Ultrafine Condensation Particle Counter Research Articles

Integrated microfluidic-based ultrafine water condensation particle counter (UWCPC) for monitoring of airborne nanoparticle generation and growth mechanisms

This study reports a newly developed condensation particle counter for nanoparticle source tracking, growth mechanism analysis, and wide area nanoparticle monitoring.

Volatility of aircraft exhaust ultrafine particles inferred from field measurements at Narita International Airport

We conducted field measurements of aerosols near a runway at Narita International Airport (NRT) in February 2018 to characterize the physical and chemical properties of aircraft exhaust ultrafine particles (UFPs; diameter <100 nm). An ultrafine condensation particle counter (UCPC; d50 = 2.5 nm), a condensation particle counter (CPC; d50 = 10 nm), and an engine exhaust particle sizer (EEPS; 6.0–523 nm) were used to measure the particle number concentrations and size distributions in ambient air. The sample flow for the UCPC and CPC was passed through an evaporation tube for heated measurements (150 °C, 250 °C, or 350 °C) or through a bypass tube for unheated measurements. The evaporation tube temperature (Ttube) of 350 °C was used as a threshold point for the separation of volatile and non-volatile particles. The removal efficiency of the volatile particles at intermediate temperatures (<350 °C) was evaluated in the laboratory using triacontane (C30) and tetracontane (C40) as test compounds. The critical temperature at which the laboratory-generated 30-nm C30 and C40 particles were almost entirely removed was ∼130 °C and ∼250 °C, respectively. The particle number concentrations measured by the UCPC, CPC, and EEPS at NRT were used to investigate the volatility of aircraft exhaust UFPs under real-world operating conditions. The number fraction of the non-volatile particles strongly depended on the geometric mean diameter (GMD) of the unheated particle number size distributions, whereas the vaporization temperature of the volatile particles did not exhibit significant dependency on GMD. The particle number fraction remaining, calculated for the selected evaporation tube temperature (Ttube), indicates that ∼50% and ≳ 90% of the volatile particles were removed at Ttube = 150 °C and 250 °C, respectively, on a number basis. These results suggest that a large fraction (more than half by number) of the volatile UFPs emitted from aircraft was equally or less volatile than the 30 nm pure C30 particles and only a small fraction of the volatile UFPs was equally or less volatile than the 30 nm pure C40 particles.

Sulfuric acid-dimethylamine particle formation enhanced by functional organic acids: an integrated experimental and theoretical study.

Atmospheric new particle formation (NPF), which has been observed globally in clean and polluted environments, is an important source of boundary-layer aerosol particles and cloud condensation nuclei, but the fundamental mechanisms leading to multi-component aerosol formation have not been well understood. Here, we use experiments and quantum chemical calculations to better understand the involvement of carboxylic acids in initial NPF from gas phase mixtures of carboxylic acid, sulfuric acid (SA), dimethylamine, and water. A turbulent flow tube coupled to an ultrafine condensation particle counter with particle size magnifier has been set up to measure NPF. Experimental results show that pyruvic acid (PA), succinic acid (SUA), and malic acid (MA) can enhance sulfuric acid-dimethylamine nucleation in the order PA < SUA < MA with a greater enhancement observed at lower SA concentrations. Computational results indicate that the carboxylic and hydroxyl groups are related to the enhancement. This experiment-theory study shows the formation of multi-component aerosol particles and the role of the organic functional group, which may aid in understanding the role of organics in aerosol nucleation and growth in polluted areas, and help to choose organic molecules of specific structures for simulation.

Characteristics of sub-10 nm particle emissions from in-use commercial aircraft observed at Narita International Airport

Abstract. The characterization of ultrafine particle emissions from jet aircraft equipped with turbofan engines, which are commonly used in civil aviation, is an important issue in the assessment of the impacts of aviation on climate and human health. We conducted field observations of aerosols and carbon dioxide (CO2) near a runway at Narita International Airport, Japan, in February 2018. We used an ultrafine condensation particle counter (UCPC) and a condensation particle counter (CPC) with unheated and 350 ∘C heated operation modes to investigate the contributions of sub-10 nm size ranges to the total and the non-volatile particle number concentrations. The performance of the 350 ∘C heated mode was tested in the laboratory to verify the consistency with existing methods for non-volatile particle measurements. We also used a scanning mobility particle sizer with unheated and 350 ∘C heated modes and an engine exhaust particle sizer for the measurements of particle number size distributions. Spiked increases in the particle number concentrations and CO2 mixing ratios were observed to be associated with the directions of wind from the runway, which can be attributed to diluted aircraft exhaust plumes. We estimated the particle number emission indices (EIs) for discrete take-off plumes using the UCPC, CPC, and CO2 data. The median values of the total and the non-volatile particle number EIs for diameters larger than 2.5 nm as derived from the UCPC data were found to be 1.1×1017 and 5.7×1015 kg per fuel, respectively. More than half the particle number EIs were in the size range smaller than 10 nm for both the total and the non-volatile particles in most of the cases analyzed in this study. The significance of sub-10 nm size ranges for the total particles in the diluted plumes was qualitatively consistent with previous studies, but that for the non-volatile particles was unexpected. Possible factors affecting the similarities and differences compared with the previous findings are discussed.

Performance comparison of SMPSs with soft X-ray and Kr-85 neutralizers in a humid atmosphere

Scanning mobility particle sizer (SMPS) is widely used for particle number size distribution measurements of submicron particles. In this work, two TSI® SMPSs equipped with a soft X-ray neutralizer and a Kr-85 neutralizer, respectively, were operated in parallel to measure particle number size distributions of ambient air. An independent TSI® ultrafine condensation particle counter (CPC) was used as a reference to measure the total concentration of particles in the ambient air. Our results show that the total particle concentrations measured by the two SMPSs were comparable with each other, while their size-resolved concentration ratios were size-dependent and relative humidity (RH)-dependent. Neutralizer was found to be essential to quickly bring small particles to charge equilibrium in field measurements, as indicated by the comparison of particle number size distributions measured by the Kr-85 SMPS with those inverted from naturally charged particles. The total particle concentrations measured by two SMPSs tend to exceed those by the reference CPC at high RH, hinting that the particle concentrations measured by SMPSs could be overestimated at high RH. This study urges a better understanding of the bipolar charging processes under high RH conditions.

Counting on chemistry: laboratory evaluation of seed-material-dependent detection efficiencies of ultrafine condensation particle counters

Abstract. Condensation particle counters (CPCs) are crucial instruments for detecting sub-10 nm aerosol particles. Understanding the detection performance of a CPC requires thorough characterization under well-controlled laboratory conditions. Besides the size of the seed particles, chemical interactions between the working fluid and the seed particles also influence the activation efficiencies. However, common seed particle materials used for CPC characterizations are not chosen with respect to chemical interactions with vapor molecules of the working fluid by default. Here, we present experiments on the influence of the seed particle material on the detection efficiencies and the 50 % cutoff diameters of commonly used CPCs for the detection of sub-10 nm particles. A remarkable set consisting of six different and commercially available particle detectors, including the newly developed TSI V-WCPC 3789 and a tuned TSI 3776, was tested. The corresponding working fluids of the instruments are n-butanol, diethylene glycol and water. Among other materials we were able to measure detection efficiencies with nanometer-sized organic seed particles reproducibly generated by the oxidation of β-caryophyllene vapor in a flow tube. Theoretical simulations of supersaturation profiles in the condensers were successfully related to measured detection efficiencies. Our results demonstrate the importance of chemical similarities between seed particles and the working fluids used when CPCs are characterized. We anticipate our study to contribute to a deeper understanding of chemical interactions during heterogeneous nucleation processes.

Precision characterization of three ultrafine condensation particle counters using singly charged salt clusters in the 1–4 nm size range generated by a bipolar electrospray source

Molecular singly charged clusters generated by electrospray sources are commonly used for calibration measurements of ultrafine Condensation Particle Counters (CPCs) in the sub-2 nm size range. Thi...

Activation of sub 2 nm Water Soluble and Insoluble Standard Ions with Saturated Vapors of Butanol in a Boosted TSI ultrafine CPC

Tetraheptylammonium bromide (THABr), tetrabutylammonium bromide (TBABr) and tetraethylammonium bromide (TEABr) dissolved in methanol or water methanol mixtures (~1 mM) produce via positive electrospray atomization and high resolution classification electrical classification standard clean ions (monomer and dier) which are singly charged. THABr is hydrophobic and insoluble in water, TBABr and TEABr are hygroscopic and water soluble (0.6 and 2.8 kg/L respectively). These ions are used to study the effect of hygroscopicity on the activation of aerosol particles in the sub 2 nm range via the detection efficiency measurement of a boosted ultrafine TSI condensation particle counter (3025A). Water solubility of particles seems to play a role in the activation and growth with butanol vapor in the CPC (condensation particle counter) independently of the size.

Performance evaluation of conventional type conductive cooling continuous flow compact water-based CPC (Hy-WCPC)

In this study, a water-based compact handheld condensation particle counter (Hy-WCPC) is developed and its performance is evaluated. The Hy-WCPC is a small and light water-based CPC and the operating principle is the same as the conventional continuous flow conductive cooling alcohol-based condensation particle counters (CPC). This study presents the particle material dependent Hy-WCPC cut-off sizes and the particle concentration counting linearity between the Hy-WCPC and electrometer by generating silver, sodium chloride, zinc and paraffin particles. Moreover, the comparison between the Hy-WCPC and commercially available ultrafine CPC (TSI 3776) for ambient airborne particles is presented. The cut-off sizes of the Hy-WCPC for silver and paraffin particles are 3.61nm and 5.30nm, respectively. For sodium chloride and zinc particles, the Hy-WCPC lower detection limit is achieved less than 4nm. Moreover, the particle concentration counting linearity between the Hy-WCPC and electrometer is presented. The excellent particle number concentration counting linearity agreement between the Hy-WCPC and electrometer is shown for the laboratory generated particles. Also, the particle concentration counting linearity between the Hy-WCPC and the TSI 3776 for outdoor ambient airborne particles is shown. The reasonable agreement between the Hy-WCPC and the TSI 3776 was obtained. In the long-term measurement of outdoor ambient airborne particles for 7 days, this agreement had been maintained, however, after 7 days, the TSI 3776 did not operate properly due to the high humidity, while the Hy-WCPC was operating without the problem.

Intercomparison of a Personal CPC and Different Conventional CPCs

ABSTRACTWe here report on a study that examines the performance of a water based personal condensation particle counter (CPC) PUFP C100 (Enmont, LLC) when sampling a variety of different test aerosols. Three additional CPCs were included in the study, namely, the general purpose water based CPC model 3787 (TSI) as well as the more than 20 year old CPC model 3022 (TSI) and ultrafine CPC model 3025A (TSI), both based on butanol. The responses of these CPCs were compared to a reference ultrafine CPC model 3776 (TSI). Test aerosols included hydrophilic NaCl, moderately hydrophobic carbon and highly hydrophobic DEHS aerosols of various sizes and concentrations. The CPC PUFP C100 measured according to its specifications with high precision and accuracy as long as the particles were not highly hydrophobic, but failed to adequately measure the concentrations of highly hydrophobic DEHS aerosols. Its detection efficiency for very small particles, e.g., 5.4 nm, was decreased, which was expected based on its particle size detection limit. The TSI water CPC model 3787 showed a similar behavior for all aerosols, except that this CPC was able to accurately measure the concentration of 5.4 nm NaCl particles. The concentrations measured with the two old and unserviced butanol CPCs were highly correlated with the concentrations delivered by the reference CPC. Nevertheless, the concentrations measured with both old CPCs were clearly below the reference concentrations.

Experimental Investigation of a Condensation Particle Counter Challenged by Particles with Varying Wettability to Working Liquid

ABSTRACTThe counting efficiency of an in-house laminar flow Condensation Particle Counter (CPC) was investigated experimentally. The CPC was challenged by different sources of particles (ambient particles, and combustion particles generated from CH4 and C2H4), and the counting efficiency of the in-house ultrafine CPC (IUCPC) was obtained by comparing particle concentration data measured by the IUCPC with that measured by a reference instrument, TSI CPC 3775. The counting efficiency is closely related to the contact angle (an indication of the wettability of particles by the working fluid) and the combination of the saturator and the condenser temperatures. The particles from different sources appeared to have different contact angles, in other words, different wettability by the working liquid.

Quantifying the effects of operational parameters on the counting efficiency of a condensation particle counter using response surface Design of Experiments (DoE)

The size-resolved counting efficiency of an in-house ultrafine condensation particle counter (IUCPC) being challenged by sodium chloride (NaCl) particles was experimentally determined with a reference electrometer TSI 3068B. The influence of several operational parameters including the saturator temperature (35 to 45℃), the condenser temperature (10 to 25℃), the capillary sample flow rate (30 to 60mL/min) and the total flow rate (300 to 400mL/min) on the cut-off size D50 (particle diameter with 50% counting efficiency) was investigated using response surface design of experiments (DoE). Thirty one test points with varying operational conditions including 7 replicated test points were performed to evaluate the primary effects of operational parameters and their interactive effects on the cut-off size D50 of the IUCPC. The results indicated that the saturator temperature and the condenser temperature had a greater impact on the cut-off size D50 than the capillary flow rate and the total flow rate. CFD simulation demonstrated that high capillary flow rate in the IUCPC could induce a wider diffusion zone for the core aerosol flow, making more particles enter low supersaturation area near the wall. According to the ANOVA (analysis of variance), the most influential factor for the cut-off size D50 was the condenser temperature, followed by the saturator temperature, the total flow rate and the capillary flow rate. Some interactive effects from combinations of factors on the D50 are also significant. R-squared value of 0.9176 implied that the ultimate model for the IUCPC D50 consistently fits the experimental results.

Modification and laboratory evaluation of a TSI ultrafine condensation particle counter (Model 3776) for airborne measurements

ABSTRACTA butanol-type ultrafine condensation particle counter (UCPC, Model 3776, TSI, Inc., Shoreview, MN, USA), which can achieve a 50% detection efficiency diameter (d50) of 2.5 nm using a capillary-sheath structure, was modified and tested in the laboratory for airborne measurements. The aerosol flow rate through the capillary is a key factor affecting the quantification of aerosol particle number concentrations. A pressure-dependent correction factor for the aerosol flow rate was determined using a newly added mass flow meter for the sheath flow and the external calibration system. The effect of particle coincidence in the optical sensing volume was evaluated using an aerosol electrometer (AE, Model 3068B, TSI, Inc.) as a reference. An additional correction factor for the coincidence effect was derived to improve the quantification accuracy at higher concentrations. The particle detection efficiency relative to the AE was measured for mobility diameters of 3.1–50 nm and inlet absolute pressures of 10...

An optimized two-step derivatization method for analyzing diethylene glycol ozonation products using gas chromatography and mass spectrometry

The ozonation of hydroxyl compounds (e.g., sugars and alcohols) gives a broad range of products such as alcohols, aldehydes, ketones, and carboxylic acids. This study developed and optimized a two-step derivatization procedure for analyzing polar products of aldehydes and carboxylic acids from the ozonation of diethylene glycol (DEG) in a non-aqueous environment using gas chromatography–mass spectrometry. Experiments based on Central Composite Design with response surface methodology were carried out to evaluate the effects of derivatization variables and their interactions on the analysis. The most desirable derivatization conditions were reported, i.e., oximation was performed at room temperature overnight with the o-(2,3,4,5,6-pentafluorobenzyl) hydroxyl amine to analyte molar ratio of 6, silylation reaction temperature of 70°C, reaction duration of 70min, and N,O-bis(trimethylsilyl)-trifluoroacetamide volume of 12.5μL. The applicability of this optimized procedure was verified by analyzing DEG ozonation products in an ultrafine condensation particle counter simulation system.

Intercomparison of a portable and two stationary mobility particle sizers for nanoscale aerosol measurements

During occupational exposure studies, the use of conventional scanning mobility particle sizers (SMPS) provides high quality data but may convey transport and application limitations. New instruments aiming to overcome these limitations are being currently developed. The purpose of the present study was to compare the performance of the novel portable NanoScan SMPS TSI 3910 with that of two stationary SMPS instruments and one ultrafine condensation particle counter (UCPC) in a controlled atmosphere and for different particle types and concentrations.The results show that NanoScan tends to overestimate particle number concentrations with regard to the UCPC, particularly for agglomerated particles (ZnO, spark generated soot and diesel soot particles) with relative differences >20%. The best agreements between the internal reference values and measured number concentrations were obtained when measuring compact and spherical particles (NaCl and DEHS particles). With regard to particle diameter (modal size), results from NanoScan were comparable < [± 20%] to those measured by SMPSs for most of the aerosols measured. The findings of this study show that mobility particle sizers using unipolar and bipolar charging may be affected differently by particle size, morphologies, particle composition and concentration. While the sizing accuracy of the NanoScan SMPS was mostly within ±25%, it may miscount total particle number concentration by more than 50% (especially for agglomerated particles), thus making it unsuitable for occupational exposure assessments where high degree of accuracy is required (e.g., in tier 3). However, can be a useful instrument to obtain an estimate of the aerosol size distribution in indoor and workplace air, e.g., in tier 2.

Fast and precise measurement in the sub-20 nm size range using a Scanning Mobility Particle Sizer

An increasing number of studies are focusing on the detection and investigation of nanometer-sized particles. One important tool is the Scanning Mobility Particle Sizer (SMPS). In the case of dynamic processes like nucleation events, the lower detection threshold as well as the measurement time are important system parameters. High accuracy of the applied voltage as a function of time during fast scanning is required. Short scan times additionally yield a broadening and smearing of the measured size distribution. Here, the performance of the Nano-SMPS using the new TSI classifier (TSI 3082) in combination with either the nano water condensation particle counter (TSI 3788) or the ultrafine condensation particle counter (TSI 3776) was investigated. The focus of this work is the performance of the system at the lower detection limit as a function of the scan time. Fast scan times as short as 3s were tested. The reproducibility of the aerosol size distribution and number concentration for different distributions and materials was investigated. The tested substances included different proteins, sucrose and polystyrene latex reference particles. The sizing reproducibility and accuracy for all tested scan times was within 3%. The measured total number concentration was captured with a precision of ±3% for all tested scan times.

Growth of sulphuric acid nanoparticles under wet and dry conditions

Abstract. New particle formation, which greatly influences the number concentrations and size distributions of an atmospheric aerosol, is often followed by a rapid growth of freshly formed particles. The initial growth of newly formed aerosol is the crucial process determining the fraction of nucleated particles growing to cloud condensation nuclei sizes, which have a significant influence on climate. In this study, we report the laboratory observations of the growth of nanoparticles produced by nucleation of H2SO4 and water in a laminar flow tube at temperatures of 283, 293 and 303 K, under dry (a relative humidity of 1%) and wet conditions (relative humidity of 30%) and residence times of 30, 45, 60 and 90 s. The initial H2SO4 concentration spans the range from 2 × 108 to 1.4 × 1010 molecule cm−3 and the calculated wall losses of H2SO4 were assumed to be diffusion limited. The detected particle number concentrations, measured by the Ultrafine Condensation Particle Counter (UCPC) and Differential Mobility Particle Sizer (DMPS), were found to depend strongly on the residence time. Hygroscopic particle growth, presented by growth factors, was found to be in good agreement with the previously reported studies. The experimental growth rates ranged from 20 nm h−1 to 890 nm h−1 at relative humidity (RH) 1% and from 7 nm h−1 to 980 nm h−1 at RH 30% and were found to increase significantly with the increasing concentration of H2SO4. Increases in the nucleation temperature had a slight enhancing effect on the growth rates under dry conditions. The influence of relative humidity on growth was not consistent – at lower H2SO4 concentrations, the growth rates were higher under dry conditions while at H2SO4 concentrations greater than 1 × 1010 molecule cm−3, the growth rates were higher under wet conditions. The growth rates show only a weak dependence on the residence time. The experimental observations were compared with predictions made using a numerical model, which investigates the growth of particles with three different extents of neutralization by ammonia, NH3: (1) pure H2SO4 – H2O particles; (2) particles formed by ammonium bisulphate, (NH4)HSO4; (3) particles formed by ammonium sulphate, (NH4)2SO4. The highest growth rates were found for ammonium sulphate particles. Since the model accounting for the initial H2SO4 concentration predicted the experimental growth rates correctly, our results suggest that the commonly presumed diffusional wall losses of H2SO4 in case of long-lasting experiments are not so significant. We therefore assume that there are not only losses of H2SO4 on the wall, but also a flux of H2SO4 molecules from the wall into the flow tube, the effect being more profound under dry conditions and at higher temperatures of the tube wall. Based on a comparison with the atmospheric observations, our results indicate that sulphuric acid alone cannot explain the growth rates of particles formed in the atmosphere.

Comparison of three nanoparticle sizing instruments: The influence of particle morphology

The TSI Fast Mobility Particle Sizer (FMPS), Engine Exhaust Particle Sizer (EEPS), and Scanning Mobility Particle Sizer (SMPS) provide size distributions for 6–560 nm particles. The aim of this study was to perform comprehensive equivalence testing of these three particle sizing instruments with particles of contrasting chemical and physical characteristics (urban ambient, diesel exhaust, and laboratory-generated particulate). It was observed that the EEPS and FMPS measurements agreed to within 15% thus concluding that data from these instruments may be considered equivalent. Parallel measurements with the SMPS showed that when measuring diesel exhaust particulate during ISO8178 Mode 9 operation there is significant overestimation of particle concentrations by both the EEPS and the FMPS in the 20–120 nm size range (25–38% overestimation). This overestimation also occurred for near-road measurement of heavy emitter vehicle plumes in ambient samples (up to 75% overestimation). Laboratory-generated soot agglomerate particles, whose shape was verified by transmission electron microscopy, were also tested. The agglomerate nature of diesel soot particulate was the dominant cause of the overestimation; parallel measurements with an FMPS and an Ultrafine Condensation Particle Counter of the laboratory-generated soot particulate showed overestimation by up to a factor of three.

Comparability of mobility particle sizers and diffusion chargers

A large study on the comparability of various aerosol instruments was conducted. The study involved altogether 24 instruments, including eleven scanning, sequential and fast mobility particle sizers (five Grimm SMPS+C, three TSI SMPS and three FMPS) with different settings and differential mobility analyzers (DMAs), twelve instruments based on unipolar diffusion charging to determine size integrated concentrations and in some cases mean particle size (five miniDiSCs of the University of Applied Sciences and Arts Northwestern Switzerland, four Philips Aerasense nanoTracers, two TSI Nanoparticle Surface Area Monitors and one Grimm nanoCheck) and one TSI ultrafine condensation particle counter (UCPC). All instruments were simultaneously challenged with particles of various sizes, concentrations and morphologies. All measurement results were compared with those from a freshly calibrated SMPS for size distributions and the UCPC for number concentration. In general, all SMPSs showed good comparability with particularly the sizing agreeing to within a few percent. Differences in the determined number concentration were somewhat more pronounced, but the largest deviations could be tracked back to the use of an older software version. The comparability of the FMPSs was shown to be lower, with discrepancies on the order of ±25% for sizing and ±30% for total concentrations. The discrepancies between FMPSs and the internal reference SMPS seemed to be influenced by particle size and morphology. Total number and/or lung deposited surface area concentrations measured with unipolar diffusion charger based instruments generally agreed to within ±30% with the internal references (CPC for number concentrations; lung deposited surface area derived from SMPS measurements), as long as the particle size distributions of the test aerosols were within the specified limits for the instruments. When the upper size limit was exceeded, deviations of up to several hundred percent were detected.

Evaluation of a newly developed diffusion denuder for atmospheric aerosol separation from co-pollutant gases

This paper presents the design, development and performance evaluation of a non-selective membrane based single annular tube diffusion denuder employed to separate co-pollutant gases from the aerosol of interest. The experiments were carried out on a single annular tube diffusion denuder and the gas removal efficiencies were experimentally determined using a laboratory scale setup as well as under ambient conditions. Using a simple combustion source, the removal efficiency of carbon monoxide was calculated for different main flow (MF) and flush flow (FF) combinations and was found to be in the range of 94–100%. The overall soot particle transmission efficiency was found to be in the range of 70–99% for particle size between 0.3μm and 2μm. Overall, transmission efficiencies for submicron particles were also evaluated using an ultrafine condensation particle counter. After the controlled laboratory testing of the prototype denuder, experiments were conducted using ambient air as the test aerosol. This prototype denuder provided a much higher efficiency of gaseous removal in a single stage as compared to earlier reported values. Its simple and easy operation makes it a promising device to use as compared with other commonly employed chemical adsorption based alternate tools.