Single Particle Laser Mass Spectrometry Applied to Differential Ice Nucleation Experiments at the AIDA Chamber

Experiments conducted at the Aerosol Interactions and Dynamics in the Atmosphere (AIDA) chamber located in Karlsruhe, Germany permit investigation of particle properties that affect the nucleation of ice at temperature and water vapor conditions relevant to cloud microphysics and climate issues. Ice clouds were generated by heterogeneous nucleation of Arizona test dust (ATD), illite, and hematite and homogeneous nucleation of sulfuric acid. Ice crystals formed in the chamber were inertially separated from unactivated, or “interstitial” aerosol particles with a pumped counterflow virtual impactor (PCVI), then evaporated. The ice residue (i.e., the aerosol which initiated ice nucleation plus any material which was scavenged from the gas- and/or particle-phase), was chemically characterized at the single particle level using a laser ionization mass spectrometer. In this manner the species that first nucleated ice could be identified out of a mixed aerosol population in the chamber. Bare mineral dust particles were more effective ice nuclei (IN) than similar particles with a coating. Metallic particles from contamination in the chamber initiated ice nucleation before other species but there were few enough that they did not compromise the experiments. Nitrate, sulfate, and organics were often detected on particles and ice residue, evidently from scavenging of trace gas-phase species in the chamber. Hematite was a more effective ice nucleus than illite. Ice residue was frequently larger than unactivated test aerosol due to the formation of aggregates due to scavenging, condensation of contaminant gases, and the predominance of larger aerosol in nucleation.     

A Method for Single Particle Mass Spectrometry of Ice Nuclei

High altitude cirrus clouds play an important role in the terrestrial radiation budget. Cirrus clouds are composed of ice particles that generally form on only a small subset, from 1 in 10 to 1 in 10 5 , of the background aerosol. Ice particles may form due to the homogeneous freezing of aqueous aerosols or by the action of heterogeneous ice nuclei (IN). IN possess the ability to form ice at a higher temperature for a given vapor pressure of water than is required for homogeneous freezing. Apart from a few studies of refractory components, the chemical composition of these climatically important particles remains largely unknown. Almost nothing has been reported about the semivolatile and volatile components of IN. One of the principal reasons is that collection of cirrus precursors ideally should take place immediately after ice formation, before significant alteration of the crystals due to particle and gas-phase scavenging. Here we describe a method to measure the concentration and activation conditions of aerosols by exposure to temperatures and relative humidities (RH) similar to those that initiate cirrus cloud formation in the atmosphere. Laser mass spectrometry was subsequently used to investigate only those particles that nucleated ice. With this technique we were able to differentiate particles known to act as IN from those that entered the ice phase homogeneously. Deployment to study aerosol effects on ice formation in cirrus clouds is presented, although this method is applicable to the entire tropospheric mixed-phase and ice-phase regimes.     

Development and characterization of a “store and create” microfluidic device to determine the heterogeneous freezing properties of ice nucleating particles

Abstract

Understanding heterogeneous ice nucleation induced by ice nucleating particles (INPs) is hindered by analytical challenges in accurately determining the freezing temperature spectrum, abundance, and physicochemical properties of INPs. Here we evaluate the performance of a microfluidic device that employs a “store and create” approach to measure the ice nucleation properties of approximately 600 uniformly sized nanoliter water droplets. These droplets are immersed in surfactant-free environmentally sustainable squalene oil and do not contact the polymer walls of the microfluidic device. The device interfaced with a cold plate temperature controller has a greatly reduced background freezing temperature spectrum for filtered water droplets compared to conventional microliter droplet-on-substrate freezing methods. Droplets containing particles of interest are readily generated on-chip from a suspension of particles in water. Background freezing for 6 nL water droplets exhibits a median freezing temperature of ?33.7?±?0.4?°C, close to the theoretical freezing temperature of ?34.5?°C. The immersion freezing temperature spectra obtained from Snomax bacterial and illite mineral particles compares well with literature data, and the freezing contribution from either type of particle can be separated from a mixed suspension. Our approach generates a highly uniform droplet size distribution, causes no clogging of the microfluidic device, and is capable of reproducible droplet refreezes. The high-resolution freezing spectra obtained from large droplet number arrays enables the use of the derivative INP temperature spectrum analysis to quantitatively distinguish between different classes of INPs. The lower and consistent filtered water background freezing temperature enables measurements of almost the entire immersion freezing temperature regime from ?33 to 0?°C, and quantification of weaker but often abundant INPs such as those found in biomass-burning smoke aerosol.

Copyright © 2019 American Association for Aerosol Research     

Modeling New Particle Formation During Air Pollution Episodes: Impacts on Aerosol and Cloud Condensation Nuclei

The impact of new particle formation on regional air quality and CCN formation is for the first time explored using the UAM-AERO air quality model. New particles are formed by ternary nucleation of sulfuric acid, ammonia and water; subsequent growth of clusters to large sizes is driven by condensation of sulfuric acid and organic vapors, as described by the recently developed nano-Köhler theory. Application of the model in Athens (GAA) and Marseilles (GMA) reveals higher sulfuric acid condensational sink and gaseous sulfuric acid (hence nucleation rate) for the latter. However, limited quantities of organic vapors in the GMA inhibit the growth of the formed clusters; therefore new particle formation is more efficient in the GAA. A sensitivity analysis demonstrates that (1) uncertainty in vaporization enthalpy does not affect organic carbon formed by nucleation, and (2) an accommodation coefficient of unity gives excellent agreement of condensation sink with in-situ observations. Nucleation affects the aerosol size distribution, and can be an important contributor to CCN; locally it can be more important than chemical ageing of pre-existing aerosols.     

Large aerosol particles as freezing nuclei

Aerosol particles ingested by cloud supply nuclei which initiate formation of ice. These particles may either condense water or collide with cloud droplets thus becoming hydrosol particles. Ice nucleation through freezing was found to be time-dependent; nucleation sites are being formed or exposed continuously on the surfaces of hydrosol particles. In severe storms large soil particles (dia. > 40 μm) accrete cloud droplets; they freeze the accreted supercooled water at temperatures warmer than the ice nucleation temperature of their submicron- and micron-sized shed particles. Solid phase (ice) formation in clouds cannot be reconstructed by determining freezing temperature spectra of hydrosol present in precipitatation samples where surfaces of hydrosolized aerosol particles have already undergone physical and chemical changes.     

Sizing Small Sulfuric Acid Particles with an Ultrafine Particle Condensation Nucleus Counter

The sizing capability of an ultrafine particle condensation nucleus counter (which uses butanol as the condensing fluid) equipped with pulse height analysis was evaluated in terms of particle composition for sulfuric acid aerosol and sulfuric acid aerosol to which gas-phase ammonia had been added. The response of the counter depended on composition for a range of particle sizes when the water partial pressure was low. For water partial pressures < 5 Torr and for particles > 4 nm in diameter, the response (pulse heights) of the instrument to particles of a given size was substantially different for sulfuric acid particles and those that were neutralized with ammonia. For water partial pressures > 5 Torr, however, neutralizing the particles with ammonia had little effect on pulse height distributions. For particles smaller than 4 nm diameter the pulse heights were insensitive to exposure to ammonia.     

Investigation of Surface Properties of Ultrafine Particles by Application of a Multistep Condensation Nucleus Counter

The fate of atmospheric ultrafine particles is determined by their size, chemical composition, and especially by their physical and chemical surface properties. To characterize the surface of ultrafine particles, their behavior as condensation nuclei can be used. Monodisperse ultra-fine particles with different surface structures were investigated by observing the onset of droplet formation at a fixed electrical mobility diameter. Droplet growth was detected by application of a multistep condensation nucleus counter (CNC). The particles were generated under well-controlled conditions and monodisperse fractions were obtained using an electrostatic classifier. For studying the influence of changes in the surface structure, ultrafine sulfuric acid droplets were coated with different organic materials. Different surface films required different supersaturations for droplet growth depending on the molecular structure and layer thickness of the material used for coating. Therefore it was concluded that certain compounds, enriched on the particle surface, affect condensation of water vapor in such a way that higher supersaturations are required in comparison to the particle core material. Additionally, it was observed that remarkably high supersaturations of water vapor were required for condensation on particles consisting of the following materials: metals, carbon, and Aerosil (spherical silica particles).     

MEASURED ATMOSPHERIC NEW PARTICLE FORMATION RATES: IMPLICATIONS FOR NUCLEATION MECHANISMS

Measured production rates of tropospheric ultrafine particles (~3nm diameter) are reported for the first time and are shown to be orders of magnitude greater than nucleation rates predicted by the binary theory of homogeneous nucleation for sulfuric acid and water. Furthermore, the functional dependence of observed particle formation rates on sulfuric acid vapor concentrations is much weaker than predicted by binary theory. We present arguments to show that these discrepancies might be due to the participation of a species such as ammonia which could stabilize subcritical clusters, thereby enhancing nucleation rates. The data suggest that atmospheric nucleation may occur by a collision-limited process, rather than by a condensation/evaporation controlled process as is assumed in the classical theory.     

Experiments and insights of desalination by a freezing/thawing method at low subcooling

Desalination by freezing/thawing method was a very important method to obtain fresh water from sea water. In this work, desalination by freezing/thawing method was conducted with initial sodium chloride of 3.5 wt% in consideration of stirring speed, freezing time and subcooling. The subcooling ranged from 1.2 K to 4 K. The optimum conditions for desalination in this work were stirring speed of 200 r·min^-1, freezing time of 120 min, and subcooling of 3 K. The results also showed that sodium chloride cannot be effectively removed by once freezing/thawing process. The maximum removal efficiency of sodium chloride was 64.3%. Two major reasons resulting in the impurity of obtained melted water by freezing/thawing method were proposed. The first reason was the inevitable adhesion of salt solution to the surface of ice, which could be removed easily by distilled water flushing. The second reason was that salt solution was heterogeneously wrapped in the accumulated ice, which was difficult to be removed by distilled water flushing. The liquid flushing method was proposed to verify the conjecture, and the results were in accordance with the two reasons mentioned above. Additional method, such as multiple flushing liquid method, was suggested to be used during the freezing/thawing process for effectively removing sodium chloride, and obtaining fresh water.     

Experiments and insights of desalination by a freezing/thawing method at low subcooling

Desalination by freezing/thawing method was a very important method to obtain fresh water from sea water. In this work, desalination by freezing/thawing method was conducted with initial sodium chloride of 3.5 wt% in consideration of stirring speed, freezing time and subcooling. The subcooling ranged from 1.2 K to 4 K. The optimum conditions for desalination in this work were stirring speed of 200 r·min⁻¹, freezing time of 120 min, and subcooling of 3 K. The results also showed that sodium chloride cannot be effectively removed by once freezing/thawing process. The maximum removal efficiency of sodium chloride was 64.3%. Two major reasons resulting in the impurity of obtained melted water by freezing/thawing method were proposed. The first reason was the inevitable adhesion of salt solution to the surface of ice, which could be removed easily by distilled water flushing. The second reason was that salt solution was heterogeneously wrapped in the accumulated ice, which was difficult to be removed by distilled water flushing. The liquid flushing method was proposed to verify the conjecture, and the results were in accordance with the two reasons mentioned above. Additional method, such as multiple flushing liquid method, was suggested to be used during the freezing/thawing process for effectively removing sodium chloride, and obtaining fresh water.     

Investigating dissolution of colemanite in sulfuric acid solutions by particle size measurements

Dissolution properties of colemanite and gypsum formation in sulfuric acid were investigated by measuring size distribution of particles in the reaction cell with time. After termination of the reaction, the remained material in the cell was analyzed to find out unreacted and reacted fractions. The results showed that the reaction of colemanite particles with sulfuric acid led to reduction in particle sizes and the degree of reduction depended on acids concentration and reaction time. The dissolution period and point of gypsum formation were clearly distinguished and marked on particle size plots.     

超声辅助冷冻对湿面筋蛋白中冰晶粒度分布及总水含量的影响

超声辅助食品冷冻过程是一种新的技术。本文通过对湿面筋蛋白中冰晶粒度分布及总水含量的检测,探讨超声改善冷冻食品品质的微观作用机制,为超声冷冻新技术在食品化工中的应用奠定化学工程学基础。测定了有无超声环境下冷冻的湿面筋蛋白经过不同冷冻贮藏时间后总水含量, 结果显示：随着冷冻贮藏时间的延长,超声环境下冷冻的湿面筋蛋白中总水含量比传统环境下高。用扫描电镜和压汞仪间接观察和分析了冷冻的湿面筋蛋白中冰晶的形状和粒度分布。研究表明,适宜的功率超声辅助下,冷冻过程能在湿面筋蛋白内部形成细小且分布均匀的冰晶体,减少面筋蛋白网络结构的破坏,从而改善冷冻食品的品质。     

钛白废酸循环利用工艺的研究

钛白废酸循环利用工艺是采用反渗透法将质量分数为20%的钛白废酸浓缩到45%,一部分作为酸解用酸的稀释水,一部分用作硫酸锰的酸解用酸,剩余的45%的浓废酸与质量分数为98%的浓硫酸调配增浓、冷冻、除杂,作为补充水送到硫酸生产装置的吸收系统再制酸。以德天化工为例,实施该工艺每年可减排废酸14.29万t,节约中和废水的石灰2.86万t,减排废水11.43万t,原材料硫酸消耗节省2.86万t,表明该工艺具有技术先进性和推广性。     

Formation Mechanism of Cracks During the Freeze Drying of Gelcast Ceramic Parts

The near‐net shaping of gelcast ceramic parts can be achieved using freeze‐drying technology. It was discovered that the cracks probably occurred inside the part during freeze drying due to the formation of liquid water. To explain the formation mechanism of cracks, the electrical resistance method was employed to measure the part's eutectic temperature which can be used to determine the freezing and melting state of the part. Affecting factors on cracking were investigated by testing the temperature and water loss of the part during the drying stage, and the cracks inside the part were detected through computed tomography (CT). It was found that when the temperature of the part was higher than the eutectic temperature, the ice crystals at the sublimation front would melt, resulting in the formation of wet green body. The cracks will occur inside the part because great capillary forces are formed in the wet green body. Cracks could be controlled through reducing heat supply by lowing shelf temperature, decreasing pressure of the drying chamber or lowering the dried layer resistance against water vapor by improving the freezing temperature or reducing the solid loading of the part.     

基于CFD⁃DEM的水下切粒装置水室内颗粒流动过程数值模拟

基于CFD?DEM耦合方法,研究了颗粒在水室内的流动状态,分析了不同刀盘转速、粒子水通入量和水室出口角度对造粒过程的影响,发现提高刀盘转速、增加粒子水通入量和水室出口倾斜一定的角度都有利于水室内颗粒的排出。进一步研究了颗粒与碎屑在水室内的流动,发现在水室出口处二者的流动基本呈现出一定的分离角度。     

A New Electrospray Aerosol Generator with High Particle Transmission Efficiency

A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed.     

A New Electrospray Aerosol Generator with High Particle Transmission Efficiency

A new single-capillary electrospray (ES) aerosol generator has been developed for monodisperse particle production with maximal transmission efficiency. The new generator consists of both a spray chamber in a point-to-orifice-plate configuration and a charge reduction chamber that can hold up to 4 Nuclespot ionizers (Model P-2042, NRD Inc.). The 2 chambers are partitioned by an orifice plate. To optimize the particle transmission efficiency of the prototype, a systematic study was performed on the generator by varying the system setup and operation. Two key dimensions of the generator setup, the orifice diameter and the distance from the capillary tip to the orifice plate, were varied. Fluorescence analysis was applied to characterize the loss of ES-generated particles at different locations of the prototype. It was found that particle loss in the generator could be reduced by either increasing the orifice diameter or decreasing the distance between the capillary tip and the orifice plate. Increasing either the total radioactivity of the ionizers or the flowrate of the particle carrier gas also further decreased the particle loss in the system. The maximum particle transmission efficiency of 88.0% was obtained with the spray chamber fully opened to the charge reduction chamber, the capillary tip at the same level as the orifice plate, and 4 bipolar ionizers installed.     

Supercooling of water droplets in jet aviation fuel

Ice formation in aircraft fuel systems is an ongoing problem with potentially disastrous consequences. Unfortunately, the icing of fuel systems is poorly understood. It is well known that at temperatures below 0 °C particles of H₂O suspended in fuel can exist as crystalline ice or metastable supercooled water. In this paper we show that micron sized water droplets immersed in Jet A-1 aviation fuel can exist in a metastable supercooled state to around −36 °C. In fact, the majority of droplets in our experiments froze homogeneously showing that the fuel itself did not catalyse ice formation. We suggest that H₂O particles will remain in a supercooled liquid state until they come into contact with a suitable solid surface in an aircraft’s fuel system or the temperature falls below the homogeneous freezing limit.     

STUDY FOR NATURAL GAS HYDRATE CONVERSED FROM ICE

Natural gas hydrates are crystalline clathrate compounds composed of water and gases of small molecular diameters that can be used for storage and transport of natural gas as a novel method. In the paper a series of experiments of aspects and kinetics for hydrate formed from natural gas and ice were carried out on the industrial small scale production apparatus. The experimental results show that formation conditions of hydrate conversed from ice are independent of induction time, and bigger degrees of supersaturation and supercooling improved the driving force and advanced the hydrate formation. Superpressure is also favorable for ice particle conversion to hydrate. In addition, it was found there have an optimal reaction time during hydrate formation.