The Marine Stratus/Stratocumulus Experiment (MASE): Aerosol-cloud relationships in marine stratocumulus

The Marine Stratus/Stratocumulus Experiment (MASE) field campaign was undertaken in July 2005 off the coast of Monterey, California to evaluate aerosol-cloud relationships in the climatically important regime of eastern Pacific marine stratocumulus. Aerosol and cloud properties were measured onboard the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft. One cloud that was clearly impacted by ship emissions as well as the ensemble of clouds observed over the entire mission are analyzed in detail. Results at both the individual and ensemble scales clearly confirm the Twomey effect (first indirect effect of aerosols) and demonstrate drizzle suppression at elevated aerosol number concentration. For the ship track impacted cloud, suppressed drizzle in the track led to a larger cloud liquid water path (LWP) at the same cloud thickness, in accord with the so-called second indirect effect. Ensemble averages over all clouds sampled over the entire 13-flight mission show the opposite effect of aerosol number concentration on LWP, presumably the result of other dynamic influences (e.g., updraft velocity and ambient sounding profile). Individual polluted clouds were found to exhibit a narrower cloud drop spectral width in accord with theoretical prediction (M.-L. Lu and J. H. Seinfeld, Effect of aerosol number concentration on cloud droplet dispersion: A large-eddy simulation study and implications for aerosol indirect forcing, Journal of Geophysical Research, 2006). This field experiment demonstrates both the indirect aerosol effect on ship track perturbed clouds, as well as the subtleties involved in extracting these effects over an ensemble of clouds sampled over a 1-month period

Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds

Recent experimental evidence indicates that heterogeneous chemical reactions play an important role in the gas-particle partitioning of organic compounds, contributing to the formation and growth of secondary organic aerosol in the atmosphere. Here we present laboratory chamber studies of the reactive uptake of simple carbonyl species (formaldehyde, octanal, trans,trans-2,4-hexadienal, glyoxal, methylglyoxal, 2,3-butanedione, 2,4-pentanedione, glutaraldehyde, and hydroxyacetone) onto inorganic aerosol. Gas-phase organic compounds and aqueous seed particles (ammonium sulfate or mixed ammonium sulfate/sulfuric acid) are introduced into the chamber, and particle growth and composition are monitored using a differential mobility analyzer and an Aerodyne Aerosol Mass Spectrometer. No growth is observed for most carbonyls studied, even at high concentrations (500 ppb to 5 ppm), in contrast with the results from previous studies. The single exception is glyoxal (CHOCHO), which partitions into the aqueous aerosol much more efficiently than its Henry's law constant would predict. No major enhancement in particle growth is observed for the acidic seed, suggesting that the large glyoxal uptake is not a result of particle acidity but rather of ionic strength of the seed. This increased partitioning into the particle phase still cannot explain the high levels of glyoxal measured in ambient aerosol, indicating that additional (possibly irreversible) pathways of glyoxal uptake may be important in the atmosphere

The Marine Stratus/Stratocumulus Experiment (MASE): Aerosol-cloud relationships in marine stratocumulus

Journal of Geophysical Research, Vol. 112, D10209The article of record as published may be located at http://dx.doi.org/10.1029/2006JD007985.The Marine Stratus/Stratocumulus Experiment (MASE) field campaign was undertaken in July 2005 off the coast of Monterey, California to evaluate aerosol-cloud relationships in the climatically important regime of eastern Pacific marine stratocumulus. Aerosol and cloud properties were measured onboard the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft. One cloud that was clearly impacted by ship emissions as well as the ensemble of clouds observed over the entire mission are analyzed in detail. Results at both the individual and ensemble scales clearly confirm the Twomey effect (first indirect effect of aerosols) and demonstrate drizzle suppression at elevated aerosol number concentration. For the ship track impacted cloud, suppressed drizzle in the track led to a larger cloud liquid water path (LWP) at the same cloud thickness, in accord with the so-called second indirect effect. Ensemble averages over all clouds sampled over the entire 13-flight mission show the opposite effect of aerosol number concentration on LWP, presumably the result of other dynamic influences (e.g., updraft velocity and ambient sounding profile). Individual polluted clouds were found to exhibit a narrower cloud drop spectral width in accord with theoretical prediction (M.-L. Lu and J. H. Seinfeld, Effect of aerosol number concentration on cloud droplet dispersion: A large-eddy simulation study and implications for aerosol indirect forcing, Journal of Geophysical Research, 2006). This field experiment demonstrates both the indirect aerosol effect on ship track perturbed clouds, as well as the subtleties involved in extracting these effects over an ensemble of clouds sampled over a 1-month period

Cloud condensation nuclei activity, closure, and droplet growth kinetics of Houston aerosol during the Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS)

In situ cloud condensation nuclei (CCN) measurements were obtained in the boundary layer over Houston, Texas, during the 2006 Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS) campaign onboard the CIRPAS Twin Otter. Polluted air masses in and out of cloudy regions were sampled for a total of 22 flights, with CCN measurements obtained for 17 of these flights. In this paper, we focus on CCN closure during two flights, within and downwind of the Houston regional plume and over the Houston Ship Channel. During both flights, air was sampled with particle concentrations exceeding 25,000 cm^(−3) and CCN concentrations exceeding 10,000 cm^(−3). CCN closure is evaluated by comparing measured concentrations with those predicted on the basis of measured aerosol size distributions and aerosol mass spectrometer particle composition. Different assumptions concerning the internally mixed chemical composition result in average CCN overprediction ranging from 3% to 36% (based on a linear fit). It is hypothesized that the externally mixed fraction of the aerosol contributes much of the CCN closure scatter, while the internally mixed fraction largely controls the overprediction bias. On the basis of the droplet sizes of activated CCN, organics do not seem to impact, on average, the CCN activation kinetics

New particle formation from photooxidation of diiodomethane (CH_2I_2)

Photolysis of CH_2I_2 in the presence of O_3 has been proposed as a mechanism leading to intense new particle formation in coastal areas. We report here a comprehensive laboratory chamber study of this system. Rapid homogeneous nucleation was observed over three orders of magnitude in CH_2I_2 mixing ratio, down to a level of 15 ppt (∼4 × 10^8 molec. cm^(−3)) comparable to the directly measured total gas-phase iodine species concentrations in coastal areas. After the nucleation burst, the observed aerosol dynamics in the chamber was dominated by condensation of additional vapors onto existing particles and particle coagulation. Particles formed under dry conditions are fractal agglomerates with mass fractal dimension, D_f ∼ 1.8–2.5. Higher relative humidity (65%) does not change the nucleation or growth behavior from that under dry conditions, but results in more compact and dense particles (D_f ∼ 2.7). On the basis of the known gas-phase chemistry, OIO is the most likely gas-phase species to produce the observed nucleation and aerosol growth; however, the current understanding of this chemistry is very likely incomplete. Chemical analysis of the aerosol using an Aerodyne Aerosol Mass Spectrometer reveals that the particles are composed mainly of iodine oxides but also contain water and/or iodine oxyacids. The system studied here can produce nucleation events as intense as those observed in coastal areas. On the basis of comparison between the particle composition, hygroscopicity, and nucleation and growth rates observed in coastal nucleation and in the experiments reported here, it is likely that photooxidation of CH_2I_2, probably aided by other organic iodine compounds, is the mechanism leading to the observed new particle formation in the west coast of Ireland

Szenci Molnár Albert epigrammája a Scandell-antológiában

The composition of secondary organic aerosol (SOA) from the ozonolysis of C5−C8 cycloalkenes and α-pinene, as well as the effects of hydrocarbon precursor structure and particle-phase acidity on SOA formation, have been investigated by a series of controlled laboratory chamber experiments. A liquid chromatography−mass spectrometer and an ion trap mass spectrometer are used concurrently to identify and to quantify SOA components with molecular weights up to 1600 Da. Diacids, carbonyl-containing acids, diacid alkyl esters, and hydroxy diacids are the four major classes of low-molecular-weight (MW \u3c 250 Da) components in the SOA; together they comprise 42−83% of the total SOA mass, assuming an aerosol density of 1.4 g/cm3. In addition, oligomers (MW \u3e 250 Da) are found to be present in all SOA. Using surrogate standards, it is estimated that the mass fraction of oligomers in the total SOA is at least 10% for the cycloalkene systems (with six or more carbons) and well over 50% for the α-pinene system. Higher seed particle acidity is found to lead to more rapid oligomer formation and, ultimately, to higher SOA yields. Because oligomers are observed to form even in the absence of seed particles, organic acids produced from hydrocarbon oxidation itself may readily promote acid catalysis and oligomer formation. The distinct effects of carbon numbers, substituent groups, and isomeric structures of the precursor hydrocarbons on the composition and yield of SOA formed are also discussed

Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes

The ozonolyses of six monoterpenes (α-pinene, β-pinene, 3-carene, terpinolene, α-terpinene, and myrcene), two sesquiterpenes (α-humulene and β-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). Several gas-phase oxidation products, formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, and nopinone, were identified and calibrated. Aerosol yields, and the yields of these identified and calibrated oxidation products, as well as many higher m/z oxidation products observed with the PTR-MS, varied significantly between the different parent terpene compounds. The sum of measured oxidation products in the gas and particle phase ranged from 33 to 77% of the carbon in the reacted terpenes, suggesting there are still unmeasured products from these reactions. The observations of the higher molecular weight oxidation product ions provide evidence of previously unreported compounds and their temporal evolution in the smog chamber from multistep oxidation processes. Many of the observed ions, including m/z 111 and 113, have also been observed in ambient air above a Ponderosa pine forest canopy, and our results confirm they are consistent with products from terpene + O_3 reactions. Many of these products are stable on the timescale of our experiments and can therefore be monitored in field campaigns as evidence for ozone oxidative chemistry

Measurements of Secondary Organic Aerosol from Oxidation of Cycloalkenes, Terpenes, and m-Xylene Using an Aerodyne Aerosol Mass Spectrometer

The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photooxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of “effective” density of the SOA in the range of 0.64−1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, CO2+ ion fragment of oxygenated organics, and higher “Δ” values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative “Δ” values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in “Δ” patterns, is observed in the ozonolysis of α-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA