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.     

Effect of Vaporizer Temperature on Ambient Non-Refractory Submicron Aerosol Composition and Mass Spectra Measured by the Aerosol Mass Spectrometer

Aerodyne Aerosol Mass Spectrometers (AMS) are routinely operated with a constant vaporizer temperature (T_vap) of 600°C in order to facilitate quantitative detection of non-refractory submicron (NR-PM₁) species. By analogy with other thermal desorption instruments, systematically varying T_vap may provide additional information regarding NR-PM₁ chemical composition and relative volatility, and was explored during two ambient studies. The performance of the AMS generally and the functional integrity of the vaporizer were not negatively impacted during vaporizer temperature cycling (VTC) periods. NR-PM₁ species signals change substantially as T_vap decreases with that change being consistent with previous relative volatility measurements: large decreases in lower volatility components (e.g., sulfate, organic aerosol [OA]) with little, if any, decrease in higher volatility components (e.g., nitrate, ammonium) as T_vap decreases. At T_vap < 600°C, slower evaporation was observed as a shift in particle time-of-flight distributions and an increase in “particle beam blocked” (background) concentrations. Some chemically reduced (i.e., C_xH_y⁺) OA ions at higher m/z are enhanced at lower T_vap, indicating that this method may improve the analysis of some chemically reduced OA systems. The OA spectra changes dramatically with T_vap; however, the observed trends cannot easily be interpreted to derive volatility information. Reducing T_vap increases the relative O:C and CO₂⁺, contrary to what is expected from measured volatility. This is interpreted as continuing decomposition of low volatility species that decreases more slowly (as T_vap decreases) than does the evaporation of reduced species. The reactive vaporizer surface and the inability to reach T_vap much below 200°C of the standard AMS limit the ability of this method to study the volatility of oxidized OA species.

Copyright 2015 American Association for Aerosol Research     

Characterization of an Aerodyne Aerosol Mass Spectrometer (AMS): Intercomparison with Other Aerosol Instruments

The Aerodyne Aerosol Mass Spectrometer (AMS) provides size-resolved chemical composition of non-refractory (vaporized at 600°C under vacuum) submicron aerosols with a time resolution of the order of minutes. Ambient measurements were performed in Tokyo between February 2003 and February 2004. We present intercomparisons of the AMS with a Particle-Into-Liquid Sampler combined with an Ion Chromatography analyzer (PILS-IC) and a Sunset Laboratory semi-continuous thermal-optical carbon analyzer. The temperature of the AMS inlet manifold was maintained at > 10 ^? C above the ambient dew point to dry particles in the sample air (relative humidity (RH) in the inlet < 53%). Assuming a particle collection efficiency of 0.5 for the AMS, the mass concentrations of inorganic species (nitrate, sulfate, chloride, and ammonium) measured by the AMS agree with those measured by the PILS-IC to within 26%. The mass concentrations of organic compounds measured by the AMS correlate well with organic carbon (OC) mass measured by the Sunset Laboratory carbon analyzer (r ² = 0.67–0.83). Assuming the same collection efficiency of 0.5 for the AMS organics, the linear regression slope is found to be 1.8 in summer and 1.6 in fall. These values are consistent with expected ratios of organic matter (OM) to OC in urban air.     

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.     

Characterization of Organic Particles from Incense Burning Using an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer

Incense burning is a common ritual in Asian communities both indoors in residential homes and outdoors in temple premises. Organic particles from burning of incense sticks, incense coils, and mosquito coils after extensive dilution (>1000×) were characterized by the Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The obtained mass spectra in general resemble those reported for biomass burning aerosols. Ion peaks with m/z values higher than 100 accounted for 15%–25% of the organic signals in the unit-mass-resolution (UMR) mass spectra. In the high-resolution (HR) mass spectra, the ion peaks at m/z 60 and 73 are found to be related to the sugar anhydrides as in particles from other biomass burning processes. In addition, the ion peaks at m/z 107, 121, 137, 151, 167, and 181, some of which (e.g., m/z 137 and 167) have been observed in particles from biomass burning but not yet assigned, were assigned to lignin-related components. Elemental analysis from the HR data reveals that a large portion of particulate organics from incense burning are oxygenated (O/C between 0.3 and 0.5) and unsaturated (and/or cyclic) in nature. Results from this study also highlight that mass spectra from HR-ToF-AMS measurements concerning primary emissions such as incense burning contain very useful information in the high m/z (>100) region about the chemical characteristics of those primary organic particles.

Copyright 2012 American Association for Aerosol Research     

A VUV Photoionization Aerosol Time-of-Flight Mass Spectrometer with a RF-Powered VUV Lamp for Laboratory-Based Organic Aerosol Measurements

A vacuum ultraviolet (VUV) photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) has been developed for real-time, quantitative chemical analysis of organic particles in laboratory environments. A nozzle of ～ 0.12 mm orifice combined with an aerodynamic lens assembly and a three stage differential pumping system is used to sample particles at atmospheric pressure. The particles are vaporized on a thermal heater, and then the nascent vapor is photoionized by light generated with a RF-powered VUV lamp. A 0.41 V/cm electric field is used to drive the ions from the ionization region into the ion extraction region where a positive electric pulse repels the ions into a reflectron mass spectrometer. The mass resolution of the spectrometer is ～ 350 and the detection limit is ～ 400 μ m ³ . The signal intensities observed are linear with the mass concentration of aerosols. Oleic acid particles are well quantified with an uncertainty of 15% in mass concentrations ranging from 3.9 mg/m ³ to 392 mg/m ³ . The VUV-ATOFMS has substantial potential for the use in laboratory investigations on organic aerosol chemistry.     

气溶胶飞行时间质谱仪分析间-二甲苯光氧化颗粒相产物

在自制的烟雾腔内,用紫外光照射间-二甲苯、亚硝酸甲酯、一氧化氮和清洁空气的混合物,可以启动间-二甲苯和羟基自由基(OH)的光氧化反应和一系列的后续反应,产生非挥发性和半挥发性有机化合物.半挥发性有机化合物可以在气态和粒子态之间进行分配,产生二次有机气溶胶粒子.采用实时测量气溶胶粒子粒径大小和化学成分的气溶胶飞行时间质谱仪快速、实时地测量了这些粒子的尺度、它们的分子成分和粒径分布.通过化学分析,得到酚、醛、酮和羧酸等重要的间-二甲苯光氧化产物,为讨论间-二甲苯光氧化反应机理提供了新的信息.     

Collection Efficiency of the Aerosol Mass Spectrometer for Chamber-Generated Secondary Organic Aerosols

The collection efficiency (CE) of the aerosol mass spectrometer (AMS) for chamber-generated secondary organic aerosol (SOA) at elevated mass concentrations (range: 19–207 μg m^?3; average: 64 μg m^?3) and under dry conditions was investigated by comparing AMS measurements to scanning mobility particle sizer (SMPS), Sunset semi-continuous carbon monitor (Sunset), and gravimetric filter measurements. While SMPS and Sunset measurements are consistent with gravimetric filter measurements throughout a series of reactions with varying parent hydrocarbon/oxidant combinations, AMS CE values were highly variable ranging from unity to <15%. The majority of mass discrepancy reflected by low CE values does not appear to be due to particle losses either in the aerodynamic lens system or in the vacuum chamber as the contributions of these mechanisms to CE are low and negligible, respectively. As a result, the largest contribution to CE in the case of chamber-generated SOA appears to be due to particle bounce at the vaporizer surface before volatilization, which is consistent with earlier studies that have investigated the CE of ambient and select laboratory-generated particles. CE values obtained throughout the series of reactions conducted here are also well correlated with the f ₄₄/f ₅₇ ratio, thereby indicating both that the composition of the organic fraction has an important impact on the CE of chamber-generated SOA and that this effect may be linked to the extent to which the organic fraction is oxidized.

Copyright 2013 American Association for Aerosol Research     

Comparison of a Quadrupole and a Time-of-Flight Aerosol Mass Spectrometer during the Feldberg Aerosol Characterization Experiment 2004

The Feldberg Aerosol Characterization Experiment (FACE-2004) took place from July 13–August 4, 2004 at the Taunus Observatory on the “Kleiner Feldberg” (825 m a.m.s.l.) in Central Germany. The experiment included (amongst others) size-resolved chemical characterization of non-refractory aerosol components. One of the experiment's objectives was to better understand and to characterize recently developed aerosol measurement instrumentation by intercomparison with other co-located instruments. One of these instruments was the Aerodyne Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS).

Here we compare the datasets obtained by the ToF-AMS with those obtained by the well-characterized co-located Quadrupole Aerosol Mass Spectrometer (Q-AMS). A good agreement between the recently developed ToF-AMS with the established Q-AMS is reported here for all species measured with the two instruments for a time period where both instruments operated under well-calibrated conditions. During measurements with reduced detector gain after a pump failure changed species concentrations were measured with the ToF-AMS that did not agree with those measured with the Q-AMS. These changes were different for the individual species and could be attributed to the influence of the ion detection threshold as was shown by model calculations.

For efficient and user-friendly processing of ToF-AMS raw data a data processing software package was developed. Since this is the first time this software was used for field data, it is described in some detail here.     

A Computationally Efficient Aerosol Nucleation/ Condensation Method: Pseudo-Steady-State Sulfuric Acid

In order to model accurately the size and number of atmospheric particles, it is necessary to predict aerosol nucleation rates. However, the explicit prediction of the sulfuric acid vapor concentration may become computationally intensive when nucleation and condensation are simultaneously occurring. In this article, we develop and test a computationally efficient solution to the problem of solving for the sulfuric acid vapor concentration. Rather than explicitly solving the differential equation for the temporal profile of sulfuric acid vapor, we assume that the sulfuric acid vapor is at the concentration in steady state with its source (oxidation of SO₂) and sinks (condensation and nucleation); this is known as the Pseudo-Steady-State Approximation (PSSA). Two versions of a box model with online size-resolved aerosol microphysics were developed to test the PSSA; (1) a “benchmark model” that solves explicitly for the sulfuric acid vapor concentration, and (2) a “PSSA model” that uses the PSSA. A wide array of atmospheric conditions was used to compare the benchmark and PSSA models. The mean difference in the total number of particles in the two models with diameters larger than 10 nm was only 1.8% and 1.1% in lower troposphere simulations after 2 and 6 hours, and 3.8% and 2.3% in the upper troposphere simulations after 2 and 6 h. The PSSA model was faster in 97% of the tests, more than ten times faster in 91% of the points, and more than 100 times faster in 69% of the tests.     

Collection Efficiencies in an Aerodyne Aerosol Mass Spectrometer as a Function of Particle Phase for Laboratory Generated Aerosols

The Aerodyne Aerosol Mass Spectrometer (AMS) is a useful tool to study ambient particles. To be quantitative, the mass or (number) of particles detected by the AMS relative to the mass (or number) of particles sampled by the AMS, or the AMS collection efficiency (CE), must be known. Here we investigated the effect of particulate phase on AMS CE for ammonium nitrate, ammonium sulfate, mixed ammonium nitrate/ammonium sulfate, and ammonium sulfate particles coated with an organic liquid. Dry, solid ammonium sulfate particles were sampled with a CE of 24 ± 3%. Liquid droplets and solid particles that were thickly coated with a liquid organic were collected with a CE of 100%. Mixed phase particles, solid particles thinly coated with liquid organic, and metastable aqueous ammonium sulfate droplets had intermediate CEs. The higher CEs for liquid particles compared with solid particles were attributed to wet or coated particles tending to stick upon impact with the AMS vaporizer, while a significant fraction of solid particles bounced prior to vaporization/detection. The consistency of single particle signals indicated that the phase (and hence CE) of mixed component particles did not affect the AMS sensitivity to a particular chemical species once volatilization occurred. Particle phase might explain a significant fraction of the variable AMS CEs reported in the literature. For example, ambient particles that were liquid (e.g., composition dominated by ammonium nitrate or acidic sulfate) have been reported to be sampled with 100% CE. In contrast, most ambient particle measurements report CEs of < 100% (typically~ 50%).     

Soot Particle Aerosol Mass Spectrometer: Development,Validation, and Initial Application

The Soot Particle Aerosol Mass Spectrometer (SP-AMS) was developed to measure the chemical and physical properties of particles containing refractory black carbon (rBC). The SP-AMS is an Aerodyne Aerosol Mass Spectrometer (AMS) equipped with an intracavity laser vaporizer (1064 nm) based on the Single Particle Soot Photometer (SP2) design, in addition to the resistively heated, tungsten vaporizer used in a standard AMS. The SP-AMS can be operated with the laser vaporizer alone, with both the laser and tungsten vaporizers, or with the tungsten vaporizer alone. When operating with only the laser vaporizer, the SP-AMS is selectively sensitive to laser-light absorbing particles, such as ambient rBC-containing particles as well as metal nanoparticles, and measures both the refractory and nonrefractory components. When operated with both vaporizers and modulating the laser on and off, the instrument measures the refractory components of absorbing particles and the nonrefractory particulate matter of all sampled particles. The SP-AMS design, mass spectral interpretation, calibration, and sensitivity are described. Instrument calibrations yield a sensitivity of greater than 140 carbon ions detected per picogram of rBC mass sampled, a 3σ detection limit of less than 0.1 μg·m^?3 for 60 s averaging, and a mass-specific ionization efficiency relative to particulate nitrate of 0.2 ± 0.1. Sensitivities were found to vary depending upon laser-particle beam overlap. The utility of the instrument to characterize ambient rBC aerosol is demonstrated.

Copyright 2012 American Association for Aerosol Research     

循环水加酸改善水质工艺

汽轮机凝汽器循环冷却水消耗水量大,采用循环水加酸改善水质工艺,在增大循环水的浓缩倍率(由2．6上升至3．3)的同时,控制加酸后循环水的pH值,电厂新鲜水补水量由200t／h降低到160t／h,阻垢剂的用量也相应减少,经济效益良好。     

Evaluation of Composition-Dependent Collection Efficiencies for the Aerodyne Aerosol Mass Spectrometer using Field Data

In recent years, Aerodyne aerosol mass spectrometers (AMS) have been used in many locations around the world to study the size-resolved, nonrefractory chemical composition of ambient particles. In order to obtain quantitative data, the mass or (number) of particles detected by the AMS relative to the mass (or number) of particles sampled by the AMS, i.e., the AMS collection efficiency (CE) must be known. Previous studies have proposed and used parameterizations of the AMS CE based on the aerosol composition and sampling line relative humidity. Here, we evaluate these parameterizations by comparing AMS mass concentrations with independent measurements of fine particle volume or particle-into-liquid sampler (PILS) ion chromatography measurements for 3 field campaigns with different dominant aerosol mixtures: (1) acidic sulfate particles, (2) aerosol containing a high mass fraction of ammonium nitrate, and (3) aerosol composed of primarily biomass burning emissions. The use of the default CE of 0.5 for all campaigns resulted in 81–90% of the AMS speciated and total mass concentrations comparing well with fine particle volume or PILS measurements within experimental uncertainties, with positive biases compared with a random error curve. By using composition-dependent CE values (sometimes as a function of size) which increased the CE for the above aerosol types, the fraction of data points within the measurement uncertainties increased to more than 92% and the mass concentrations decreased by ～5–15% on an average. The CE did not appear to be significantly dependent on changes in organic mass fraction although it was substantial in the 3 campaigns (47, 30, and 55%).

Copyright 2012 American Association for Aerosol Research     

Thermal Desorption Chemical Ionization Mass Spectrometer for Ultrafine Particle Chemical Composition

A thermal desorption chemical ionization mass spectrometer has been developed for real time, quantitative chemical analysis of ultrafine particles. The technique combines recently developed nanoparticle separation and collection techniques with highly sensitive chemical analysis provided by selected ion chemical ionization mass spectrometry. Sensitivity tests using laboratory-generated ammonium sulfate particles in the diameter range 10-16 nm show that sulfate and ammonium can be quantified with as little as 1 pg of collected aerosol mass. Such sensitivity makes this instrument suitable for real time measurements of the chemical composition of sub-10 nm particles reported recently from nucleation events.     

Size Calibration Corrections for the Active Scattering Aerosol Spectrometer Probe (ASASP-100X)

The response of the active scattering aerosol spectrometer probe (ASASP-100X) is affected by the optical properties of measured particles. Response functions of the ASASP-100X probe were calculated for different complex refractive indices corresponding to different types of atmospheric aerosol particles under various relative humidity conditions. Based on these response functions, corrected calibration bin diameters were determined for 15 size channels at six relative humidity values (0%, 50%, 70%, 80%, 90%, and 99%) and three typical aerosol types (rural, urban, and maritime). Sample calculations with these corrected calibration data show that a significant underestimation of the aerosol volume distribution can result if uncorrected manufacturer's size calibration data are used.     

浅谈镀铬液中硫酸的质量浓度

从故障分析入手,阐述了镀铬液中硫酸的质量浓度主要根据ρ(CrO3)与ρ(SO42-)比值,其大小直接影响着镀铬质量.当镀液中金属杂质的积累并超过一定数值时,会造成镀层产生缺陷.采用增加硫酸质量浓度提高ρ(SO42-)与ρ(CrO3)比值的方法,可以改善镀液性能、排除故障.     

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).