Repeatability and intermediate precision of a mass concentration calibration system

Many aerosol instruments require calibration to make accurate measurements. A centrifugal particle mass analyzer (CPMA) and aerosol electrometer can be used to calibrate aerosol instruments that measure mass concentration. To understand the sources of uncertainty in the calibration method, two CPMA-electrometer systems were tested to measure the repeatability and intermediate precision of the system, where the repeatability is the standard deviation of several measurements using the same system over a short period of time, and the intermediate precision is the standard deviation of several measurements using different instruments with different calibrations over a long period of time. It was found that the repeatability of the CPMA and the aerosol electrometer were both 0.8%, while the intermediate precision was 1.3% and 2.2%, respectively. The intermediate precision of the aerosol electrometers determined here compares well with a broader study by national metrology institutes which determined an intermediate precision of ～1.7%. By propagation of uncertainty, it is expected that a CPMA-electrometer system would have repeatability of 1.1% and an intermediate precision of ～2.1%. This compares favorably to thermal-optical analysis methods which aim to measure black carbon mass concentrations for instrument calibration, which have a repeatability in the range of 8.5–20% and reproducibility in the range of 20–26% for elemental carbon. Thus, the CPMA-electrometer method may be a good alternative to existing instrument calibration procedures.

Copyright © 2019 American Association for Aerosol Research     

Response of real-time black carbon mass instruments to mini-CAST soot

Soot is a climate forcer and a dangerous air pollutant that has been increasingly regulated. In aviation, regulatory measurements of soot mass concentration in the exhaust of aircraft turbine engines are to be based on measurements of black carbon (BC) calibrated to elemental carbon (EC) content of diffusion flame soot. The calibration soot must currently meet only one criterion: minimum EC to total carbon (TC) ratio of 0.8. However, not including soot properties other than the EC/TC ratio may potentially lead to discrepancies between different BC measurements. We studied the response of two instruments, the AVL Micro-Soot Sensor (MSS) and the Artium Laser-Induced Incandescence 300 (LII), to soot from two miniature combustion aerosol standard (mini-CAST) burners. By changing the air-fuel ratio, premixing nitrogen into the fuel, and using a catalytic stripper to remove volatile compounds, we produced a wide range of particle morphologies and EC contents. As the EC content decreased, both the instruments underreported the EC mass, but the LII diverged more severely. Upon closer investigation of eight conditions with EC/TC > 0.8, the LII underreporting was found independent of primary particle size, but increased with decreasing geometric mean diameter of the soot agglomerates. As the geometric mean diameter decreased from 160 nm to 50 nm, the differences between the LII and MSS increased from 15% to 50%. The results suggest that in addition to EC content, calibration procedures for the regulatory BC measurements may need to take particle size distributions into account.

© 2016 American Association for Aerosol Research     

Evaluation of a Heated-Inlet for Calibration of the SP2

Black carbon (BC) calibration standards, such as fullerene soot, are routinely used to calibrate single-particle soot photometer (SP2) instruments. Impurities in BC standards create uncertainties in these calibrations, and thus it is desirable to remove non-BC compounds from the aerosol, though removal processes must not significantly alter BC microphysical properties. We present a series of experiments using mobility- and mass-selected fullerene soot particles to assess the performance of a high-temperature denuder system for treating BC prior to SP2 analysis. Particle mass, incandescence, and scattering properties were measured by tandem aerosol particle mass analyzers and an SP2, after thermal treatment at a range of temperatures and residence times (RT). For a longer RT (e.g., ～6 s at 300°C), monodisperse fullerene soot particles of initial mass 1.4 fg decreased in mass with increasing temperature, by 3% at 300°C to 15% at 600°C. Mass losses were similar for fullerene soot particles of initial mass 10.7 fg. The peak height of the particle laser-induced incandescence (LII) and scattering intensities of the 10.7 fg fullerene soot increased by 7% and 3%, respectively, at 300°C, and by over 15% and 10% at 400°C, possibly due to microphysical changes after heating. When sampling through a 300°C denuder with a particle RT of 2.5 s, the LII intensity of ambient BC particles of initial mass 1.1 fg increased by 8%. In light of these results, denuder temperatures of ～300°C with 0.4 s ≤ RT ≤ 2.5 s are recommended for SP2 calibration.

Copyright 2013 American Association for Aerosol Research     

Development of an Automatic Beta Gauge Particulate Sampler with Filter Cassette Mechanism

A beta gauge particulate sampler for measuring the aerosol mass concentration in the ambient air is described. The instrument is automatically calibrated with two self-calibration mass standards during each sampling period, while it samples particles continuously with minimum sampling dead-time loss. Key design features of the instrument based on the attenuation of beta radiation include filter cassette mechanism, auto-calibration system, low sampling dead-time, high sensitivity, and straightforward audit procedures. The instrument consists of three main components: PM 10 inlet, mechanical filter movement system, and control and data processing system. The mechanical filter movement system includes particle collection system with filter cassette magazine, g -ray measuring module and particle sampling module, auto-calibration system, and flow control system. The control and data processing system performs filter cassette movement control, sampling pump control, and data analysis. The instrument has been tested in the field to compare the measurement results with those by gravimetric mass measurement. The developed beta gauge instrument has been proved to be an efficient measuring guage for the ambient particulate mass determination.     

Extending the Faraday cup aerosol electrometer based calibration method up to 5 µm

A Faraday cup aerosol electrometer based electrical aerosol instrument calibration setup from nanometers up to micrometers has been designed, constructed, and characterized. The set-up utilizes singly charged seed particles, which are grown to the desired size by condensation of diethylhexyl sebacate. The calibration particle size is further selected with a Differential Mobility Analyzer (DMA). For micrometer sizes, a large DMA was designed, constructed, and characterized. The DMA electrical mobility resolution was found to be 7.95 for 20?L/min sheath and 2?L/min sample flows. The calibration is based on comparing the instrument’s response against the concentration measured with a reference Faraday cup aerosol electrometer. The set-up produces relatively high concentrations in the micrometer size range (more than 2500 1/cm³ at 5.3?µm). A low bias flow mixing and splitting between the reference and the instrument was constructed from a modified, large-sized mixer and a four-port flow splitter. It was characterized at different flow rates and as a function of the particle size. Using two of the four outlet ports at equal 1.5?L/min flow rates, the particle concentration bias of the flow splitting was found to be less than ±1% in the size range of 3.6?nm–5.3?µm. The developed calibration set-up was used to define the detection efficiency of a condensation particle counter from 3.6?nm to 5.3?µm with an expanded measurement uncertainty (k?=?2) of less than 4% over the entire size range and less than 2% for most of the measurement points.

Copyright © 2018 American Association for Aerosol Research     

Instrument Busy Time and Mass Measurement using Aerosol Time-of-Flight Mass Spectrometry

Aerosol Time-of-Flight Mass Spectrometry (ATOFMS) instruments have been used widely to measure the size and composition of single ambient aerosol particles. ATOFMS data do not directly and quantitatively represent aerosol composition because the instruments exhibit non-linear response to particle concentration, size, and composition. Our approach is to analyze separately the components of non-linear ATOFMS response using field sampling data in order to understand ATOFMS response to ambient aerosols so that ATOFMS data can be scaled to more closely represent ambient aerosols. In this work we examine the effect of instrument busy time, mainly the time to process and save data, on ATOFMS response to ambient aerosols sampled during the 1999 Bakersfield Instrument Intercomparison Study (BIIS). During this study an ATOFMS instrument was operated alternately in normal and fast scatter data acquisition modes. In fast scatter mode, the instrument does not record mass spectra, minimizing instrument busy time; these data were used to determine particle arrival rates. Busy time in normal mode was found by a comparison of the number of particles detected to that expected for a Poisson process modified to include busy time. During the BIIS experiment, the ATOFMS instrument was busy between 5 and 95% of the nominal sampling time; thus busy time cannot be ignored for accurate quantitative analysis of ATOFMS data. ATOFMS data were scaled for on-line time and transmission efficiency, found by comparison with reference aerosol measurements, in order to estimate fine particle mass concentrations. Fine aerosol mass concentrations from scaled ATOFMS data demonstate semi-quantitative agreement with independent measurements using Beta Attenuation Monitors. We recommend that ATOFMS instruments be modified to measure busy time directly.     

A New Laser Induced Incandescence–Mass Spectrometric Analyzer (LII-MS) for Online Measurement of Aerosol Composition Classified by Black Carbon Mixing State

We developed a laser induced incandescence–mass spectrometric analyzer (LII-MS) for online measurements quantifying the aerosol chemical compositions with respect to the mixing state of black carbon (BC). The LII-MS is developed as a tandem series comprising an LII chamber to detect and vaporize BC-containing particles and a particle trap laser desorption mass spectrometer (PT-LDMS: Takegawa et al. 2012). The PT-LDMS collects aerosol particles transferred from the LII chamber and quantifies the chemical compositions. A newly designed collection probe, coupled with the sheath-air inlet nozzle of the LII chamber, enables a high throughput of aerosol particles without significant dilution. Total aerosol particles can be analyzed in the PT-LDMS by turning off the laser (MS mode), and the aerosol particles externally mixed with BC can be analyzed by turning on the laser (LII-MS mode). The difference in the PT-LDMS signals between the MS and LII-MS modes yields the chemical composition of materials internally mixed with BC. Performance of the developed instrument was evaluated in the laboratory by generating BC particles internally-mixed with oleic acid (OL) and BC particles externally mixed with ammonium sulfate particles. Preliminary results from ambient measurements are also presented and discussed.

Copyright 2014 American Association for Aerosol Research     

Improving the signal-to-noise ratio of Faraday cup aerosol electrometer based aerosol instrument calibrations

This study introduces a new bipolar measurement routine for particle number concentration calibrations. In the new routine, singly-charged particles of opposite polarities are measured sequentially with a Faraday cup aerosol electrometer (FCAE). We compared the bipolar routine to the traditional FCAE routine, where particle signal and electrometer offset are measured in turns, by calibrating a single CPC on a wide particle number concentration range (from 1000 to 77,000 cm^?3) with both routines. By increasing the signal-to-noise ratio, the bipolar routine decreases the type A uncertainty of the calibration especially at low particle concentrations. In practice, the new routine enables shortening the measurement times by 80% at the lowest particle concentrations which, in practice, corresponds to hours.

Copyright © 2016 American Association for Aerosol Research     

An intercomparison of aerosol absorption measurements conducted during the SEAC4RS campaign

During the SEAC⁴RS campaign in 2013, inflight measurements of light-absorption by aerosol in biomass burning and agriculture fire plumes were collected along with concomitant measurements of aerosol extinction, scattering, and black carbon mass concentration. Here, we compare three measurements of aerosol absorption coefficients: from a photoacoustic spectrometer (PAS), a particle soot absorption photometer (PSAP), and a continuous light absorption photometer (CLAP). Each of these absorption measurements was collected in three visible spectral regions: red, green, and blue (although the precise wavelength and bandwidth vary with each instrument). The absorption measurements were compared during the plumes, in the boundary layer, and in the free troposphere. The slopes from the comparison ranged from 0.6 to 1.24. For biomass burning plumes, the uncertainty in the absorption measurements translates into a range in single scattering albedos of 0.93–0.94 at a wavelength of 660?nm, 0.94–0.95 at 532?nm and 0.92–0.95 at 405?nm. Overall, the aerosol absorption instruments agreed within their stated accuracies. Comparisons with simultaneous measurements of refractive black carbon mass concentration (collected by a single particle soot photometer), were used to derive the mass absorption coefficients (MAC). For all wavelengths, the MAC was high by greater than a factor of three compared to the expected MAC for black carbon.

© 2018 American Association for Aerosol Research     

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.     

A Novel Optical Instrument for Estimating Size Segregated Aerosol Mass Concentration in Real Time

A novel optical instrument has been developed that estimates size segregated aerosol mass concentration (i.e., PM ₁₀ , PM ₄ , PM _2.5 , and PM ₁ ) over a wide concentration range (0.001–150 mg/m ³ ) in real time. This instrument combines photometric measurement of the particle cloud and optical sizing of single particles in a single optical system. The photometric signal is calibrated to approximate the PM _2.5 fraction of the particulate mass, the size range over which the photometric signal is most sensitive. The electrical pulse heights generated by light scattering from particles larger than 1 micron are calibrated to approximate the aerodynamic diameter of an aerosol of given physical properties, from which the aerosol mass distribution can be inferred. By combining the photometric and optical pulse measurements, this instrument can estimate aerosol mass concentrations higher than typical single particle counting instruments while providing size information and more accurate mass concentration information than traditional photometers. Experiments have shown that this instrument can be calibrated to measure aerosols with very different properties and yet achieve reasonable accuracy.     

Overall Performance Evaluation of Aerosol Number Samplers

At present, there is neither an officially accepted size-selective fiber (aerosol number) sampler, nor are there established performance criteria. In this work, a prototype preclassifier (multihole impactor) was used to connect a conventional asbestos sampler so that the aerosol penetration test and particle counting process could be performed. The bias, as a function of particle size, was defined as the difference between the measured penetration curve and the target ISO/ACGIH/CEN respirable convention. The imprecision was the standard error with reference to the mean aerosol penetration curve. A statistical term, one standard error shift (OSES) was used in a previous study to combine the sampling bias and imprecision. The bias and imprecision could be for aerosol number, aerosol mass, or even surface area. In this work, an additional step was taken by introducing another statistical term, maximum sampling shift (MSS), to further combine the OSES with the counting imprecision. For the surrogate sampler tested, the particle counting imprecision increased with increasing particle diameter and decreased with increasing geometric standard deviation. The particle counting imprecision was comparable with the OSES, and the resultant MSS map was actually the summation of imprecision and OSES.     

Large Particle Size Distribution in Five U.S. Cities and the Effect on a New Ambient Participate Matter Standard (PM10)

A mobile aerosol-sampling system was used to determine the large particle ambient aerosol size distribution (up to approximately 100 μm particle diameter) in five cities across the United States: Birmingham, Alabama; Research Triangle Park, North Carolina; Philadelphia, Pennsylvania; Phoenix, Arizona; and Riverside, California. A mobile wide range aerosol classifier (WRAC) developed at the University of Florida was used. The study shows that any measurement of ambient particulate matter with a size-fractionating inlet sampler will be influenced by the ambient particle size distribution.

Mass distribution measurements determined by the WRAC were compared with mass measurements obtained simultaneously using TSP Hi-Vol and 15 μm cut-size inhalable particulate network samplers. Aerosol size-classification results showed the presence of a large particle mass mode at all sites sampled. The position and magnitude of the large particle mode varied and was not a simple function of concentration. The percentage of the total aerosol mass collected by the present EPA reference method high-volume air sampler varied from about 85 to 95%. The percentage of total aerosol mass less than 10 μm varied from about 50 to 90%, depending on the sampling location and sampling condition.     

Simulation of Particle Size-Selective Air Samplers Placed in a Polydisperse Aerosol

The results of a numerical simulation of several air sampling instruments are presented. They are assumed to sample the same aerosol, with a log-normal particle-size distribution. Four instruments were studied: the 10-mm nylon cyclone, the MRE 113A gravimetric sampler, the CPM 3, and the CIP 10. The experimental data of particle collection efficiency were reduced by a model for each instrument. The model used combines two cumulative log-normal distribution functions, in order to have a good degree of flexibility necessary for representing the data of some devices that exhibit a maximum in efficiency (CPM 3, CIP 10). The concentrations “measured” by several air samplers were compared with each other; the differences were analyzed as functions of the aerosol parameters: mass median aerodynamic diameter and σ_g. The results that were obtained and those calculated from standard collection efficiencies, defining the conventional alveolar fraction of the aerosol, were also taken into account. This simulation method can be extended to any type of instrument and aerosol, and enables the prediction of the maximal deviations that could be observed between different instruments, or between one instrument and some reference standards.     

An Aerosol Chemical Speciation Monitor (ACSM) for Routine Monitoring of the Composition and Mass Concentrations of Ambient Aerosol

We present a new instrument, the Aerosol Chemical Speciation Monitor (ACSM), which routinely characterizes and monitors the mass and chemical composition of non-refractory submicron particulate matter in real time. Under ambient conditions, mass concentrations of particulate organics, sulfate, nitrate, ammonium, and chloride are obtained with a detection limit <0.2 μg/m³ for 30 min of signal averaging. The ACSM is built upon the same technology as the widely used Aerodyne Aerosol Mass Spectrometer (AMS), in which an aerodynamic particle focusing lens is combined with high vacuum thermal particle vaporization, electron impact ionization, and mass spectrometry. Modifications in the ACSM design, however, allow it to be smaller, lower cost, and simpler to operate than the AMS. The ACSM is also capable of routine stable operation for long periods of time (months). Results from a field measurement campaign in Queens, NY where the ACSM operated unattended and continuously for 8 weeks, are presented. ACSM data is analyzed with the same well-developed techniques that are used for the AMS. Trends in the ACSM mass concentrations observed during the Queens, NY study compare well with those from co-located instruments. Positive Matrix Factorization (PMF) of the ACSM organic aerosol spectra extracts two components: hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA). The mass spectra and time trends of both components correlate well with PMF results obtained from a co-located high resolution time-of-flight AMS instrument.     

Calibration of a particle mass spectrometer using polydispersed aerosol particles

Routine calibrations of online aerosol chemical composition analyzers are important for assessing data quality during field measurements. The combination of a differential mobility analyzer (DMA) and condensation particle counter (CPC) is a reliable, conventional method for calibrations. However, some logistical issues arise, including the use of radioactive material, quality control, and deployment costs. Herein, we propose a new, simple calibration method for a particle mass spectrometer using polydispersed aerosol particles combined with an optical particle sizer. We used a laser-induced incandescence–mass spectrometric analyzer (LII-MS) to test the new method. Polydispersed aerosol particles of selected chemical compounds (ammonium sulfate and potassium nitrate) were generated by an aerosol atomizer. The LII section was used as an optical particle sizer for measuring number/volume size distributions of polydispersed aerosol particles. The calibration of the MS section was performed based on the mass concentrations of polydispersed aerosol particles estimated from the integration of the volume size distributions. The accuracy of the particle sizing for each compound is a key issue and was evaluated by measuring optical pulse height distributions for monodispersed ammonium sulfate and potassium nitrate particles as well as polystyrene latex particles. A comparison of the proposed method with the conventional DMA-CPC method and its potential uncertainties are discussed.

Copyright © 2018 American Association for Aerosol Research     

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.     

An inter-comparison of black-carbon-related instruments in a laboratory study of biomass burning aerosol

Black carbon (BC)-containing particles are the most strongly light absorbing aerosols in the atmosphere. Measurements of BC are challenging because of its semi-empirical definition based on physical properties and not chemical structure, the complex and continuously changing morphology of the corresponding particles, and the effects of other particulate components on its absorption. In this study, we compare six available commercial continuous instruments measuring BC using biomass burning aerosol. The comparison involves a Soot Particle Aerosol Mass Spectrometer (SP-AMS), a Single-Particle Soot Photometer (SP2), an aethalometer, a Multiangle Absorption Photometer (MAAP), and a blue and a green photoacoustic extinctiometer (PAX). An SP-AMS collection efficiency equal to 0.35 was measured for this aerosol system. The corrected SP-AMS BC mass measurements agreed within 6% with the SP2 refractory BC mass values. Two regimes of behavior were identified for the optical instruments corresponding to high and low organic/BC ratio. The mass absorption cross-sections (MAC) measured varied from 26% to two times the instrument default values depending on the instrument and the regime. The presence of high organic aerosol concentration in this system can lead to overestimation of the BC mass by the optical instruments by as much as a factor of 2.7. In general, the discrepancy among the BC measurements increased as the organic carbon content of the BC-containing particles increased.

© 2018 American Association for Aerosol Research     

Reproducibility of Single Particle Chemical Composition during a Heavy Duty Diesel Truck Dynamometer Study

The chemical reproducibility of single particle mass spectrometry (SPMS) instruments is complicated by numerous factors, including uncertainties in the laser desorption/ionization process leading to shot-to-shot variability in single particle mass spectra, excessive fragmentation of carbonaceous species, as well as a relatively low duty cycle (1-10 Hz). With source apportionment being a major application for these instruments, proper source profiles must be determined from major aerosol sources. This brief communication illustrates, for the first time, the chemical reproducibility of an aerosol time-of-flight mass spectrometer (ATOFMS) sampling highly transient heavy duty diesel (HDD) truck exhaust emissions from a transportable heavy duty vehicle emissions testing laboratory, which includes a dilution tunnel as well as a residence chamber.In addition to examining the reproducibility of ATOFMS using a complex mixture of "real" aerosol particles, the chemical reproducibility of a dynamometer system at the single particle level is tested. The results presented indicate that for future studies, truck-to-truck and source-to-source variations can be attributed to chemical differences and not just to innate variations due to instrumental variability.