The Effect of Using a New Parameterization of Nucleation in the WRF-Chem Model on New Particle Formation in a Passive Volcanic Plume

We investigated the role of the passive volcanic plume of Mount Etna (Italy) in the formation of new particles in the size range of 2.5–10 nm through the gas-to-particle nucleation of sulfuric acid (H2SO4) precursors, formed from the oxidation of SO2, and their evolution to particles with diameters larger than 100 nm. Two simulations were performed using the Weather Research and Forecasting Model coupled with chemistry (WRF-Chem) under the same configuration, except for the nucleation parameterization implemented in the model: the activation nucleation parameterization (JS1 = 2.0 × 10−6 × (H2SO4)) in the first simulation (S1) and a new parameterization for nucleation (NPN) (JS2 = 1.844 × 10−8 × (H2SO4)1.12) in the second simulation (S2). The comparison of the numerical results with the observations shows that, on average, NPN improves the performance of the model in the prediction of the H2SO4 concentrations, newly-formed particles (~2.5–10 nm), and their growth into larger particles (10–100 nm) by decreasing the rates of H2SO4 consumption and nucleation relative to S1. In addition, particles formed in the plume do not grow into cloud condensation nuclei (CCN) sizes (100–215 nm) within a few hours of the vent (tens of km). However, tracking the size evolution of simulated particles along the passive plume indicates the downwind formation of particles larger than 100 nm more than 100 km far from the vent with relatively high concentrations relative to the background (more than 1500 cm−3) in S2. These particles, originating in the volcanic source, could affect the chemical and microphysical properties of clouds and exert regional climatic effects over time.

Synthesis and applications of zinc oxide for removal of various pollutants: A review

The versatility of zinc oxide applications in the removal of various pollutants has attracted a wide interest of researchers in the past decade. Numerous studies reported on zinc oxide synthesis pathways and resulting nanoparticle morphologies, applications, formation mechanisms and synthesis parameters. In this review the reported zinc oxide synthesis methods are classified into chemical, physical and biological routes; they are evaluated in terms of the required chemicals, synthesis conditions and the resulting morphologies and properties of zinc oxide. The chemical route of zinc oxide synthesis covers precipitation, micro-emulsion, solgel, solvothermal and hydrothermal paths. The physical route includes laser ablation and high energy ball milling, while the biological route covers plant extracts and microbe mediated synthesis. The mechanisms of zinc oxide formation of the mentioned routes are based on one or more of the following processes: particle nucleation, diffusional growth, Ostwald ripening, particle aggregation and sintering. The most influencing synthesis parameters overall are temperature, drying duration and additives’ effect. Higher temperatures (>200°C) commonly produce larger particles of zinc oxide (> 80 nm); the prolong duration (> 60 min) often results in the agglomeration and sintering of zinc oxide particles. However, additives may mitigate agglomeration extent. Overall, the chemical route is more preferable due to its flexibility that is also linked to the greater variability of zinc oxide particles. The physical method produces more consistent zinc oxide particles but requires higher energy inputs. The biological method is very promising and associated with low chemicals consumptions and good quality of zinc oxide.

Continuous Differential Microemulsion Polymerization to Prepare Nanosized Polymer Latices in Microreactors

Microreactors are a promising platform for continuous synthesis of polymer latices when combined with emulsion polymerization. However, this application has long been haunted by fouling and clogging problems. In this work, we proposed the strategy of conducting differential microemulsion polymerization in microreactors within a biphasic slug flow and achieved rapid and stable preparation of nanosized PMMA latices (polymeric content as high as 15.7% with average particle size smaller than 20 nm). We started by exploring the temperature thresholds with thermal and redox initiation, the effect of initiator concentration, and the kinetic characteristics of microemulsion polymerization at different temperatures. Then, as for the differential microemulsion polymerization, extensive investigation was made into the effects of the volumetric flow ratio, the prepolymerization time, the initiator concentration, and the solid content of the initial microemulsion. Finally, we compared the differential microemulsion polymerization with the soap-free emulsion polymerization in the slug flow. The striking advantages in the polymerization rate, the average particle diameter, and the size distribution reflected higher density of particle nuclei, larger specific surface area of particles, and the pivotal effect of the persistent particle nucleation in the microemulsion polymerization.

Identifying source regions of air masses sampled at the tropical high-altitude site of Chacaltaya using WRF-FLEXPART and cluster analysis

Observations of aerosol and trace gases in the remote troposphere are vital to quantify background concentrations and identify long-term trends in atmospheric composition on large spatial scales. Measurements made at high altitude are often used to study free-tropospheric air; however such high-altitude sites can be influenced by boundary layer air masses. Thus, accurate information on air mass origin and transport pathways to high-altitude sites is required. Here we present a new method, based on the source–receptor relationship (SRR) obtained from backwards WRF-FLEXPART simulations and a k-means clustering approach, to identify source regions of air masses arriving at measurement sites. Our method is tailored to areas of complex terrain and to stations influenced by both local and long-range sources. We have applied this method to the Chacaltaya (CHC) GAW station (5240 m a.s.l.; 16.35∘ S, 68.13∘ W) for the 6-month duration of the “Southern Hemisphere high-altitude experiment on particle nucleation and growth” (SALTENA) to identify where sampled air masses originate and to quantify the influence of the surface and the free troposphere. A key aspect of our method is that it is probabilistic, and for each observation time, more than one air mass (cluster) can influence the station, and the percentage influence of each air mass can be quantified. This is in contrast to binary methods, which label each observation time as influenced by either boundary layer or free-troposphere air masses. Air sampled at CHC is a mix of different provenance. We find that on average 9 % of the air, at any given observation time, has been in contact with the surface within 4 d prior to arriving at CHC. Furthermore, 24 % of the air has been located within the first 1.5 km above ground level (surface included). Consequently, 76 % of the air sampled at CHC originates from the free troposphere. However, pure free-tropospheric influences are rare, and often samples are concurrently influenced by both boundary layer and free-tropospheric air masses. A clear diurnal cycle is present, with very few air masses that have been in contact with the surface being detected at night. The 6-month analysis also shows that the most dominant air mass (cluster) originates in the Amazon and is responsible for 29 % of the sampled air. Furthermore, short-range clusters (origins within 100 km of CHC) have high temporal frequency modulated by local meteorology driven by the diurnal cycle, whereas the mid- and long-range clusters' (>200 km) variability occurs on timescales governed by synoptic-scale dynamics. To verify the reliability of our method, in situ sulfate observations from CHC are combined with the SRR clusters to correctly identify the (pre-known) source of the sulfate: the Sabancaya volcano located 400 km north-west from the station.

Investigation of Thermophysical Properties of Nanomagnetite-based Polymer Materials

In this work, samples of magnetite nanoparticles are synthesized using various synthetic methods. It is shown that of the existing methods of magnetite synthesis, the most widespread is the method of coprecipitation of Fe2+ and Fe3+ salts. Less common, but of interest due to the slower and more controlled kinetics of particle nucleation, is the Fe2+ oxidation method. However, magnetite is unstable and under external influences its phase transition to maghemite can occur, which leads to a change in magnetic characteristics and a change in biological responses. After analyzing the results of the study of samples by the XRD method, the following conclusions can be drawn: The magnetite phase was identified by the characteristic peaks in the diffraction patterns for all samples, except for the sample with EDTA, which may be a consequence of an insufficient amount of the introduced oxidant, or poor diffusion of the oxidant to iron ions due to the formed chelate complex. It can be concluded that magnetite is a promising material for its use in industry and medicine.

The SALTENA experiment: Comprehensive observations of aerosol sources, formation and processes in the South American Andes

This paper presents an introduction to the Southern hemisphere high altitude experiment on particle nucleation and growth (SALTENA). This field campaign took place between December 2017 and June 2018 (wet to dry season) at Chacaltaya (CHC), a GAW (Global Atmosphere Watch) station located at 5240 m a.s.l. in the Bolivian Andes. Concurrent measurements were conducted at two additional sites in El Alto (4000 m a.s.l.) and La Paz (3600 m a.s.l.). The overall goal of the campaign was to identify the sources, understand the formation mechanisms and transport, and characterize the properties of aerosol at these stations. State-of-the-art instruments were brought to the station complementing the ongoing permanent GAW measurements, to allow a comprehensive description of the chemical species of anthropogenic and biogenic origin impacting the station and contributing to new particle formation. In this overview we first provide an assessment of the complex meteorology, air mass origin, and boundary layer – free troposphere interactions during the campaign using a 6-month high-resolution WRF (Weather Research and Forecasting) simulation coupled with FLEXPART (FLEXible PARTicle dispersion model). We then show some of the research highlights from the campaign, including i) chemical transformation processes of anthropogenic pollution while the air masses are transported to the CHC station from the metropolitan area of La Paz/El Alto, ii) volcanic emissions as an important source of atmospheric sulfur compounds in the region, iii) the characterization of the compounds involved in new particle formation, and iv) the identification of long-range transported compounds from the Pacific or the Amazon basin. We conclude the article with a presentation of future research foci. The SALTENA dataset highlights the importance of comprehensive observations in strategic high-altitude locations, especially the undersampled Southern Hemisphere.

Formation of oxidized gases and secondary organic aerosol from a commercial oxidant-generating electronic air cleaner

Airborne virus transmission during the COVID-19 pandemic increased the demand for indoor air cleaners. While some commercial electronic air cleaners could be effective in reducing primary pollutants and inactivating bioaerosol, studies on the formation of secondary products from oxidation chemistry during their use are limited. Here, we measured oxygenated volatile organic compounds (OVOCs) and the chemical composition of particles generated from a hydroxyl radical generator in an office. During operation, enhancements in OVOCs, especially low-molecular-weight organic and inorganic acids, were detected. Rapid increases in particle number and volume concentrations were observed, corresponding to the formation of highly-oxidized secondary organic aerosol (SOA) (O:C ~1.3). The organic mass spectra showed an enhanced signal at m/z 44 (CO2+) and the aerosol evolved with a slope of ~ -1 in the Van Krevelen diagram. These results suggest that organic acids generated during VOC oxidation contributed to particle nucleation and SOA formation. Nitrate, sulfate, and chloride also increased during the oxidation without a corresponding increase in ammonium, suggesting organic nitrate, organic sulfate, and organic chloride formation. As secondary species are reported to have detrimental health effects, further studies are needed to evaluate potential OVOCs and SOA formation from electronic air cleaners in different indoor environments.

High Homogeneous Freezing Onsets of Sulfuric Acid Aerosol at Cirrus Temperatures

Homogeneous freezing of aqueous solution aerosol particles is an important process for cloud ice formation in theupper troposphere. There the air temperature is low, the ice supersaturation can be high, and the concentration of ice-nucleating particles is too low to initiate and dominate cirrus cloud formation by heterogeneous ice nucleation processes. The most common description to quantify homogeneous freezing processes is based on the water activity criterion (WAC) as proposed by Koop et al. (2000). The WAC describes the homogeneous nucleation rate coefficients only as a function of the water activity, temperature and size of the aqueous aerosol particles, which makes this approach well applicable in numerical models. In this study, we investigate the homogeneous freezing behaviour of aqueous sulfuric acid aerosol particles by means of a comprehensive collection of laboratory homogeneous freezing experiments conducted at the AIDA (Aerosol Interaction and Dynamicsin the Atmosphere) cloud simulation chamber, which were conducted as part of 17 measurement campaigns since 2007. The most recent experiments were conducted during October 2020 with special emphasis on temperatures below 200 K. Aqueous sulfuric acid aerosol particles were generated at high purity by particle nucleation in a gas flow composed of clean synthetic air and sulfuric acid vapor, which was added to the AIDA chamber. The resulting chamber aerosol had number concentrations from 30 cm−3 up to several 1000 cm−3 with particle diameters ranging from about 30 nm to 1.1 μm. Homogeneous freezing of the aerosol particles was measured at simulated cirrus formation conditions in a wide range of temperatures between 185 K and 230 K with a steady increase of relative humidity during each experiment. At temperatures between about 205 K and about 230 K, the AIDA results agree well with the WAC-based predictions of homogeneous freezing onsets. At lower temperatures, however, the AIDA results show an increasing deviation from the WAC-based predictions towards higher freezing onsets. For temperatures between 185 K and 205 K, the WAC-based ice saturation ratios for homogeneous freezing onsets increase from about 1.6 to 1.7, whereas the AIDA measurements show an increase from about 1.7 to 2.0 in the same temperature range. Based on our experimental results, we suggest a new fit line as a parameterization for the onset conditions of homogeneous freezing of sulfuric acid aerosol particles. As a next step, we propose the new parameterization to be implemented in atmospheric models as an improved version of the WAC-based parameterization from Koop et al. (2000). The new homogeneous freezing thresholds may have significant impacts on the prediction of cirrus cloud occurrence and related cloud radiative effects.

Identifying source regions of air masses sampled at the tropical high-altitude site of Chacaltaya using WRF-FLEXPART and cluster analysis

Observations of aerosol and trace gases in the remote troposphere are vital to quantify background concentrations and identify long term trends in atmospheric composition on large spatial scales. Measurements made at high altitude are often used to study free tropospheric air however such high-altitude sites can be influenced by boundary layer air masses. Thus, accurate information on air mass origin and transport pathways to high altitude sites is required. Here we present a new method, based on the source-receptor relationship (SRR) obtained from backwards WRF-FLEXPART simulations and a k-means clustering approach, to identify source regions of air masses arriving at measurement sites. Our method is tailored to areas of complex terrain and to stations influenced by both local and long-range sources. We have applied this method to the Chacaltaya (CHC) GAW station (5240 m a.s.l.,16.35° S, 68.13° W) for the 6-month duration of the “Southern hemisphere high altitude experiment on particle nucleation and growth” (SALTENA) to identify where sampled air masses originate and to quantify the influence of the boundary layer and the free troposphere. A key aspect of our method is that it is probabilistic and for each observation time, more than one air mass (cluster) can influence the station and the percentage influence of each air mass can be quantified. This is in contrast to binary methods, which label each observation time as influenced either by boundary layer or free troposphere air masses. We find that on average, 9% of the air sampled at CHC, at any given observation time, has been in contact with the surface within 4 days prior to arriving at CHC, 24% of the air was located below 1.5 km above ground level and consequently, 76% of the measured air masses at CHC represent free tropospheric air. However, pure free-tropospheric influences are rare and often samples are concurrently influenced by both boundary-layer and free-tropospheric air masses. A clear diurnal cycle is present with very few air masses that have been in contact with the surface being detected at night. The 6-month analysis also shows that the most dominant air mass (cluster) originates in the Amazon and is responsible for 29% of the sampled air. Furthermore, short-range clusters (origins within 100 km of CHC) have high temporal frequency modulated by local meteorology driven by the diurnal cycle whereas the mid- and long-range clusters’ (>200 km) variability occurs on timescales governed by synoptic-scale dynamics. To verify the reliability of our method, in-situ sulfate observations from CHC are combined with the SRR clusters to correctly identify the (pre-known) source of the sulfate: the Sabancaya volcano located 400 km northwest from the station.

Stratospheric chemistry and aerosol modeling in CAMS with the IFS-CB05-BASCOE-GLOMAP (ICBG) system: evaluation in quiescent conditions and in a volcanic eruption.

<p>We present interactive stratospheric aerosol simulations with the ICBG system, a  global tropospheric-stratospheric combined aerosol-chemistry model which is an extension to the ECMWF Integrated Forecasting System (IFS), and is developed as part of the Copernicus Atmosphere Monitoring Service (CAMS). ICBG is the result of the merging of two existing CAMS configurations of the IFS:</p><ul><li>The IFS-GLOMAP tropospheric-stratospheric aerosol microphysics system, which has the GLOMAP-mode aerosol scheme configured for forecast-cycling experiments within the IFS,</li> <li>The IFS-CB05-BASCOE tropospheric (CB05) – stratospheric (BASCOE) chemistry scheme, which is also an established configuration of the IFS within CAMS.</li> </ul><p>During the first phase of CAMS, the stratospheric chemistry scheme IFS-BASCOE was extended to include the stratospheric sulphur chemistry from the UM-UKCA model, with sulphuric acid production rates from IFS-BASCOE passed each timestep to the aerosol scheme IFS-GLOMAP for aerosol particle nucleation and condensation. The aerosol surface area densities (SAD) simulated by IFS-GLOMAP simulated are similarly passed each timestep to the stratospheric chemistry scheme IFS-BASCOE for  heterogeneous reactions. In a recent progression of this strato-tropospheric modelling system, the climatology for meteoric smoke particles (MSP) used in UM-UKCA has also been implemented. Thus the simulated stratospheric aerosol layer comprises not only pure sulphuric particles nucleated homogeneously but also meteoric-sulphuric particles formed from the MSPs.</p><p>We  evaluate the simulated stratosphere aerosol layer in quiescent conditions, comparing it to SAGE-II measurements from the 1998-2002 period. The simulated stratospheric sulfate burden, aerosol extinction, stratospheric aerosol optical depth (sAOD) and surface area density (SAD) agree well with the SAGE-II retrievals. We also show results from ICBG simulations of the volcanic aerosol cloud from a large-magnitude tropical eruption (Pinatubo, June 1991, VEI6) and a medium-magnitude eruption at a northern mid-latitude (Raikoke, June 2019, VEI4).</p>