Uusien pienhiukkasten muodostuminen ja kasvu sekä hiukkasten lukumääräkokojakaumassa havaittavat kutistumistapahtumat läntisessä Saudi-Arabiassa

Ilmakehän aerosolihiukkasilla on merkittäviä vaikutuksia ilmastoon ja ihmisten terveyteen. Suuri osa näistä aerosolihiukkasista on peräisin uusien pienhiukkasten muodostumistapahtumista eli NPF-tapahtumista (New Particle Formation). NPF-tapahtumissa ilmakehän höyryistä muodostuu pienhiukkasia, jotka alkavat kasvaa. Tämä tutkielma käsittelee läntisessä Saudi-Arabiassa tehdyissä aerosolimittauksissa havaittuja NPF-tapahtumia. Tarkoituksena on määrittää NPF-tapahtumien yleisyys sekä näiden voimakkuutta ja siten ilmasto- ja terveysvaikutuksellista potentiaalia kuvaavat muodostumis- ja kasvunopeudet. Lisäksi erityisen mielenkiinnon kohteena ovat nk. kutistumistapahtumat, joissa NPF-tapahtumissa syntyneiden hiukkasten moodin keskimääräisen halkaisijan havaitaan pienenevän kasvuvaiheen jälkeen. NPF-tapahtumien tunnistaminen sekä muodostumis- ja kasvunopeuksien määrittäminen perustuivat aerosolihiukkasten lukumääräkokojakaumamittausten analysointiin. Muodostumisnopeudet laskettiin vuomenetelmällä ja kasvunopeudet seuraamalla automaattisesta moodisovitusalgoritmista saatujen halkaisijoiden aikakehitystä. NPF-tapahtumien tunnistaminen perustui lukumääräkokojakaumien visuaaliseen tarkasteluun. NPF-tapahtumien piirteisiin vaikuttavia tekijöitä selvitettiin lähinnä käytettävissä olevien meteorologisten suureiden mittausten sekä dispersiomallilla laskettujen ilmamassojen lähdealueiden avulla. Lukumääräkokojakaumamittausten analysointi osoitti, että NPF-tapahtumat ovat tarkastellulla mittauspaikalla hyvin yleisiä ja voimakkaita. NPF-päivien esiintymistiheys oli 73 % luokitelluista päivistä (454 kpl) ja keskimääräiset muodostumis- ja kasvunopeudet olivat 13,5 cm-3 s-1 (J7nm) ja 8,2 nm h-1 (GR7-12nm). 76 %:ssa NPF-tapahtumista havaittiin lisäksi kutistumistapahtuma. Kutistumistapahtumien esiintymistiheys sekä muodostumis- ja kasvunopeudet olivat hieman suurempia kesäkuukausina, kun taas NPF-tapahtumien yleisyydellä ei ollut selkeää vuodenaikaisvaihtelua. NPF-tapahtumat ja niiden voimakkuus ovat mitä todennäköisimmin riippuvaisia rannikon puolelta kulkeutuvista antropogeenisistä päästöistä. Tähän viittaa erityisesti se, että pienhiukkasten muodostumista ei havaittu lainkaan sisämaasta peräisin olevissa ilmamassoissa. Kutistumistapahtumat eivät vaikuttaneet olevan yhteydessä hiukkasten haihtumista lisääviin tekijöihin (lämpötilan kasvu, ilmamassojen sekoittuminen). Ilmamassojen lähdealueiden ja antropogeenisten päästöjen horisontaalisen jakauman tarkastelu viittasivat puolestaan näennäiseen kutistumisprosessiin. Tässä moodin halkaisijan pieneneminen aiheutuisi haihtumisen sijaan heikommista NPF-tapahtumista peräisin olevien, ja siten vähemmän kasvaneiden hiukkasten havaitsemisesta

Urban Aerosol Particle Size Characterization in Eastern Mediterranean Conditions

Characterization of urban particle number size distribution (PNSD) has been rarely reported/performed in the Middle East. Therefore, we aimed at characterizing the PNSD (0.01–10 µm) in Amman as an example for an urban Middle Eastern environment. The daily mean submicron particle number concentration (PNSub) was 6.5 × 103–7.7 × 104 cm−3 and the monthly mean coarse mode particle number concentration (PNCoarse) was 0.9–3.8 cm−3 and both had distinguished seasonal variation. The PNSub also had a clear diurnal and weekly cycle with higher concentrations on workdays (Sunday–Thursday; over 3.3 × 104 cm−3) than on weekends (below 2.7 × 104 cm−3). The PNSub constitute of 93% ultrafine fraction (diameter < 100 nm). The mean particle number size distributions was characterized with four well-separated submicron modes (Dpg,I, Ni): nucleation (22 nm, 9.4 × 103 cm−3), Aitken (62 nm, 3.9 × 103 cm−3), accumulation (225 nm, 158 cm−3), and coarse (2.23 µm, 1.2 cm−3) in addition to a mode with small geometric mean diameter (GMD) that represented the early stage of new particle formation (NPF) events. The wind speed and temperature had major impacts on the concentrations. The PNCoarse had a U-shape with respect to wind speed and PNSub decreased with wind speed. The effect of temperature and relative humidity was complex and require further investigations

Characterization of Urban New Particle Formation in Amman—Jordan

We characterized new particle formation (NPF) events in the urban background of Amman during August 2016–July 2017. The monthly mean of submicron particle number concentration was 1.2 × 104–3.7 × 104 cm−3 (exhibited seasonal, weekly, and diurnal variation). Nucleation mode (10–15 nm) concentration was 0.7 × 103–1.1 × 103 cm−3 during daytime with a sharp peak (1.1 × 103–1.8 × 103 cm−3) around noon. We identified 110 NPF events (≈34% of all days) of which 55 showed a decreasing mode diameter after growth. The NPF event occurrence was higher in summer than in winter, and events were accompanied with air mass back trajectories crossing over the Eastern Mediterranean. The mean nucleation rate (J10) was 1.9 ± 1.1 cm−3 s−1 (monthly mean 1.6–2.7 cm−3 s−1) and the mean growth rate was 6.8 ± 3.1 nm/h (4.1–8.8 nm/h). The formation rate did not have a seasonal pattern, but the growth rate had a seasonal variation (maximum around August and minimum in winter). The mean condensable vapor source rate was 4.1 ± 2.2 × 105 molecules/cm3 s (2.6–6.9 × 105 molecules/cm3 s) with a seasonal pattern (maximum around August). The mean condensation sink was 8.9 ± 3.3 × 10−3 s−1 (6.4–14.8 × 10−3 s−1) with a seasonal pattern (minimum around June and maximum in winter)

The isotropic Compton profile difference across the phase transition of VO2_2

We studied the isotropic Compton profile of the prototypical oxide VO$_2$ across the temperature induced electronic and structural phase transition at T$_C$ $\approx$ 340 K. We show that the phase transition leaves an observable signal, which facilitates Compton scattering studies of electronic structure and phase transitions in complex solids in powder form. We compare the experimental results with density functional theory calculations and find agreement in the shape of the difference profile, although the amplitude of the observed features is overestimated. The origin of the disagreement is discussed and we argue that it mainly originates mostly correlation effects beyond our current calculations and possibly to some extent, from thermal motion

Density functional simulation of resonant inelastic X-ray scattering experiments in liquids : acetonitrile

In this paper we report an experimental and computational study of liquid acetonitrile (H3C-C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C-C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.In this paper we report an experimental and computational study of liquid acetonitrile (H3C-C equivalent to N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C-C equivalent to NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.Peer reviewe

Measurement report : New particle formation characteristics at an urban and a mountain station in northern China

Atmospheric new particle formation (NPF) events have attracted increasing attention for their contribution to the global aerosol number budget and therefore their effects on climate, air quality and human health. NPF events are regarded as a regional phenomenon, occurring over a large area. Most observations of NPF events in Beijing and its vicinity were conducted in populated areas, whereas observations of NPF events on mountaintops with low anthropogenic emissions are still rare in China. The spatial variation of NPF event intensity has not been investigated in detail by incorporating both urban areas and mountain measurements in Beijing. Here, we provide NPF event characteristics in summer 2018 and 2019 at urban Beijing and a comparison of NPF event characteristics - NPF event frequency, formation rate and growth rate - by comparing an urban Beijing site and a background mountain site separated by similar to 80 km from 14 June to 14 July 2019, as well as giving insights into the connection between both locations. During parallel measurements at urban Beijing and mountain background areas, although the median condensation sink during the first 2 h of the common NPF events was around 0.015(-1) at both sites, there were notable differences in formation rates between the two locations (median of 5.42 cm(-3) s(-1) at the urban site and 1.13 cm(-3) s(-1) at the mountain site during the first 2 h of common NPF events). In addition, the growth rates in the 7-15 nm range for common NPF events at the urban site (median of 7.6 nm h(-1)) were slightly higher than those at the mountain site (median of 6.5 nm h(-1)). To understand whether the observed events were connected, we compared air mass trajectories as well as meteorological conditions at both stations. Favorable conditions for the occurrence of regional NPF events were largely affected by air mass transport. Overall, our results demonstrate a clear inhomogeneity of regional NPF within a distance of similar to 100 km, possibly due to the discretely distributed emission sources.Peer reviewe

Exciton energy-momentum map of hexagonal boron nitride

Understanding and controlling the way excitons propagate in solids is a key for tailoring materials with improved optoelectronic properties. A fundamental step in this direction is the determination of the exciton energy-momentum dispersion. Here, thanks to the solution of the parameter-free Bethe- Salpeter equation (BSE), we draw and explain the exciton energy-momentum map of hexagonal boron nitride (h-BN) in the first three Brillouin zones. We show that h-BN displays strong excitonic effects not only in the optical spectra at vanishing momentum $\mathbf{q}$, as previously reported, but also at large $\mathbf{q}$. We validate our theoretical predictions by assessing the calculated exciton map by means of an inelastic x-ray scattering (IXS) experiment. Moreover, we solve the discrepancies between previous experimental data and calculations, proving then that the BSE is highly accurate through the whole momentum range. Therefore, these results put forward the combination BSE and IXS as the tool of choice for addressing the exciton dynamics in complex materials.Understanding and controlling the way excitons propagate in solids is a key for tailoring materials with improved optoelectronic properties. A fundamental step in this direction is the determination of the exciton energy-momentum dispersion. Here, thanks to the solution of the parameter-free Bethe-Salpeter equation (BSE), we draw and explain the exciton energy-momentum map of hexagonal boron nitride (h-BN) in the first three Brillouin zones. We show that h-BN displays strong excitonic effects not only in the optical spectra at vanishing momentum q, as previously reported, but also at large q. We validate our theoretical predictions by assessing the calculated exciton map by means of an inelastic x-ray scattering (IXS) experiment. Moreover, we solve the discrepancies between previous experimental data and calculations, proving then that the BSE is highly accurate through the whole momentum range. Therefore, these results put forward the combination BSE and IXS as the tool of choice for addressing the exciton dynamics in complex materials.Peer reviewe

Size-resolved particle number emissions in Beijing determined from measured particle size distributions

The climate and air quality effects of aerosol particles depend on the number and size of the particles. In urban environments, a large fraction of aerosol particles originates from anthropogenic emissions. To evaluate the effects of different pollution sources on air quality, knowledge of size distributions of particle number emissions is needed. Here we introduce a novel method for determining size-resolved particle number emissions, based on measured particle size distributions. We apply our method to data measured in Beijing, China, to determine the number size distribution of emitted particles in a diameter range from 2 to 1000 nm. The observed particle number emissions are dominated by emissions of particles smaller than 30 nm. Our results suggest that traffic is the major source of particle number emissions with the highest emissions observed for particles around 10 nm during rush hours. At sizes below 6 nm, clustering of atmospheric vapors contributes to calculated emissions. The comparison between our calculated emissions and those estimated with an integrated assessment model GAINS (Greenhouse Gas and Air Pollution Interactions and Synergies) shows that our method yields clearly higher particle emissions at sizes below 60 nm, but at sizes above that the two methods agree well. Overall, our method is proven to be a useful tool for gaining new knowledge of the size distributions of particle number emissions in urban environments and for validating emission inventories and models. In the future, the method will be developed by modeling the transport of particles from different sources to obtain more accurate estimates of particle number emissions.Peer reviewe

Influence of organic aerosol molecular composition on particle absorptive properties in autumn Beijing

Publisher Copyright: © 2022 Jing Cai et al.Organic aerosol (OA) is a major component of fine particulate matter (PM), affecting air quality, human health, and the climate. The absorptive and reflective behavior of OA components contributes to determining particle optical properties and thus their effects on the radiative budget of the troposphere. There is limited knowledge on the influence of the molecular composition of OA on particle optical properties in the polluted urban environment. In this study, we characterized the molecular composition of oxygenated OA collected on filter samples in the autumn of 2018 in Beijing, China, with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). Three haze episodes occurred during our sampling period with daily maximum concentrations of OA of 50, 30, and 55 μg m-3. We found that the signal intensities of dicarboxylic acids and sulfur-containing compounds increased during the two more intense haze episodes, while the relative contributions of wood-burning markers and other aromatic compounds were enhanced during the cleaner periods. We further assessed the optical properties of oxygenated OA components by combining detailed chemical composition measurements with collocated particle light absorption measurements. We show that light absorption enhancement (Eabs) of black carbon (BC) was mostly related to more oxygenated OA (e.g., dicarboxylic acids), likely formed in aqueous-phase reactions during the intense haze periods with higher relative humidity, and speculate that they might contribute to lensing effects. Aromatics and nitro-aromatics (e.g., nitrocatechol and its derivatives) were mostly related to a high light absorption coefficient (babs) consistent with light-absorbing (brown) carbon (BrC). Our results provide information on oxygenated OA components at the molecular level associated with BrC and BC particle light absorption and can serve as a basis for further studies on the effects of anthropogenic OA on radiative forcing in the urban environment.Peer reviewe