Secondary Organic Aerosol Formation via Multiphase Reaction of Hydrocarbons in Urban Atmospheres Using the CAMx Model Integrated with the UNIPAR model

The prediction of Secondary Organic Aerosol (SOA) in regional scales is traditionally performed by using gas-particle partitioning models. In the presence of inorganic salted wet aerosols, aqueous reactions of semivolatile organic compounds can also significantly contribute to SOA formation. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model utilizes explicit gas chemistry to better predict SOA mass from multiphase reactions. In this work, the UNIPAR model was incorporated with the Comprehensive Air Quality Model with Extensions (CAMx) to predict the ambient concentration of organic matter (OM) in urban atmospheres during the Korean-United States Air Quality (2016 KORUS-AQ) campaign. The SOA mass predicted with the CAMx-UNIPAR model changed with varying levels of humidity and emissions and in turn, has the potential to improve the accuracy of OM simulations. The CAMx-UNIPAR model significantly improved the simulation of SOA formation under the wet condition, which often occurred during the KORUS-AQ campaign, through the consideration of aqueous reactions of reactive organic species and gas-aqueous partitioning. The contribution of aromatic SOA to total OM was significant during the low-level transport/haze period (24–31 May 2016) because aromatic oxygenated products are hydrophilic and reactive in aqueous aerosols. The OM mass predicted with the CAMx-UNIPAR model was compared with that predicted with the CAMx model integrated with the conventional two product model (SOAP). Based on estimated statistical parameters to predict OM mass, the performance of CAMx-UNIPAR was noticeably better than the conventional CAMx model although both SOA models underestimated OM compared to observed values, possibly due to missing precursor hydrocarbons such as sesquiterpenes, alkanes, and intermediate VOCs. The CAMx-UNIPAR model simulation suggested that in the urban areas of South Korea, terpene and anthropogenic emissions significantly contribute to SOA formation while isoprene SOA minimally impacts SOA formation.

Synthesis, Structure, and Properties of EuLnCuSe3 (Ln = Nd, Sm, Gd, Er)

EuLnCuSe3 (Ln = Nd, Sm, Gd, Er), due to their complex composition, should be considered new materials with the ability to purposefully change the properties. Samples of the EuLnCuSe3 were prepared using Cu, rare earth metal, Se (99.99%) by the ampoule method. The samples were obtained by the crystallization from a melt and annealed at temperatures 1073 and 1273 K. The EuErCuSe3 crystal structure was established using the single-crystal particle. EuErCuSe3 crystallizes in the orthorhombic system, space group Cmcm, KCuZrS3 structure type, with cell parameters a = 4.0555 (3), b = 13.3570 (9), and c = 10.4602 (7) Å, V = 566.62 (6) Å3. In structure EuErCuSe3, erbium ions are coordinated by selenium ions in the octahedral polyhedron, copper ions are in the tetrahedral coordination, europium ions are between copper and erbium polyhedra layers and are coordinated by selenium ions as two-cap trigonal prisms. The optical band gap is 1.79 eV. At 4.7 K, a transition from the ferrimagnetic state to the paramagnetic state was detected in EuErCuSe3. At 85 and 293 K, the compound is in a paramagnetic state. According to XRPD data, EuLnCuSe3 (Ln = Nd, Sm, Gd) compounds have a Pnma orthorhombic space group of the Eu2CuS3 structure type. For EuSmCuSe3, a = 10.75704 (15) Å, b = 4.11120 (5) Å, c = 13.37778 (22) Å. In the series of EuLnCuSe3 compounds, the optical band gap increases 1.58 eV (Nd), 1.58 eV (Sm), 1.72 eV (Gd), 1.79 eV (Er), the microhardness of the 205 (Nd), 210 (Sm), 225 (Gd) 235 ± 4 HV (Er) phases increases, and the thermal stability of the phases increases significantly. According to the measurement data of differential scanning calorimetry, the EuNdCuSe3 decomposes, according to the solid-phase reaction T = 1296 K, ΔH = 8.2 ± 0.8 kJ/mol. EuSmCuSe3 melts incongruently T = 1449 K, ΔH = 18.8 ± 1.9 kJ/mol. For the EuGdCuSe3, two (Tα↔β = 1494 K, ΔHα↔β = 14.8 kJ/mol, Tβ↔γ = 1530 K, ΔHβ↔γ = 4.8 kJ/mol) and for EuErCuSe3 three polymorphic transitions (Tα↔β = 1561 K, ΔHα↔β = 30.3 kJ/mol, Tβ↔γ = 1579 K, ΔHβ↔γ = 4.4 kJ/mol, and Tγ↔δ = 1600 K, ΔHγ↔δ = 10.1 kJ/mol). The compounds melt incongruently at the temperature of 1588 K, ΔHmelt = 17.9 ± 1.8 kJ/mol and 1664 K, ΔHmelt = 25.6 ± 2.5 kJ/mol, respectively. Incongruent melting of the phases proceeds with the formation of a solid solution of EuSe and a liquid phase.

Porosity Effect of the Silver Catalyst in Hydrogen Peroxide Monopropellant Thruster

In monopropellant system, hydrogen peroxide is used with catalyst to create an exothermic reaction. Catalyst made of silver among the popular choice for this application. Since the catalyst used is in porous state, the effect of its porosity in the hydrogen peroxide monopropellant thruster performances is yet unknown. The porosity changes depending on factors including catalyst pact compaction pressure, bed dimension, and type of catalyst used. As researches on this topic is relatively small, the optimum porosity value is usually left out. The performance of the thruster indicated by the pressure drop across the catalyst bed. Porosity of the catalyst bed adds additional momentum sink to the momentum equation that contributes to the pressure gradient which lead to pressure loss inside thruster. The effect of porosity influences the performance and precision of the thruster. Study of the pressure drop by the catalyst bed requires a lengthy period and expensive experiments, however, numerical simulation by mean of Computational Fluid Dynamics (CFD) can be an alternative. In this paper, 90 wt% hydrogen peroxide solution with silver catalyst is studied in order to investigate the influence of porosity to the performances of the thruster, and to find the optimum porosity of the thruster. Species transport model is applied in the single-phase reaction simulation using the EDM for turbulence-chemistry interaction. Through this study, the effect of porosity towards the thruster performances represented in term of pressure drop, exit velocity, bed temperature, and thrust, and porosity of 0.4 found to be as an optimal value.

Red Carbon: a Carbon-Oxygen-based covalent semiconductor for selective amine sensing

The requirements for organic semiconductor materials and new methods for their synthesis at low temperature have risen over the last decades, especially due to concerns of sustainability. Herein, we present an innovative method for the synthesis of a so-called “red carbon” thin film, being composed of carbon and oxygen, only. This material was already described by Kappe and Ziegler at the beginning of the 20th century, but now can complement the current research on covalent organic semiconductor materials. The herein described red carbon can be homogeneous deposited on glass substrates as thin ilms which reveal a highly ordered structure. The films are highly reactive towards amines and were employed as amine vapor sensors for a scope of analogous amines. The gas-to-solid phase reaction causes a significant change of the films optical properties in all cases, blue-shifting the bandgap and the photoluminescence spectra from the red to the near UV range. The irreversible chemical reaction between the thin film and the vapor was also exploited for the preparation of nitrogen containing thin carbon films. We expect the herein presented red carbon material is of interest not only for sensing applications, but also in optoelectronics.

Chemical Transformation of α-Pinene derived Organosulfate via Heterogeneous OH Oxidation: Implications for Sources and Environmental Fates of Atmospheric Organosulfates

Organosulfur compounds are found to be ubiquitous in atmospheric aerosols — a majority of which are expected to be organosulfates (OSs). Given the atmospheric abundance of OSs, and their potential to form a variety of reaction products upon ageing, it is imperative to study the transformation kinetics and chemistry of OSs to better elucidate their atmospheric fates and impacts. In this work, we investigated the chemical transformation of an α-pinene derived organosulfate (C10H17O5SNa, αpOS-249) through heterogeneous OH oxidation at a relative humidity of 50 % in an oxidation flow reactor (OFR). The aerosol-phase reaction products were characterized using the high-performance liquid chromatography-electrospray ionization-high resolution mass spectrometry and the ion chromatography. By monitoring the decay rates of αpOS-249, the effective heterogeneous OH reaction rate was measured to be (6.72 ± 0.55) × 10−13 cm3 molecule−1 s−1. This infers an atmospheric lifetime of about two weeks at an average OH concentration of 1.5 × 106 molecules cm–3. Product analysis shows that OH oxidation of αpOS-249 can yield more oxygenated OSs having a nominal mass-to-charge ratio (m/z) at 247 (C10H15O5S−), 263 (C10H15O6S−), 265 (C10H17O6S−), 277 (C10H13O7S−), 279 (C10H15O7S−), and 281 (C10H17O7S−). The formation of fragmentation products, including both small OSs (C < 10) and inorganic sulfates, is found to be insignificant. These observations suggest that functionalization reactions are likely the dominant processes and that multigenerational oxidation possibly leads to formation of products with one or two hydroxyl and carbonyl functional groups adding to αpOS-249. Furthermore, all product ions except m/z = 277 have been detected in laboratory generated α-pinene derived secondary organic aerosols as well as in atmospheric aerosols. Our results reveal that OSs freshly formed from the photochemical oxidation of α-pinene could react further to form OSs commonly detected in atmospheric aerosols through heterogeneous OH oxidation. Overall, this study provides more insights into the sources, transformation, and fate of atmospheric OSs.

STUDY OF TECHNICAL CELLULOSE AS A MATRIX-SORBENT TO DEVELOP EXPRESS ANALYTIC SYSTEM FOR WATER SAFETY CONTROL

The study presented by the authors is devoted to the study of the properties and the possibility of using technical cellulose from non-wood plant raw materials as a solid-phase matrix to obtain solid-phase reactive indicator systems by the following methods: synthesis method on the base of a hetarylformazane immobilized on a cellulose matrix and development of analytical systems based on preconcentration of the determined metal ion by a matrix with subsequent its «revealing» by the formazan («revealing» method). The article focuses on determination of optimal combinations of chromogenic organic reagents (hetarylformazanes) and cellulose-based matrices for developing solid-phase reaction-based indicator systems. Adsorption features of formazan reagents onto cellulose matrices was studied. It has been established the relation between the reagent molecule structure, composition of cellulose matrix and analytical properties of the test-systems synthesized to determine metal ions. Different approaches were developed and applied to reveal the visually observable and easily measured effect due to cellulose properties as well as properties of hetarylformazanes fixed on the surface of the matrix. This fact allows to control sensitivity and selectivity of solid-phase reactive indicator systems for water quality assessment.

Formation and Evolution of Secondary Particulate Matter During Heavy Haze Pollution Episodes in Northeast China in Winter

Based on the simultaneous observation of fine particulate matter (PM2.5) and its chemical components in four heavy haze pollution episodes at 14 sampling sites in northeast China from 2017 to 2019, the formation and existence of sulfate (SO42-) and nitrate (NO3-) secondary contaminants under different stages of the pollution episodes, and different meteorological and emission conditions were compared. The results yielded three main findings. (1) Organic carbon (OC) was the most important component of PM2.5, followed by NO3-,SO42-,and ammonium (NH4+). Nitrate surpassed sulfate as the most important secondary inorganic component over the study period. (2) The significant increase in atmospheric OC, SO42-, and NO3-concentrations was an important reason for haze formation. Meteorological factors such as wind direction, wind speed, temperature (T), relative humidity (RH), and atmospheric oxidability played an important role in secondary pollutant formation. (3) There were two potential SO42- formation mechanisms. The first was the gas-phase reaction of the hydroxyl radical(OH·) leading to the oxidation of nitrogen dioxide (NO2) and sulfur dioxide (SO2),and high ozone (O3) concentrations. A high atmospheric oxidability and high winter Ts were very important for SO42- formation. The second mechanism occurred under neutral or weakly alkaline conditions when large amounts of SO2 could enter aerosol droplets, and NO2 was more likely to react in the aqueous phase with SO2 to increase the output of SO42-. Nitrate formation was may be mainly due to the homogeneous gas-phase reaction of OH· with NO2, SO2, and ammonia(NH3). The highest NO3 concentration was observed under mild winter Ts, high RH, high atmospheric oxidability (O3 and nitrous acid (HONO)), high NH3 concentrations, and suitable light conditions. The differences in SO42- formation between northeast China and other regions were mainly a result of the suppression of the aqueous reaction of SO42- due to the low T in winter and low-sulfur coal emissions, which resulted in the gas-phase oxidation process with the highest SO42- production capacity becoming an important process. However, the aqueous reaction process was the most common mechanism of SO42- production in northeast China.

Visualizing the three-step freezing process and three-phase reaction not predicted by the (NH4) 2SO4/H2O phase diagram

According to the conventional phase diagrams, aqueous solutions freeze at the liquidus and are frozen/solid below the eutectic solidus. Herein, using differential scanning calorimetry (DSC) and optical cryo-microscopy (OC-M), we demonstrate that hy-poeutectic, eutectic 40 wt% (NH4)2SO4 and hypereutectic (NH4)2SO4/H2O remain liquid well below the eutectic solidus before freezing in three steps: fast-slow-fast. The first fast freezing produces a ramified ice microstructure (IM) and freeze-concentrated solution (FCS) containing up to ~70 wt% (NH4)2SO4. As temperature decreases further, the slow freezing of FCS precedes its fast freezing, which produces a striped IM and (NH4)2SO4 microcrystals. Videos recorded upon warming of frozen (NH4)2SO4/H2O reveal a new three-phase reaction, which is the recrystallization of ice and (NH4)2SO4 microcrystals into the lamellar eutectic ice-(NH4)2SO4 superlattice. This work demonstrates limitations of the (NH4)2SO4/H2O phase diagram and pro-poses an effective strategy for studying other deeply supercooled solutions whose behavior is not predicted by the phase dia-gram.

Numerical Simulation of Gas Phase Reaction for Epitaxial Chemical Vapor Deposition of Silicon Carbide by Methyltrichlorosilane in Horizontal Hot-Wall Reactor

Methyltrichlorosilane (CH3SiCl3, MTS) has good performance in stoichiometric silicon carbide (SiC) deposition and can be facilitated at relatively lower temperature. Simulations of the chemical vapor deposition in the two-dimensional horizontal hot-wall reactor for epitaxial processes of SiC, which were prepared from MTS-H2 gaseous system, were performed in this work by using the finite element method. The chemistry kinetic model of gas-phase reactions employed in this work was proposed by other researchers. The total gas flow rate, temperature, and ratio of MTS/H2 were the main process parameters in this work, and their effects on consumption rate of MTS, molar fraction of intermediate species and C/Si ratio inside the hot reaction chamber were analyzed in detail. The phenomena of our simulations are interesting. Both low total gas flow rate and high substrate temperature have obvious effectiveness on increasing the consumption rate of MTS. For all cases, the highest three C contained intermediates are CH4, C2H4 and C2H2, respectively, while the highest three Si/Cl contained intermediates are SiCl2, SiCl4 and HCl, respectively. Furthermore, low total gas flow results in a uniform C/Si ratio at different temperatures, and reducing the ratio of MTS/H2 is an interesting way to raise the C/Si ratio in the reactor.