Hygroscopic growth and CCN activity of secondary organic aerosol produced from dark ozonolysis of γ-terpinene.

The hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) particles produced during dark ozonolysis of γ-terpinene under different reaction conditions were investigated. The SOA particles were produced in the presence or absence of cyclohexane, an OH scavenger; 1,3,5-trimethylbenzene, an anthropogenic volatile organic compound; and (NH4)2SO4 seed particles. A hygroscopicity tandem differential mobility analyzer was used to determine the GFs of the SOA particles at RHs ≤ 93%. For some experiments, a CCN counter was used for size-resolved measurement of CCN activation at supersaturation (S) in the range of 0.1 to 1%. The single hygroscopicity parameter κ was derived from both the GF and CCN measurements. Under subsaturated conditions, all the SOA (except those in the presence of the (NH4)2SO4 seeds) showed small GF values. These GFs demonstrated that SOA mass loading affected the GF. A decrease in the SOA mass loading led to increased GF and corresponding κGFvalues. However, in a supersaturation regime, the SOA mass loading and the size of the particles did not significantly alter the CCN activity of the SOA. Our CCN measurements showed higher κCCN values (κCCN = 0.20-0.24) than those observed in most monoterpene ozonolysis studies (κCCN = 0.1-0.14). This difference may have been due to the presence of the two endocyclic double bonds in the γ-terpinene structure, which may have affected the SOA chemical composition, in contrast to monoterpenes that contain an exocyclic double bond. Our comparisons of sub- and supersaturated conditions showed a larger range of κ values than other experiments. Average κCCN/κGF ratios of ~7 and 14 were obtained in the unseeded SOA experiments at low and high SOA mass loadings, respectively. The average κCCN of 0.23 indicated that the SOA produced during ozonolysis of γ-terpinene exhibited fairly high CCN activity.

Complex refractive index of volcanic ash aerosol in the infrared, visible, and ultraviolet.

Very fine silicate-rich volcanic ash, generated by explosive volcanic eruptions, can efficiently be traced downwind with infrared satellite sounders. Their measurements can also be used to derive physical parameters, such as optical depths and effective radii. However, one of the key requirements for accurate retrievals is a good knowledge of the complex refractive index (CRI) of the ash under investigation. In the past, the vast majority of the studies used the CRIs from Pollack et al. [Icarus19, 372 (1973)ICRSA50019-103510.1016/0019-1035(73)90115-2], which are based on measurements of thin slices of volcanic rock, and therefore are not representative for airborne volcanic ash particles. Here, we report measurements of the CRI of volcanic ash in suspension, generated from samples collected from recent high-impact eruptions in Chile (Puyehue-Cordón Caulle, Calbuco, and Chaitén), Iceland (Eyjafjallajökull and Grímsvötn), and Italy (Etna). The samples cover a wide range of ${{\rm SiO}_2}$SiO2 content (46% to 76%) as confirmed by an X-ray fluorescence analysis. In the experimental setup, volcanic ash was suspended in nitrogen through mechanical agitation. Extinction spectra were recorded in the infrared, visible, and ultraviolet spectral regions. The particle size distribution within the airflow was also recorded. An iterative algorithm allowed us to obtain fully consistent CRIs for the six samples, compatible with the observed extinction spectra and the Kramers-Krönig relations. While a good agreement is found with other recently reported CRIs in the UV/Vis, larger differences are found in the longwave infrared spectral region.

Uptake of ozone and modification of lipids in Betula Pendula pollen.

Pollen allergy risk is modified by air pollutants, including ozone, but the chemical modifications induced on pollen grains are poorly understood. Pollen lipidic extract has been shown to act as an adjuvant to the allergenic reaction and therefore, the modification of lipids by air pollutants could have health implications. Birch pollen was exposed in vitro to ozone to explore the reactivity of O3 on its surface and on its lipidic fraction. Uptake coefficients of ozone were determined for ozone concentration of 117 ppb on the surface of native birch pollen (8.6 ±â€¯0.8 × 10-6), defatted pollen (9.9 ±â€¯0.9 × 10-6), and for crushed pollen grains (34±3 × 10-6). The mass of ozone uptaken was increased by a factor of four for crushed pollen compared to native pollen showing a higher susceptibility to ozone of cytoplasmic granules and broken pollen grains. A total mass of extractible lipids of 27 mg per gram of birch pollen was found and a fraction of these lipids was identified and quantified (fatty acids, alkanes, alkenes and aldehydes). The distribution of lipids was modified by ozone exposure of 115 and 1000 ppb for 16 h with the following reactivity: consumption of alkene, formation of aldehydes and formation of nonanoic acid and octadecanoic acid. The quantity of ozone trapped in the lipidic fraction during 15 min at 115 ppb is enough to contribute to the reactivity of one-third of the alkenes demonstrating that pollen could be susceptible to an atmospheric increase of ozone concentration even for a very short duration complicating the understanding of the link between pollen allergy and pollution.

Kinetic of NO2 uptake by Phleum pratense pollen: chemical and allergenic implications.

Phleum pratense pollen was exposed to NO(2) in a reactor allowing a continuous analysis of NO(2) concentration by FTIR. The uptake coefficient of NO(2) on pollen was calculated postulating a first order kinetic reaction and a value of (1.1 ± 0.1) x 10(-7) was determined. NO(2) uptake was faster when the pollen water content was increased and when the pollen was pre-treated with ozone. The effect of NO(2) exposure on pollen allergic properties was investigated by quantifying Th2- and Th1-associated chemokines in a model of human dendritic cells. Cellular analysis clearly showed that cells exposed to fumigated pollen favored the production of chemokines known to promote Th2-cell responses. Altogether these data demonstrate that NO(2) uptake by pollen directly correlates with increased Th2 response in human cells,and are in favor of the involvement of NO(2) pollution in the increase of allergic diseases.

Reactive and nonreactive ozone uptake during aging of oleic acid particles.

The ozonolysis of submicrometer (150 nm) oleic acid (OL) particles in an aerosol flow tube has been studied for a wide range of initial ozone concentrations from 25 ppb to 1100 ppb. Both reactants were monitored, as well as the four main reaction products (nonanal, azelaic acid, nonanoic acid, and 9-oxononanoic), by gas chromatography-mass spectrometer, high resolution-time of flight-aerosol mass spectrometer, proton transfer reaction-time of flight-mass spectrometer, and ozone analyzer. The values for the initial uptake coefficients derived from each reactant decay are in the same range: γO3-0 = (1.5 ± 0.1) × 10(-3) and γOL-0 = (1.0 ± 0.2) × 10(-3). The ozone uptake coefficient is highly decreased when particles are in an advanced oxidized state (γO3-∞ = 5 × 10(-5)). Concerning reaction products, nonanal was mainly observed in the gas-phase (∼80%) with a carbon yield of ∼29%. Nonanoic, azelaic, and 9-oxonanonoic acids have been quantified in the condensed phase with carbon yields of respectively 6.6%, 5.3%, and 31.4%. The changes in chemical composition induce a slight rise in particle density, whereas the aerodynamic particle diameter increases by 10%. The initial molar quantities of ozone and OL were chosen to obtain different initial stoichiometries in order to explore conditions where either of them is the limiting reactant. Drastic changes in reactivity were observed as a function of the initial stoichiometry. In conditions where OL was the initial limiting reactant, up to a total of four molecules of O3 were lost from the gas phase, whereas only one OL molecule was consumed.

Heterogeneous reactivity of chlorine atoms with ammonium sulfate and ammonium nitrate particles.

In this laboratory study, model particles of ammonium sulfate (AS) and ammonium nitrate (AN) were exposed to chlorine atoms and uptake experiments were performed in a coated wall flow tube reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor using two different methods: either by depositing size-selected particles on the halocarbon wax or by spray depositing thin films using a constant output atomizer. The observed uptake coefficients vary for (NH(4))(2)SO(4), ranging from γ(Cl)(AS)≈ 1 × 10(-3) for size-selected particles to γ(Cl)(AS)≈ 6 × 10(-2) for thin films prepared by spray. An uptake coefficient of γ(Cl)(AN)≈ 2.5 × 10(-3) of Cl˙ on size-selected NH(4)NO(3) particles was measured. A heterogeneous recombination of Cl atoms to from Cl(2) molecules was observed for the two surfaces. Furthermore, an ageing process was observed for AS particles, this phenomenon leading to the formation of new chlorine species on the solid substrate.

Heterogeneous reactivity of chlorine atoms with sodium chloride and synthetic sea salt particles.

The uptake of chlorine atoms on sodium chloride (NaCl) and synthetic sea salt (SSS) particles was studied using a discharge flow reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor using two different methods: either by depositing size-selected particles on halocarbon wax or by spray depositing thin films using a constant output atomizer. The observed uptake coefficients of Cl˙ on NaCl particles are γ(NaCl)(Cl) ≈ 2 × 10(-2) for size-selected particles or γ(NaCl)(Cl) ≈ 5 × 10(-2) for thin films and for SSS particles γ(SSS)(Cl) ≈ 4 × 10(-3). Heterogeneous recombination of Cl atoms to Cl(2) molecules was observed for the two solid surfaces. The study was performed over the temperature range 258 to 353 K. The temperature dependence of the uptake was observed and the heat of adsorption of Cl˙ on NaCl particles was estimated at Q(ads) = 63 kJ mol(-1) assuming an Eley-Rideal mechanism. The role of surface adsorbed water has also been shown. The atmospheric implications of these findings are discussed briefly.

Sensitive and selective detection of OH radicals using Faraday rotation spectroscopy at 2.8 µm.

We report on the development of a Faraday rotation spectroscopy (FRS) instrument using a DFB diode laser operating at 2.8 µm for the hydroxyl (OH) free radical detection. The highest absorption line intensity and the largest gJ value make the Q (1.5) double lines of the 2Π3/2 state (υ = 1 ← 0) at 2.8 µm clearly the best choice for sensitive detection in the infrared region by FRS. The prototype instrument shows shot-noise dominated performance and, with an active optical pathlength of only 25 cm and a lock-in time constant of 100 ms, achieves a 1σ detection limit of 8.2 × 10(8) OH radicals/cm3.

Chlorofluoroiodomethane as a potential candidate for parity violation measurements.

CHFClI is among the more favorable molecules for parity violation (PV) measurements in molecules. Despite the fact that calculated PV effects are two orders of magnitude smaller than in some organometallic compounds, CHFClI displays interesting features which could make possible a new experimental PV test on this molecule. Indeed, ultrahigh resolution spectroscopy using an ultrastable CO(2) laser is favored by several intrinsic properties of this molecule. For example, the high vapor pressure of CHFClI allows investigation by supersonic beam spectroscopy. Indeed, the spectroscopic constants have been accurately determined by microwave and millimetre wave spectroscopy. This is important for the subsequent selection of an appropriate absorption band of CHFClI that could be brought to coïncide with the absorption of CO(2). Partially resolved (+)- and (-)-CHFClI enantiomers with respectively 63.3 and 20.5% ee's have been recently prepared and analyzed by molecular recognition using chiral hosts called cryptophanes. Finally, the S-(+)/R-(-) absolute configuration was ascertained by vibrational circular dichroïsm (VCD) in the gas phase.

Structural and conformational properties of 2-propenylgermane (allylgermane) studied by microwave and infrared spectroscopy and quantum chemical calculations.

The structural and conformational properties of allylgermane have been investigated using Stark and Fourier transform microwave spectroscopies, infrared spectroscopy, and high-level quantum chemical calculations. The parent species H2C=CHCH2GeH3 was investigated by microwave spectroscopy and infrared spectroscopy, while three deuterated species, namely, H2C=CDCH2GeH3, H2C=CHCHDGeH3, and H2C=CHCH2GeD3, were studied only by infrared spectroscopy. The microwave spectra of the ground vibrational state as well as of the first excited state of the torsion vibration around the sp2-sp3 carbon-carbon bond were assigned for the 70Ge, 72Ge, and 74Ge isotopomers of one conformer. This rotamer has an anticlinal arrangement for the C=C-C-Ge chain of atoms. The infrared spectrum of the gas in the 500-4000 cm(-1) range has been assigned. No evidence of additional rotameric forms other than anticlinal was seen in the microwave and infrared spectra. Several different high-level ab initio and density functional theory calculations have been performed. These calculations indicate that a less stable form, having a synperiplanar conformation of the C=C-C-Ge link of atoms, may coexist with the anticlinal form. The energy differences between the synperiplanar and anticlinal forms were calculated to be 5.6-9.2 kJ/mol depending on the computational procedure. The best approximation of the equilibrium structure of the anticlinal rotamer was found in the MP2/aug-cc-pVTZ calculations. The barrier to internal rotation of the germyl group was found to be 6.561(17) kJ/mol, from measurements of the splitting of microwave transitions caused by tunneling of the germyl group through its threefold barrier.

Structural and conformational properties of 1,2-propadienylphosphine (allenylphosphine) studied by microwave spectroscopy and quantum chemical calculations.

1,2-Propadienylphosphine (allenylphosphine), H(2)C=C=CHPH(2), has been investigated by Stark and Fourier transform microwave spectroscopy. Two rotameric forms denoted syn and gauche have been assigned. The syn form has a symmetry plane (C(s)() symmetry) where the lone electron pair of phosphorus points toward the double bonds. The phosphino group is rotated roughly 120 degrees from this position in the gauche rotamer. The dipole moment of syn was determined to be mu(a) = 1.613(23), mu(b) = 2.347(24), mu(c) = 0 (for symmetry reasons), and mu(tot) = 2.848(28) x 10(-30) C m [0.854(8) D]. The energy difference between the two forms was found to be 2.1(4) kJ/mol from relative intensity measurements with syn as the more stable conformer. Extensive quantum chemical calculations have been carried out and accurate equilibrium structures have been determined for these two rotamers, as well as for the corresponding two conformers of vinylphosphine (H(2)C=CHPH(2)).