viewed as a surrogate having an effective SVP of 0.01 ppb or less. Adding trace amounts of SO2greatly increased the nucleation rate while having negligible effect on the overall aerosol yield. We are unable to explain the observed nucleation in the α-pinene/ozone system in terms of classical nucleation theory. The nucleation rate and, more importantly, the slope of the nucleation rate versus the vapor pressure of the nucleating species would suggest that the nucleation rate in the α-pinene/ozone system may be limited by the initial nucleation steps (i.e., dimer, trimer, or adduct formation)

Sulfur Dioxide Uptake and Oxidation in Sea-Salt Aerosol

Measurements of SO2 and O3 uptake by sea-salt and NaCl aerosol were made in a 600 m3environmental chamber by measuring the rate of SO2 and O3 depletion during nebulization of seawater and NaCl solutions. The experiments were carried out with starting relative humidity between 80% and 92%, with SO2 concentrations between 35 and 60 ppb, and ozone concentrations between O and 110 ppb. For NaCl, no SO2 or O3uptake was observed. For sea-salt aerosol, uptake in the range of 0.21 and 1.2 millimoles of S per liter of (nebulized) seawater was observed. Surprisingly, no O3 uptake was observed even though the residence time of the aerosol in the chamber was long compared to the time required for the predicted S(IV)-O3 reaction to occur. Several S(IV) oxidation schemes are considered to explain these observations. The Cl-catalyzed aerobic mechanism as formulated by Zhang and Millero [1991] from empirical data best explains our observations. The Cl-catalyzed S(IV) reaction decreases rapidly with decreasing pH, making it important only at pH\u3e∼5.5. This rapid decrease with pH explains why SO2uptake was not observed in the NaCl aerosol and observed at a level approaching the sea-salt alkalinity in the case of sea-salt aerosol

In-cloud oxidation of SO2 by O3 and H2O2: Cloud Chamber Measurements and Modeling of Particle Growth

Controlled cloud chamber experiments were conducted to measure particle growth resulting from the oxidation of SO2 by O3 and H2O2 in cloud droplets formed on sulfuric acid seed aerosol. Clouds were formed in a 590 m3 environmental chamber with total liquid water contents ranging from 0.3–0.6 g m−3 and reactant gas concentrations \u3c10 ppbv for SO2 and H2O2 and \u3c70 ppbv for O3. Aerosol growth was measured by comparison of differential mobility analyzer size distributions before and after each 3–4 min cloud cycle. Predictions of aerosol growth were then made with a full microphysical cloud model used to simulate each individual experimental cloud cycle. Model results of the H2O2 oxidation experiments best fit the experimental data using the third-order rate constant of Maass et al. [1999] (k = 9.1 × 107 M−2 s−1), with relative aerosol growth agreeing within 3% of measured values, while the rate of Hoffmann and Colvert [1985] produced agreement within 4–9%, and the rate of Martin and Damschen [1981] only within 13–18%. Simulation results of aerosol growth during the O3 oxidation experiments were 60–80% less than the measured values, confirming previous results [Hoppel et al., 1994b]. Experimental results and analyses presented here show that the SO2 - O3 rate constants would have to be more than 5 times larger than currently accepted values to explain the measured growth. However, unmeasured NH3 contamination present in trace amounts (\u3c0.2 ppb) could explain the disagreement, but this is speculative and the source of this discrepancy is still unknown

Experimental and Modeling Studies of Secondary Organic Aerosol Formation and Some Applications to the Marine Boundary Layer

A series of controlled experiments were carried out in the Calspan Corporation\u27s 600 m3environmental chamber to study some secondary organic aerosol formation processes. Three precursor-ozone systems were studied: cyclopentene-ozone, cyclohexene-ozone, and α-pineneozone. Additionally, SO2 was added to the initial gas mixture in several instances and was likely present at trace levels in the ostensibly organic-only experiments. It was found that all three systems readily formed new submicron aerosols at very low reactant levels. The chemical composition of formed aerosols was consistent with some previous studies, but the yields of organic products were found to be lower in the Calspan experiments. A three-step procedure is proposed to explain the observed particle nucleation behavior: HO · production → H2SO4 formation → H2SO4-H2O (perhaps together with NH3) homogeneous nucleation. It is also proposed that some soluble organic products would partition into the newly formed H2SO4-H2O nuclei, enhance water condensation, and quickly grow these nuclei into a larger size range. While the observations in the two cycloolefin-ozone systems could be well explained by these proposed mechanisms, the exact nature of the nucleation process in the α-pinene-ozone system remains rather opaque and could be the result of nucleation involving certain organics. The results from three simple modeling studies further support these proposals. Their applicability to the marine boundary layer (MBL) is also discussed in some detail. Particularly, such a particle nucleation and growth process could play an important role in secondary aerosol formation and, quite likely, CCN formation as well in certain MBL regions

Airborne Remote Sensing of the Upper Ocean Turbulence during CASPER-East

The article of record as published may be found at http://dx.doi.org/10.3390/rs10081224This study takes on the challenge of resolving upper ocean surface currents with a suite of airborne remote sensing methodologies, simultaneously imaging the ocean surface in visible, infrared, and microwave bands. A series of flights were conducted over an air-sea interaction supersite established 63 km offshore by a large multi-platform CASPER-East experiment. The supersite was equipped with a range of in situ instruments resolving air-sea interface and underwater properties, of which a bottom-mounted acoustic Doppler current profiler was used extensively in this paper for the purposes of airborne current retrieval validation and interpretation. A series of water-tracing dye releases took place in coordination with aircraft overpasses, enabling dye plume velocimetry over 100 m to 10 km spatial scales. Similar scales were resolved by a Multichannel Synthetic Aperture Radar, which resolved a swath of instantaneous surface velocities (wave and current) with 10 m resolution and 5 cm/s accuracy. Details of the skin temperature variability imprinted by the upper ocean turbulence were revealed in 1–14,000 m range of spatial scales by a mid-wave infrared camera. Combined, these methodologies provide a unique insight into the complex spatial structure of the upper ocean turbulence on a previously under-resolved range of spatial scales from meters to kilometers. However, much attention in this paper is dedicated to quantifying and understanding uncertainties and ambiguities associated with these remote sensing methodologies, especially regarding the smallest resolvable turbulent scales and to reference depths of retrieved currents.NRLONRNSFNRL program element 61153N WUs BE023-01-41-1C04NRL program element 61153N WUs BE023-01-41-1C02NRL program element 61153N WUs BE023-01-41-6692ONR grant N0001418WX01087NSF grant OCE-154064