Hydration increases the lifetime of HSO5 and enhances its ability to act as a nucleation precursor – a computational study

Recent experimental findings indicate that HSO5 radicals may play a key role in the nucleation of atmospheric SO2 oxidation products. HSO5 radicals are metastable intermediates formed in the SO2 oxidation process, and their stability and lifetime are, at present, highly uncertain. Previous high-level computational studies have predicted rather low stabilities for HSO5 with respect to dissociation into SO3+HO2, and have predicted the net reaction HSO3+OH→SO3+HO2 to be slightly exothermal. However, these studies have not accounted for hydration of HSO5 or its precursor HSO3. In this study, we have estimated the effect of hydration on the stability and lifetime of HSO5 using the advanced quantum chemical methods CCSD(T) and G3B3. We have computed formation energies and free energies for mono- and dihydrates of OH, HSO3, HSO5, SO3 and HO2, and also reanalyzed the individual steps of the HSO3+O2→HSO5→SO3+HO2 reaction at a higher level of theory than previously published. Our results indicate that hydration is likely to significantly prolong the lifetime of the HSO5 intermediate in atmospheric conditions, thus increasing the probability of reactions that form products with more than one sulfur atom. Kinetic modeling indicates that these results may help explain the experimental observations that a mixture of sulfur-containing products formed from SO2 oxidation by OH radicals nucleates much more effectively than sulfuric acid taken from a liquid reservoir

Field measurements of hygroscopic properties and state of mixing of nucleation mode particles

International audienceAn Ultrafine Tandem Differential Mobility Analyser (UF-TDMA) has been used in several field campaigns over the last few years. The investigations were focused on the origin and properties of nucleation event aerosols, which are observed frequently in various environments. This paper gives a summary of the results of 10 nm and 20 nm particle hygroscopic properties from different measurement sites: an urban site, an urban background site and a forest site in Finland and a coastal site in western Ireland. The data can be classified in four hygroscopic growth classes: hydrofobic, less-hygroscopic, more-hygroscopic and sea-salt. Similar classification has been earlier presented for Aitken and accumulation mode particles. In urban air, the summertime 10 nm particles showed varying less-hygroscopic growth behaviour, while winter time 10 nm and 20 nm particles were externally mixed with two different hygroscopic growth modes. The forest measurements revealed diurnal behaviour of hygroscopic growth, with high growth factors at day time and lower during night. The urban background particles had growth behaviour similar to the urban and forest measurement sites depending on the origin of the observed particles. The coastal measurements were strongly affected by air mass history. Both 10 nm and 20 nm particles were hygroscopic in marine background air. The 10 nm particles produced during clean nucleation burst periods were hydrofobic. Diurnal variation and higher growth factors of 10 nm particles were observed in air affected by other source regions. External mixing was occasionally observed at all the sites, but incidents with more than two growth modes were extremely rare

Field measurements of hygroscopic properties and state of mixing of nucleation mode particles

An Ultrafine Tandem Differential Mobility Analyser (UF-TDMA) has been used in several field campaigns over the last few years. The investigations were focused on the origin and properties of nucleation event aerosols, which are observed frequently in various environments. This paper gives a summary of the results of 10 nm and 20 nm particle hygroscopic properties from different measurement sites: an urban site, an urban background site and a forest site in Finland and a coastal site in western Ireland. The data can be classified in four hygroscopic growth classes: hydrofobic, less-hygroscopic, more-hygroscopic and sea-salt. Similar classification has been earlier presented for Aitken and accumulation mode particles. In urban air, the summertime 10 nm particles showed varying less-hygroscopic growth behaviour, while winter time 10 nm and 20 nm particles were externally mixed with two different hygroscopic growth modes. The forest measurements revealed diurnal behaviour of hygroscopic growth, with high growth factors at day time and lower during night. The urban background particles had growth behaviour similar to the urban and forest measurement sites depending on the origin of the observed particles. The coastal measurements were strongly affected by air mass history. Both 10 nm and 20 nm particles were hygroscopic in marine background air. The 10 nm particles produced during clean nucleation burst periods were hydrofobic. Diurnal variation and higher growth factors of 10 nm particles were observed in air affected by other source regions. External mixing was occasionally observed at all the sites, but incidents with more than two growth modes were extremely rare

Modelling Ag-particle activation and growth in a TSI WCPC model 3785

In this work, we modelled activation and growth of silver particles in the water-operated TSI model 3785 water condensation particle counter (WCPC). Our objective was to investigate theoretically how various effects influence the counting efficiency of this CPC. Coupled fluid and particle dynamic processes were modelled with the computational fluid dynamics (CFD) code FLUENT in combination with the Fine Particle Model (FPM) to obtain profiles of temperature, vapour concentration, nucleation rate, and particle size. We found that the counting efficiency of the TSI 3785 for small particles might be affected by the presence of larger particles. Moreover, homogeneous nucleation processes can significantly influence counting efficiency

Modelling Ag-particle activation and growth in a TSI WCPC model 3785

In this work, we modelled activation and growth of silver particles in the water-operated TSI model 3785 water condensation particle counter (WCPC). Our objective was to investigate theoretically how various effects influence the counting efficiency of this CPC. Coupled fluid and particle dynamic processes were modelled with the computational fluid dynamics (CFD) code FLUENT in combination with the Fine Particle Model (FPM) to obtain profiles of temperature, vapour concentration, nucleation rate, and particle size. We found that the counting efficiency of the TSI 3785 for small particles might be affected by the presence of larger particles. Moreover, homogeneous nucleation processes can significantly influence counting efficiency

Calibration of LACIS as a CCN detector and its use in measuring activation and hygroscopic growth of atmospheric aerosol particles

A calibration for LACIS (Leipzig Aerosol Cloud Interaction Simulator) for its use as a CCN (cloud condensation nuclei) detector has been developed. For this purpose, sodium chloride and ammonium sulfate particles of known sizes were generated and their grown sizes were detected at the LACIS outlet. From these signals, the effective critical super-saturation was derived as a function of the LACIS wall temperature. With this, LACIS is calibrated for its use as a CCN detector. The applicability of LACIS for measurements of the droplet activation, and also of the hygroscopic growth of atmospheric aerosol particles was tested. The activation of the urban aerosol particles used in the measurements was found to occur at a critical super-saturation of 0.46% for particles with a dry diameter of 75 nm, and at 0.42% for 85 nm, respectively. Hygroscopic growth was measured for atmospheric aerosol particles with dry diameters of 150, 300 and 350 nm at relative humidities of 98 and 99%, and it was found that the larger dry particles contained a larger soluble volume fraction of about 0.85, compared to about 0.6 for the 150 nm particles

Intrinsic parton motion soft mechanisms and the longitudinal spin asymmetry A_LL in high energy pp -> pi X

The longitudinal double spin asymmetry A_LL in the reaction pp --> pi X has been measured at RHIC with extremely interesting consequences. If the gluon polarization in a proton were as big as needed to resolve the famous "spin crisis" then A_LL would be large and positive. Latest RHIC results indicate that A_LL is small and disfavour large positive values of the gluon polarization. We examine whether the soft mechanisms (Collins, Sivers, Boer-Mulders), essential for generating transverse single spin asymmetries, have any significant influence on A_LL, and whether they could alter the conclusion that the gluon polarization is necessarily small. It turns out that the contribution from these effects is essentially negligible.Comment: RevTeX, 9 pages, 3 eps figures. Revised and shortened version; title slightly modified; figs. 3,4 removed; a new figure for the unpol. cross section added; no changes in results and conclusions; matches the published versio

Longitudinally Polarized Photoproduction of Inclusive Hadrons Beyond the Leading Order

We present a complete next-to-leading order QCD calculation for single-inclusive large-pT hadron production in longitudinally polarized lepton-nucleon collisions, consistently including ``direct'' and ``resolved'' photon contributions. This process could be studied experimentally at a future polarized lepton-proton collider like eRHIC at BNL. We examine the sensitivity of such measurements to the so far completely unknown parton content of circularly polarized photons.Comment: 15 pages, 7 eps figure

Exploring the polarization of gluons in the nucleon

We give an overview of the current status of investigations of the polarization of gluons in the nucleon. We describe some of the physics of the spin-dependent gluon parton distribution and its phenomenology in high-energy polarized hadronic scattering. We also review the recent experimental results.Comment: 10 pages, 13 figures. Talk presented at the "Second Meeting of the APS Topical Group on Hadronic Physics", Nashville, Tennessee, October 22-24, 2006. Reference adde

Surface roughness during depositional growth and sublimation of ice crystals

Full version of an earlier discussion paper (Chou et al. 2018)Ice surface properties can modify the scattering properties of atmospheric ice crystals and therefore affect the radiative properties of mixed-phase and cirrus clouds. The Ice Roughness Investigation System (IRIS) is a new laboratory setup designed to investigate the conditions under which roughness develops on single ice crystals, based on their size, morphology and growth conditions (relative humidity and temperature). Ice roughness is quantified through the analysis of speckle in 2-D light-scattering patterns. Characterization of the setup shows that a supersaturation of 20 % with respect to ice and a temperature at the sample position as low as-40 °C could be achieved within IRIS. Investigations of the influence of humidity show that higher supersaturations with respect to ice lead to enhanced roughness and irregularities of ice crystal surfaces. Moreover, relative humidity oscillations lead to gradual ratcheting-up of roughness and irregularities, as the crystals undergo repeated growth-sublimation cycles. This memory effect also appears to result in reduced growth rates in later cycles. Thus, growth history, as well as supersaturation and temperature, influences ice crystal growth and properties, and future atmospheric models may benefit from its inclusion in the cloud evolution process and allow more accurate representation of not just roughness but crystal size too, and possibly also electrification properties.Peer reviewe