Role of sulphuric acid, ammonia and galactic cosmic rays in atmospheric aerosol nucleation.

Atmospheric aerosols exert an important influence on climate through their effects on stratiform cloud albedo and lifetime and the invigoration of convective storms. Model calculations suggest that almost half of the global cloud condensation nuclei in the atmospheric boundary layer may originate from the nucleation of aerosols from trace condensable vapours, although the sensitivity of the number of cloud condensation nuclei to changes of nucleation rate may be small. Despite extensive research, fundamental questions remain about the nucleation rate of sulphuric acid particles and the mechanisms responsible, including the roles of galactic cosmic rays and other chemical species such as ammonia. Here we present the first results from the CLOUD experiment at CERN. We find that atmospherically relevant ammonia mixing ratios of 100 parts per trillion by volume, or less, increase the nucleation rate of sulphuric acid particles more than 100-1,000-fold. Time-resolved molecular measurements reveal that nucleation proceeds by a base-stabilization mechanism involving the stepwise accretion of ammonia molecules. Ions increase the nucleation rate by an additional factor of between two and more than ten at ground-level galactic-cosmic-ray intensities, provided that the nucleation rate lies below the limiting ion-pair production rate. We find that ion-induced binary nucleation of H(2)SO(4)-H(2)O can occur in the mid-troposphere but is negligible in the boundary layer. However, even with the large enhancements in rate due to ammonia and ions, atmospheric concentrations of ammonia and sulphuric acid are insufficient to account for observed boundary-layer nucleation.

Bond energies and structures of ammonia-sulfuric acid positive cluster ions.

New particle formation in the atmosphere is initiated by nucleation of gas-phase species. The small molecular clusters that act as seeds for new particles are stabilized by the incorporation of an ion. Ion-induced nucleation of molecular cluster ions containing sulfuric acid generates new particles in the background troposphere. The addition of a proton-accepting species to sulfuric acid cluster ions can further stabilize them and may promote nucleation under a wider range of conditions. To understand and accurately predict atmospheric nucleation, the stabilities of each molecular cluster within a chemical family must be known. We present the first comprehensive measurements of the ammonia-sulfuric acid positive ion cluster system NH(4)(+)(NH(3))(n)(H(2)SO(4))(s). Enthalpies and entropies of individual growth steps within this system were measured using either an ion flow reactor-mass spectrometer system under equilibrium conditions or by thermal decomposition of clusters in an ion trap mass spectrometer. Low level ab initio structural calculations provided inputs to a master equation model to determine bond energies from thermal decomposition measurements. Optimized ab initio structures for clusters up through n = 3, s = 3 are reported. Upon addition of ammonia and sulfuric acid pairs, internal proton transfer generates multiple NH(4)(+) and HSO(4)(-) ions within the clusters. These multiple-ion structures are up to 50 kcal mol(-1) more stable than corresponding isomers that retain neutral NH(3) and H(2)SO(4) species. The lowest energy n = s clusters are composed entirely of ions. The addition of acid-base pairs to the core NH(4)(+) ion generates nanocrystals that begin to resemble the ammonium bisulfate bulk crystal starting with the smallest n = s cluster, NH(4)(+)(NH(3))(1)(H(2)SO(4))(1). In the absence of water, this cluster ion system nucleates spontaneously for conditions that encompass most of the free troposphere.

Evidence for liquid-like and nonideal behavior of a mixture of organic aerosol components.

The condensation, evaporation, and repartitioning of semivolatile organic compounds (SVOCs) in the atmosphere depends both on the phase of condensed material and the effective condensed phase vapor pressures of the SVOCs. Although direct measurements of vapor pressures of individual SVOCs exist, there are limited measurements of how the properties of a given compound changes in mixtures of multiple components that exist in the atmosphere. Here, the evaporation behavior of mixtures of dicarboxylic acids, which are common atmospheric aerosol constituents, is investigated. These measurements demonstrate that complex mixtures of the individually solid organic compounds take on liquid-like properties. Additionally, the vapor pressures of individual components show strong, identity-dependent deviations from ideality (i.e., Raoult's Law), with the vapor pressures of the smaller, more volatile compounds decreased significantly in the mixtures. The addition of an inorganic compound (NaNO(3)) further influences the nonideal behavior, again in a compound-specific manner. These results suggest that nonideal behavior of particle-phase compounds influences the abundances of organic aerosol observed in the atmosphere and in the laboratory.

Evaporation rates and vapor pressures of the even-numbered C8-C18 monocarboxylic acids.

Temperature-dependent vapor pressures of the even-numbered alkanoic monoacids from C8-C18 were measured using temperature-programmed desorption (TPD). In TPD, the evaporation rates from the samples are directly measured and the vapor pressures are subsequently determined from the Hertz-Knudsen equation. Our measurements indicate that the vapor pressures of the solid even-numbered alkanoic acids decrease monotonically with increasing carbon number by more than 6 orders of magnitude going from C8 to C18. The enthalpies of sublimation increase monotonically with carbon number, from approximately 110 to 205 kJ/mol. The liquid-phase vapor pressure was measured for oleic acid, a C18 alkenoic acid. Comparison to the estimated liquid-phase vapor pressure for the corresponding C18 alkanoic acid indicates that the liquid-phase vapor pressures of these two compounds are identical. Our measured solid-phase vapor pressures for the C14 and larger alkanoic acids are lower than in previous studies. We attribute these differences to the influence of residual solvent molecules on the previous measurements, which cause the measured vapor pressures to be too large.

Determination of evaporation rates and vapor pressures of very low volatility compounds: a study of the C4-C10 and C12 dicarboxylic acids.

A method for the measurement of evaporation rates and vapor pressures of low volatility compounds was developed and applied to the homologous series of C4-C10 and C12 dicarboxylic acids. Proton-transfer chemical ionization mass spectrometry was used to follow directly the temperature-dependent evaporation rates of aerosol samples collected on a cold plate that could be heated at a known rate. The vapor pressures of the deposited compounds were derived from observed evaporation rates through application of the Hertz-Knudsen equation. Temperature programmed desorption allowed for quantification of the enthalpy (DeltaHsub) and entropy (DeltaSsub) of sublimation of the diacids and is described. A strong odd-even dependence with respect to the total carbon number was observed in the derived diacid vapor pressures, consistent with previous measurements. However, the vapor pressures from this method were systematically lower than previous measurements. Though seen in the vapor pressure, no odd-even carbon chain length dependence was readily discernible in the measured values of DeltaHsub and DeltaSsub. Perhaps most importantly, these experimental results also suggest that residual solvent molecules (from the aerosol generation process) trapped in the diacid samples can have a considerable influence on the measured thermodynamic parameters and, if not properly accounted for, may give erroneous results.

Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study--Intercontinental Transport and Chemical Transformation 2004: performance, intercomparison, and compound identification.

We have used a newly developed proton-transfer ion-trap mass spectrometry (PIT-MS) instrument for online trace gas analysis of volatile organic compounds (VOCs) during the 2004 New England Air Quality Study-Intercontinental Transport and Chemical Transformation study. The PIT-MS instrument uses proton-transfer reactions with H3O+ ions to ionize VOCs, similarto a PTR-MS (proton-transfer reaction mass spectrometry) instrument but uses an ion trap mass spectrometer to analyze the product ions. The advantages of an ion trap are the improved identification of VOCs and a near 100% duty cycle. During the experiment, the PIT-MS instrument had a detection limit between 0.05 and 0.3 pbbv (S/N = 3 (signal-to-noise ratio)) for 2-min integration time for most tested VOCs. PIT-MS was used for ambient air measurements onboard a research ship and agreed well with a gas chromatography mass spectrometer). The comparison included oxygenated VOCs, aromatic compounds, and others such as isoprene, monoterpenes, acetonitrile, and dimethyl sulfide. Automated collision-induced dissociation measurements were used to determine the contributions of acetone and propanal to the measured signal at 59 amu; both species are detected at this mass and are thus indistinguishable in conventional PTR-MS.