An Electrostatic Lens for Focusing Charged Particles in a Mass Spectrometer

The ability to transmit particles into the ablation region of an aerosol mass spectrometer determines in part the lower size limit for particles that can be analyzed. A large fraction of small particles (< 100 nm) are lost due to processes such as Brownian diffusion that broaden the particle beam. In this work, electrostatic focusing is used to overcome the limits of aerodynamic focusing in the analysis of nanometer-sized particles by aerosol mass spectrometry. A simple tube lens is used to focus charged particles into the ablation laser beam path. The diameter of the focused beam is smaller than the fundamental aerodynamic limit imposed by Brownian motion. Measured enhancements of the hit rate for particles between 21 and 33 nm diameter are between 3 and 6. These values are lower limits for the true enhancements. The lens is also energy selective and can be used to select the mass (size) of the particles being analyzed.     

Comparison of Two Aerodynamic Lenses as an Inlet for a Single Particle Laser Ablation Mass Spectrometer

By means of a newly designed portable aerosol mass spectrometer SPLAT (Single Particle Laser Ablation Time-of-flight mass spectrometer) for the analysis of single atmospheric aerosol particles we investigated the system performance in dependency on two different aerodynamic lenses (Liu and Schreiner type) capable of focusing particles with diameters ranging from 80 nm to 800 nm and 300 nm to 3000 nm, respectively. By using the pressure regulated Schreiner lens, the instrument is independent of variations in atmospheric pressure which would lead to changing dynamical properties of the aerosol particles. Active pressure control inside the inlet system facilitates airborne measurements without complicated corrections. With the Liu setup no pressure regulation was used. Here the overall efficiency of our instrument was 7% while with the Schreiner setup 2% was achieved. The Liu lens setup is optimal for measuring submicron particles at low particle concentrations. To detect supermicron particles the Schreiner lens setup is favored. Together with these experiments we present key details of the SPLAT setup and its characterization. Our instrument is able to measure simultaneously the size and the chemical composition of individual aerosol particles larger than 300 nm in diameter. It uses forward scattered light of single aerosol particles at two positions to determine their vacuum aerodynamic diameter from the flight time between the two lasers. Chemical analysis of the particles is done by laser ablation mass spectrometry utilizing a bipolar time-of-flight mass spectrometer.     

A New Time-of-Flight Aerosol Mass Spectrometer (TOF-AMS)—Instrument Description and First Field Deployment

We report the development and first field deployment of a new version of the Aerosol Mass Spectrometer (AMS), which is capable of measuring non-refractory aerosol mass concentrations, chemically speciated mass distributions and single particle information. The instrument was constructed by interfacing the well-characterized Aerodyne AMS vacuum system, particle focusing, sizing, and evaporation/ionization components, with a compact TOFWERK orthogonal acceleration reflectron time-of-flight mass spectrometer. In this time-of-flight aerosol mass spectrometer (TOF-AMS) aerosol particles are focused by an aerodynamic lens assembly as a narrow beam into the vacuum chamber. Non-refractory particle components flash-vaporize after impaction onto the vaporizer and are ionized by electron impact. The ions are continuously guided into the source region of the time-of-flight mass spectrometer, where ions are extracted into the TOF section at a repetition rate of 83.3 kHz. Each extraction generates a complete mass spectrum, which is processed by a fast (sampling rate 1 Gs/s) data acquisition board and a PC. Particle size information is obtained by chopping the particle beam followed by time-resolved detection of the particle evaporation events. Due to the capability of the time-of-flight mass spectrometer of measuring complete mass spectra for every extraction, complete single particle mass spectra can be collected. This mode provides quantitative information on single particle composition. The TOF-AMS allows a direct measurement of internal and external mixture of non-refractory particle components as well as sensitive ensemble average particle composition and chemically resolved size distribution measurements. Here we describe for the first time the TOF-AMS and its operation as well as results from its first field deployment during the PM _2.5 Technology Assessment and Characterization Study—New York (PMTACS-NY) Winter Intensive in January 2004 in Queens, New York. These results show the capability of the TOF-AMS to measure quantitative aerosol composition and chemically resolved size distributions of the ambient aerosol. In addition it is shown that the single particle information collected with the instrument gives direct information about internal and external mixture of particle components.     

Airborne Deployment of an Instrument for the Real-Time Analysis of Single Aerosol Particles

An instrument is described that provides real-time chemical analysis of the composition of individual aerosol particles. A differentially pumped aerosol inlet transfers particles from the ambient atmosphere into the source region of a time-of-flight mass spectrometer where they impact on a heated surface and the resulting vapors are ionized by electron ionization prior to mass analysis. Labora tory calibration studies demonstrated that the instrument was capable of detecting particles with diameters greater than approximately 0.4mu m. The instrument was operated on the NASA DC-8 research aircraft as part of the 1996 SUbsonic aircraft: Contrail and Cloud Effects Special Study (SUCCESS) mission with the intent of studying the chemical composition of upper tropospheric particles. More than 25,000 aerosol particle mass spectra were recorded during 19 mission flights. Although approximately 120 of those spectra showed clear evidence of sulfate, nitrate, and other inorganic materials, the remaining spectra contained only mass peaks consistent with water. Moreover, particles were detected only while traversing clouds. These results are not consistent with expectations of the size, quantity, or composition of upper tropospheric particles. It is likely, however, that a subisokinetic aircraft sampling inlet resulted in the collection of only very large ice particles. This situation would account for both the observed preponder ance of water-only spectra and the apparent lack of particles outside of clouds. Despite the sampling problem, the instrument was able to chemically speciate aerosols directly sampled from a medium altitude aircraft. These represent the first examples of aerosol particles chemically speciated in real time from an airborne platform.     

HIGH-SPEED PARTICLE BEAM GENERATION: SIMPLE FOCUSING MECHANISMS

Modern chemical characterization instruments employ an aerosol inlet that transmits atmospheric aerosols to the low pressure source region of a time-of-flight mass spectrometer, where particles are ablated and ionized using high energy irradiation. The ions when analyzed in the mass spectrometer yield information about the elemental composition of airborne aerosols. Often, the rate at which particles are analyzed is limited by the transmission rate of the inlet used. Depending on their size, particles are lost during sampling usually due to inertial effects or diffusion. Often simple capillaries and conical nozzles are used as primary focusing elements in the formation of high-speed particle beams. Due to the basic nature of the focusing mechanism, such elements transmit particles efficiently over a narrow size range. This size range strongly depends on the nozzle geometry and operating conditions. In this work, numerical techniques are used to (a) simulate fluid and particle transport in axi-symmetric nozzles, (b) help understand and identify the mechanisms by which particle beams are formed in capillaries and conical nozzles, and (c) illustrate the contrasting nature of the beams thus formed. Particle focusing is also simulated in some typical inlets to validate the predictions and illustrate the merits and drawbacks of each design.     

Simple and Reversible Transformation of an APCI/MS/MS Into an Aerosol Mass Spectrometer: Development and Characterization of a New Inlet

The inlet of a commercial atmospheric pressure chemical ionization—mass spectrometer (APCI/MS/MS) has been modified to transform it into an aerosol mass spectrometer, named TD-API-AMS. The new inlet consists in a charcoal denuder (to trap gas phase VOCs and SVOCs) followed by the thermal-desorption unit of the APCI source. Thermal desorption and APCI were chosen because they avoid sample denaturizing while keeping good time resolution. The objectives of this paper are (1) to describe the simple and reversible modifications of the commercial APCI inlet allowing its use as an aerosol mass spectrometer and (2) to characterize the performances of this modified inlet. These performances are characterized in term of efficiency of (i) gas phase organic compounds removal, (ii) particle transmission, and (iii) particle volatilization in the thermal-desorption unit. The characterization was conduced with secondary organic aerosol (SOA) produced from the ozonolysis of α -pinene and 2-buten-1-ol in a continuous flow reactor. The results show a denuder gas phase trapping efficiency higher than 93 ± 3% while the particle transmission efficiency was nearly 100% in particle number, but decreased to as little as 85% in total particle volume. This result highlights a shift of the particle distribution towards the fine particles occurring through the denuder, due to a modification of the gas-particle equilibrium. The inlets' characterization has also shown a particle volatilization efficiency higher than 90% (in volume).     

Nanoparticle Detection by Aerosol Mass Spectrometry

An aerodynamic lens system with efficient transmission of particles in the 10-300 nm size range is used to study the efficiency of nanoparticle detection by laser ablation mass spectrometry with 193 nm and 266 nm radiation. Ideally, all particles in the beam path when the laser fires should be detected. However, the probability of particle detection is much less than 1 and dependent upon the particle type, defined by particle size and chemical composition, and the ablation conditions, defined by the laser wavelength and irradiance. Particles above 100 nm can be ablated and detected with near unit efficiency. Below 100 nm, the detection probability decreases with decreasing particle size and salt particles (sodium chloride, potassium chloride) are detected with higher efficiency than organic particles (oleic acid, 3-nitrobenzyl alcohol). The results are discussed in relation to the mechanism of laser ablation and the instrumental requirements for particle detection.     

Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Submicron Particles

The importance of atmospheric aerosols in regulating the Earth's climate and their potential detrimental impact on air quality and human health has stimulated the need for instrumentation which can provide real-time analysis of size resolved aerosol, mass, and chemical composition. We describe here an aerosol mass spectrometer (AMS) which has been developed in response to these aerosol sampling needs and present results which demonstrate quantitative mea surement capability for a laboratory-generated pure component NH₄ NO₃ aerosol. The instrument combines standard vacuum and mass spectrometric technologies with recently developed aerosol sampling techniques. A unique aerodynamic aerosol inlet (developed at the University of Minnesota) focuses particles into a narrow beam and efficiently transports them into vacuum where aerodynamic particle size is determined via a particle time-of-flight (TOF) measurement. Time-resolved particle mass detection is performed mass spectrometrically following particle flash vaporization on a resistively heated surface. Calibration data are presented for aerodynamic particle velocity and particle collection efficiency measurements. The capability to measure aerosol size and mass distributions is compared to simultaneous measurements using a differential mobility analyzer (DMA) and condensation particle counter (CPC). Quantitative size classification is demonstrated for pure component NH₄ NO₃ aerosols having mass concentrations 0.25_mu g m -3. Results of fluid dynamics calculations illustrating the performance of the aerodynamic lens are also presented and compared to the measured performance. The utility of this AMS as both a laboratory and field portable instrument is discussed.     

Real-Time Chemical Analysis of Organic Aerosols Using a Thermal Desorption Particle Beam Mass Spectrometer

An instrument has been developed for real-time, quantitative chemical analys is of organic particles in laboratory environments. In this apparatus, which we call a Thermal Desorption Particle Beam Mass Spectrometer (TDPBMS), particles are sampled into a differentially-pumped vacuum chamber, focused into a narrow, low-divergence particle beam using aerodynamic lenses, and then transported into a high-vacuum region where they impact on a heated surface, evaporate, and the vapor is mass analyzed in a quadrupole mass spectrometer. The average composition of a continuous stream of particles is thus measured in real time, and size-dependent composition can be obtained by passing the incoming aerosol through a differential mobility analyzer. The TDPBMS can analyze multi component organic particles in the 0.02-0.5mu m size range for compound concentrations 0.1-1mu g m3 without particle matrix effects. By using careful calibration techniques that account for particle shape and transport efficiency, the particulate organic components can be quantified with an estimated uncertainty of 20%. The utility of TDPBMS for laboratory studies of aerosol chemistry is demonstrated by monitoring the tridecanoic acid concentration in secondary organic aerosol formed during a smog chamber reaction of 1-tetradecene and ozone.     

Variations in the Size and Chemical Composition of Nitrate-Containing Particles in Riverside,CA

High time resolution measurements of nitrate-containing particles were made in Riverside, CA using an automated particle nitrate monitor and an aerosol time-of-flight mass spectrometer. The automated particle nitrate monitor provides quantitative data on the concentration of total particle-bound nitrate with a temporal resolution of 10 min. The aerosol time-of-flight mass spectrometer provides continuous data on aerodynamic size and single particle chemical composition. Data sets acquired with the two instruments are compared for a two-day intensive sampling period in August 1997 as part of the 1997 Southern California Ozone Study-North American Research Strategy for Tropospheric Ozone (SCOS97-NARSTO). Temporal variations in the number of nitrate-containing particles observed by the mass spectrometry system track (R² 0.73) the nitrate mass concentrations measured by the automated particle nitrate monitor. Both systems detected four periods of elevated nitrate concentrations of several hours duration. For these periods, the nitrate mass concentrations as measured by the automated particle nitrate monitor were similar, ranging from 11 to 19 mu g m3. However, the particle size and single particle composition of nitrate-containing particles as measured by the aerosol time-of-flight mass spectrometer were distinctly different. Specifically, the nitrate maxima observed in the midmorning hours were characterized by supermicrometer nitrate particles associated with either ammonium and organic species or sodium. The afternoon maxima were characterized by submicrometer ammonium nitrate particles, most of which contained organic material.     

Using ATOFMS to Determine OC/EC Mass Fractions in Particles

Historically, obtaining quantitative chemical information using laser desorption ionization mass spectrometry for analyzing individual aerosol particles has been quite challenging. This is due in large part to fluctuations in the absolute ion signals resulting from inhomogeneities in the laser beam profile, as well as chemical matrix effects. Progress has been made in quantifying atomic species using high laser powers, but very few studies have been performed quantifying molecular species. In this study, promising results are obtained using a new approach to measure the fraction of organic carbon (OC) associated with elemental carbon (EC) in aerosol particles using single particle laser desorption ionization. A tandem differential mobility analyzer (TDMA) is used to generate OC/EC particles by size selecting EC particles of a given mobility diameter and then coating them with known thicknesses of OC measured using a second DMA. The mass spectra of the OC/EC particles exiting the second DMA are measured using an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS). A calibration curve is produced with a linear correlation (R² = 0.98) over the range of OC/EC ion intensity ratios observed in source and ambient studies. Importantly, the OC/EC values measured in ambient field tests with the UF-ATOFMS show a linear correlation (R² = 0.69) with OC/EC mass ratios obtained using semi-continuous filter based thermo-optical measurements. The calibration procedure established herein represents a significant step toward quantification of OC and EC in sub-micron ambient particles using laser desorption ionization mass spectrometry.     

DRYING OF BIOMASS PARTICLES IN FIXED AND MOVING BEDS

ABSTRACT

The drying of biomass fuel particles in fixed and moving beds with hot gas or steam is considered both experimentally and theoretically. A single particle drying model is coupled with a model describing beat and moisture transfer in The gas phase of the bed. The size of the bed to reach a certain degree of drying depends mostly on the following parameters: particle size, panicle moisture content, gas inlet temperature, gas inlet moisture content and gas mass flow rate.     

High Precision Density Measurements of Single Particles: The Density of Metastable Phases

We describe a system designed to measure the size, composition, and density of individual spherical particles in real time. It uses a Differential Mobility Analyzer (DMA) to select a monodisperse particle population and the single particle mass spectrometer to measure individual particle aerodynamic diameter. Together the mobility and aerodynamic diameters yield particle density. The mass spectrometer aerodynamic sizing resolution d _{ν a} /Δ d _{ν a} is ～ 50 and > 100 for 200 nm and 800 nm particles respectively and together with the DMA the overall system resolution is 20. We demonstrate that the line shape of the aerodynamic size distribution can be used to identify asphericity. We present results from two operational schemes: one suitable for most applications, yielding particle density with a precision of ± 2.5%, and a high precision variant, that uses an internal calibrant to remove any of the systematic errors and significantly improves the measurement quality. The high precision scheme is most suitable for laboratory studies, making it possible to follow slight changes in particle density. An application of the system to measure the density of hygroscopic particles in deep metastable phases near zero relative humidity is presented. The density data presented here are consistent with conclusions reached in a number of other studies, namely, that some particle systems, once deliquesced, persist as droplets down to near zero relative humidity.     

High Speed Particle Beam Generation: A Dynamic Focusing Mechanism for Selecting Ultrafine Particles

RSMS-II is a unique characterization technique for analyzing the chemical content of individual airborne ultrafine particles in real time. Although based on earlier versions, the newest implementation offers crucial enhancements including a smart data acquisition system and a completely redesigned particle inlet. The particle inlet is based on a dynamic focusing mechanism that selectively transmits a narrow particle size range in the form of a high speed particle beam. The mean particle size that is optimally transmitted is dynamically altered by changing the nozzle source pressure, thus particles over a wide size range may be selected. Inherent in the design of dynamic focusing mechanisms is the ability to size-select particles based on their aerodynamic characteristics, thus obviating the need for additional sizing components. The principle, design, and calibration of a variable pressure inlet is presented in the current work. Characteristics are estimated employing a theoretical approach based on the Stokes number definition and supported with numerical simulations using CFD tools. Results from a preliminary effort in calibrating the inlet using monodisperse aerosol are presented. Results indicate that the size resolving capability of the inlet may be enhanced at the expense of lowered transmission rates. Finally, the capability of RSMS-II as a characterization technique is demonstrated by analyzing ultrafine atmospheric particles from a moderately polluted episode.     

Experiments on Particle Deposition in the Human Upper Respiratory System

ABSTRACT

In this study, the deposition of particles (0.3 μm to 2.5 μm in diameter) within a silicone rubber model of the human upper respiratory system was studied. The domain of the respiratory tract under investigation begins at the entrance (nostrils and mouth) and continues through to the second generation of the tracheobronchial airways (main bronchi). The particle deposition efficiency of the sample respiratory system was computed by measuring particle concentration at the inlet and outlet of the model. The regional deposition patterns of fluorescent particles (0.3 μm to 0.7 μm in diameter) was examined by measuring the fluorescent intensity with a fluorescence spectrophotometer. For simulated oral inhalation, the deposition efficiency of the oral cavity (0.9%-5.4%) is approximately the same as that of the oropharynx-trachea region (0.8%-4.8%). During simulated nasal inhalation, the deposition efficiency of the nasal region (20%-43.6%) is greater than the values of the nasopharynx-trachea region (2.8%-8.2%). The nasopharynx-trachea region exhibits a higher deposition efficiency than that of the oropharynx-trachea region. Deposition during the simultaneous oral and nasal inhalation is mostly affected by particle size. Flow rate through the model has less effect on deposition for particle diameter less than 1 μm. When particle diameter is greater than 1 μm deposition efficiencies are weakly and inversely related to the flow rate.     

Evaluation of a New Particle Trap in a Laser Desorption Mass Spectrometer for Online Measurement of Aerosol Composition

We have developed a new analyzer for the online measurement of aerosol composition: a particle trap laser desorption mass spectrometer (PT-LDMS). The main components of the instrument include an aerodynamic lens, a particle trap enclosed by a quartz cell, a quadrupole mass spectrometer (QMS), a vacuum chamber incorporating the above components, and a carbon dioxide (CO₂) laser (wavelength 10.6 μm). The aerodynamic lens generates a beam of submicron particles, which is focused on a small area on the particle trap. The particle trap consists of custom-made mesh layers, the structure of which was newly designed using engineering techniques for micro electro mechanical systems (MEMS). A large number of mesh frames are well arranged in the trap, and particles can be efficiently captured after multiple impactions on the frames. The CO₂ laser is used to vaporize aerosol compounds captured on the particle trap. The evolved gas confined within the quartz cell is analyzed using an electron impact ionization (EI) QMS to quantify the chemical composition of the particles. The concept of the PT-LDMS and first evaluation of its performance are presented, specifically focusing on the structure and performance of the particle trap.     

Detection and Analysis of Aerosol Particles by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was evaluated as a means for quantitative analysis of the size, mass, and composition of individual micron-to submicron-sized aerosol particles over a range of well-characterized experimental conditions. Conditional data analysis was used to identify LIBS spectra that correspond to discrete aerosol particles under low aerosol particle loadings. The size distributions of monodisperse particle source flows were measured using the LIBS technique for calcium- and magnesium-based aerosols. The resulting size distributions were in good agreement with independently measured size distribution data. A lower size detection limit of 175 nm was determined for the calcium- and magnesium-based particles, which corresponds to a detectable mass of approximately 3 femtograms. In addition, the accuracy of the LIBS technique for the interference-free analysis of different particle types was verified using a binary aerosol system of calcium-based and chromium particles.     

Computational Modeling of Silicon Nanoparticle Synthesis: I. A General Two-Dimensional Model

A two-dimensional model has been developed for silicon nanoparticle synthesis by silane thermal decomposition driven by laser heating in a tubular reactor. This fully coupled model includes fluid dynamics, laser heating, gas phase and surface phase chemical reactions, and aerosol dynamics which includes particle transport and evolution by convection, diffusion, thermophoresis, nucleation, surface growth, and coagulation processes. A moment method, based upon a lognormal particle size distribution, and a sectional method are used to model the aerosol dynamics. The simulation results obtained by the two methods are compared. The sectional method is capable of capturing the bimodal behavior that occurs locally during the process, while the moment method is computationally more efficient. The effect of operating parameters, such as precursor concentration, gas phase composition, inlet gas velocity and laser power input, on the characteristics of the particles produced are investigated. Higher temperature generates more large particles with higher precursor conversion. Shorter residence time, from high inlet velocity, produces more small particles at the cost of lower precursor conversion. Increasing H₂ concentration suppresses particle formation by reducing the rates of gas phase and surface reactions, leading to fewer and smaller particles. In addition, the relative importance of the interconnected mechanisms involved in the particle formation is considered. The results make clear that spatial variations in reaction conditions are the primary source of size polydispersity and generation of non lognormal overall size distributions in a laser-driven process like that considered here.     

Electrohydrodynamic Flow and Particle Transport Mechanism in Electrostatic Precipitators with Cavity Walls

The electrohydrodynamic (EHD) flow induced by the corona wind was observed in a model electrostatic precipitator (ESP) of the simple geometry composed of the plates with a cavity. And the influence of the EHD flow and the turbulence condition of inlet cross-flow on the particle behavior inside the ESP and its collection efficiency were elucidated through experimental and numerical analysis. The profiles of streamwise gas velocities and turbulence intensities were measured in the ESP with a laser Doppler anemometer.A laser beam sheet visualized particle trajectories. Collection efficiencies were measured with a particle counter. In addition, numerical computations were performed to compare with the experimental results. The numerical results showed good agreement with the experimental data. As the corona voltage increased, the gas velocities of the core flow and the circulating flow inside the cavity increased due to the corona wind and the turbulence intensity increased near the cavity region. As the corona voltage increased for the low bulk gas velocity, corona wind prevented the particle transport into the cavity. And the particle transport into the cavity by turbulent dispersion was observed as the bulk gas velocity increased. When the flow with high turbulence intensity entered the ESP, the turbulent dispersion enhanced the transport of particles into the cavity; hence, the collection efficiency was higher compared with the case of the relatively lower inlet turbulence intensity below a critical corona voltage. However, the collection efficiency was slightly lower for the high inlet turbulence than for the low inlet turbulence above the critical corona voltage due to the turbulent diffusion of particles toward the centerline downstream from the corona wire.     

Continuous Drying of Slurry in a Jet Spouted Bed

ABSTRACT

he performance of a laboratory scale jet spouted bed (JSB) for drying rice flour slurry was studied. The bed consisted of ceramic balls (5028 mm diameter) and the rice flour slurry was sprayed onto the moving particle surface near the inlet part. All the experiments were carried out at the jet spouting regime. This regime has high bed void fraction and violent movement and collision of bed particles. As a result, the dried product layer is attrited from particle surface as a fine powder and entrained from the bed by the spouting air. The experimental result were presented to show the effects of static bed height, inlet air flow rate and temperature, and feed concentration and flow rate on the outlet air temperature, thernal efficiency, and mean particle size and moisture content of the product. Asimple mathematical model, which is based on the conservation of mass and energy equations, was developed. Predicted results agreed well with those obtained from the experiment.