AMT Atmospheric Measurement Techniques AMT Atmos. Meas. Tech. 1867-8548 Copernicus Publications Göttingen, Germany 10.5194/amt-7-2121-2014 Evaluation of the performance of a particle concentrator for online instrumentation Saarikoski S. 1 2 3 Carbone S. 1 Cubison M. J. 2 3 7 Hillamo R. 1 Keronen P. https://orcid.org/0000-0001-5019-0904 4 Sioutas C. 5 Worsnop D. R. 1 4 6 Jimenez J. L. https://orcid.org/0000-0001-6203-1847 2 3 Atmospheric Composition Research, Finnish Meteorological Institute, 00101, Helsinki, Finland Cooperative Institute for Research in the Environmental Sciences, 80309, Boulder, USA Department of Chemistry and Biochemistry, University of Colorado at Boulder, 80309, Boulder, USA Department of Physics, University of Helsinki, Post Office Box 64, 00014, Helsinki, Finland Department of Civil and Environmental Engineering, University of Southern California, Los Angeles, CA, 90089, USA Aerodyne Research Inc., Billerica, MA 01821, USA now at: Tofwerk AG, 3600 Thun, Switzerland 15 07 2014 7 7 2121 2135 Copyright: © 2014 S. Saarikoski et al. 2014 This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/ This article is available from https://amt.copernicus.org/articles/7/2121/2014/amt-7-2121-2014.html The full text article is available as a PDF file from https://amt.copernicus.org/articles/7/2121/2014/amt-7-2121-2014.pdf

The performance of the miniature Versatile Aerosol Concentration Enrichment System (m-VACES; Geller et al., 2005) was investigated in laboratory and field studies using online instruments. Laboratory tests focused on the behavior of monodisperse ammonium sulfate (AS) or dioctyl sebacate (DOS) particles in the m-VACES measured with the aerodynamic particle sizer (APS) and scanning mobility particle sizer (SMPS). The ambient measurements were conducted at an urban site in Helsinki, Finland, where the operation of the m-VACES was explored in conjunction with a Soot Particle Aerosol Mass Spectrometer (SP-AMS) in addition to the SMPS. In laboratory tests, the growth of particles in water vapor produced a stable droplet size distribution independent of the original particle size. However, when the droplets were dried with the goal of measuring the original size distribution, a shift to larger particles was observed for small particle sizes (up to ~ 200 nm in mobility diameter). That growth was probably caused by water-soluble organic compounds absorbed on the water droplets from the gas phase, but not evaporated in the drying phase. In ambient measurements, a similar enrichment was observed for nitrate and sulfate in the m-VACES whereas the presence of acidic ambient particles affected the enrichment of ammonium. Gaseous ammonia was likely to be absorbed on acidic particles in the m-VACES, neutralizing the aerosol. For organics, the enrichment efficiency was comparable with sulfate and nitrate but a small positive artifact for hydrocarbons and nitrogen-containing organic compounds was noticed. Ambient and concentrated organic aerosol (OA) was analyzed further with positive matrix factorization (PMF). A three-factor solution was chosen for both of the data sets but the factors were slightly different for the ambient and concentrated OA, however, the data set used for the PMF analysis was limited in size (3 days) and therefore had substantial uncertainty. Overall, the operation of the m-VACES was not found to lead to any severe sampling artifacts. The effect of acidity could be an issue in locations where the aerosol is acidic, however, in those cases the use of a denuder (which was not used in this study) is recommended. Further ambient tests are needed for the characterization of the m-VACES as the time period for the ambient measurements was only 5 days in this study. Especially for OA additional tests are important as the chemical properties of organics can differ widely depending on time and location.

 References Aiken, A. C., DeCarlo, P. F., and Jimenez, J. L.: Elemental analysis of organic species with electron ionization high-resolution mass spectrometry, Anal. Chem., 79, 8350–8358, 2007. Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K., Ulbrich, I. M., Mohr, C., Kimmel, J. R., Sueper, D., Zhang, Q., Sun, Y., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Onasch, T. B., Alfarra, R., Prévôt, A. S. H., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez., J. L.: O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high resolution time-of-flight aerosol mass spectrometry. Environ. Sci. Technol., 42, 4478–4485, 2008. Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R., Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L. R., Trimborn, A. M., Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and Microphysical Characterization of Ambient Aerosols with the Aerodyne Aerosol Mass Spectrometer, Mass Spectrom. Rev., 26, 185–222, 2007. Chang, M. C., Sioutas, C., Kim, S., Gong Jr., H., and Linn, W. S.: Reduction of nitrate losses from filter and impactor samplers by means of concentration enrichment. Atmos. Environ., 34, 85-98, 2000. Charlson, R. J., Schwartz, S. E., Hales, J. M., Cess, R. D., Coakley, J. A. Jr., Hasen, J. E., and Hofmann, D. J.: Climate Forcing by Anthropogenic Aerosols, Science, 255, 423-430, 1992. Cho, A. K., Sioutas, C., Miguel, A. H., Kumagai, Y., Schmitz, D. A., Singh, M., Eiguren-Fernandez, A., and Froines, J. R.: Redox activity of airborne particulate matter at different sites in the Los Angeles Basin, Environ. Res., 99, 40–47, 2005. DeCarlo P. F., Kimmel J. R., Trimborn A., Northway M. J., Jayne J. T., Aiken A. C., Gonin M., Fuhrer K., Horvath T., Docherty K. S., Worsnop D. R., and Jimenez J. L.: Field-deployable, high-resolution, time-of-flight mass spectrometer, Anal. Chem., 78, 8281–8289, 2006. Demokritou, P., Gupta, T. Ferguson, S., and Koutrakis, P.: Development of a High-Volume Concentrated Ambient Particles System (Caps) for Human and Animal Inhalation Toxicological Studies, Inhal. Toxicol., 15, 111–129, 2003. Dockery, D. W., Pope, C. A., Xu, X., Spengler, J. D., Ware, J. H., Fay, M. E., Ferris, B. G., and Speizer, F. E.: An Association between Air Pollution and Mortality in Six US Cities, N. Engl. J. Med., 329, 1753–1759, 1993. Dreyfus, M. A. and Johnston, M. V.: Rapid Sampling of Individual Organic Aerosol Species in Ambient Air with the Photoionization Aerosol Mass, Aerosol Sci. Technol., 42, 18–27, 2008. Ellis, R. A., Murphy, J. G., Markovic, M. Z., VandenBoer, T. C., Makar, P. A., Brook, J., and Mihele, C.: The influence of gas-particle partitioning and surface-atmosphere exchange on ammonia during BAQS-Met, Atmos. Chem. Phys., 11, 133–145, <a href="http://dx.doi.org/10.5194/acp-11-133-2011">https://doi.org/10.5194/acp-11-133-2011</a>, 2011. Freney, E. J., Heal, M. R., Donovan, R. J., Mills, N. L., Donaldson, K., Newby, D. E., Fokkens, P. HB., and Cassee, F. R.: A single-particle characterization of a mobile Versatile Aerosol Concentration Enrichment System for exposure studies, Fibre Toxicol., 3, 8, <a href="http://dx.doi.org/10.1186/1743-8977-3-8">https://doi.org/10.1186/1743-8977-3-8</a>, 2006. Geller, G. D., Biswas, S., Fine, P. M., and Sioutas, C.: A new compact aerosol concentrator for use in conjunction with low flow-rate continuous aerosol instrumentation, J. Aerosol Sci., 36, 1006–1022, 2005. Gupta, T., Demokritou, P., and Koutrakis, P.: Development and Performance Evaluation of a High Volume Ultrafine Particle Concentrator for Inhalation Toxicological Studies, Inhal. Toxicol., 16, 1–12, 2004. Huffman, J. A., Jayne, J. T., Drewnick, F., Aiken, A. C., Onasch, T., Worsnop, D. R., and Jimenez, J. L.: Design, Modeling, Optimization, and Experimental Tests of a Particle Beam Width Probe for the Aerodyne Aerosol Mass Spectrometer, Aerosol Sci. Technol., 39, 1143–1163, <a href="http://dx.doi.org/10.1080/02786820500423782">https://doi.org/10.1080/02786820500423782</a>, 2005. Järvi, L., Hannuniemi, H., Hussein, T., Junninen, H., Aalto, P. P., Hillamo, R., Mäkelä, T., Keronen, P., Siivola, E., Vesala, T., and Kulmala, M.: The urban measurement station SMEAR III: Continuous monitoring of air pollution and surface-atmosphere interactions in Helsinki, Finland, Boreal Environ. Res., 14, 86–109, 2009. Jung, H., Arellanes, C., Zhao, Y., Paulson, S., Anastasio, C., and Wexler, A.: Impact of the Versatile Aerosol Concentration Enrichment System (VACES) on Gas Phase Species, Aerosol Sci. Technol., 44, 1113–1121, 2010. Khlystov, A., Zhang, Q., Jimenez, J. L., Stanier, C., Pandis, S. N., Canagaratna, M. R., Fine, P., Misra, C., and Sioutas, C.: In situ concentration of semi-volatile aerosol using water-condensation technology, J. Aerosol Sci., 36, 866–-880, 2005. Kim, S., Jaques, P. A., Chang, M. C., Barone, T., Xiong, C., Friedlander, S. K., and Sioutas, C.: Versatile aerosol concentration enrichment system (VACES) for simultaneous in vivo and in vitro evaluation of toxic effects of ultrafine, fine and coarse ambient particles – Part II: field evaluation, J. Aerosol Sci., 32, 1299–1314, 2001a. Kim, S., Jaques, P. A., Chang, M. C., Froines, J. R., and Sioutas, C.: Versatile aerosol concentration enrichment system (VACES) for simultaneous in vivo and in vitro evaluation of toxic effects of ultrafine, fine and coarse ambient particles – Part I: development and laboratory characterization, J. Aerosol Sci., 32, 1281–1297, 2001b. Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prévôt, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503–1522, <a href="http://dx.doi.org/10.5194/acp-7-1503-2007">https://doi.org/10.5194/acp-7-1503-2007</a>, 2007. Lee, T., Sullivan, A. P., Mack, L., Jimenez, J. L., Kreidenweis, S. M. Onasch, T. B., Worsnop, D. R., Malm, W., Wold, C. E., Hao, W. M., and Collett Jr., J. L.: Chemical smoke marker emissions during flaming and smoldering phases of laboratory open burning of wildland fuels, Aerosol Sci. Technol., 44, i–v, 2010. Massoli, P., Fortner, E. C., Canagaratna, M. R., Williams, L. R., Zhang, Q., Sun, Y., Schwab, J. J., Trimborn, A., Onasch, T. B., Demerjian, K. L., Kolb, C. E., Worsnop, D. R., and Jayne, J. T.: Pollution Gradients and Chemical Characterization of Particulate Matter from Vehicular Traffic near Major Roadways: Results from the 2009 Queens College Air Quality Study in NYC, Aerosol Sci. Technol., 46, 1201–1218, 2012. Matthew, B. M., Middlebrook, A. M., and Onasch, T. B.: Collection Efficiencies in an Aerodyne Aerosol Mass Spectrometer as a Function of Particle Phase for Laboratory Generated Aerosols, Aerosol Sci. Technol., 42, 884–898, <a href="http://dx.doi.org/10.1080/02786820802356797">https://doi.org/10.1080/02786820802356797</a>, 2008. McWhinney, R. D., Rastogi, N., Urch, B., Silverman, F., Brook, J. R., Evans, G. J., and Abbatt, J. P. D.: Characterization of the University of Toronto Concentrated Aerosol Particle Exposure Facility (CAPEF) – Effects on Fine and Ultrafine Nonrefractory Aerosol Composition, Aerosol Sci. Technol., 46, 697–707, 2012. Ning, Z., Moore, K. F., Polidori, A., and Sioutas, C.: Field Validation of the New Miniature Versatile Aerosol Concentration Enrichment System (mVACES), Aerosol Sci. Technol., 40, 1098–1110, 2006. Onasch, T. B., Trimborn, A., Fortner, E. C., Jayne, J. T., Kok, G. L., Williams, L. R., Davidovits, P., and Worsnop, D. R.: Soot Particle Aerosol Mass Spectrometer: Development, Validation, and Initial Application, Aerosol Sci. Technol., 46, 804–817, 2012. Paatero, P. and Tapper, U.: Positive Matrix Factorization – a Nonnegative Factor Model with Optimal Utilization of Error-Estimates of Data Values, Environmetrics, 5, 111–126, 1994. Ramanathan, V. and Carmichael, G.: Global and regional climate changes due to black carbon, Nat. Geosci., 1, 221–227, 2008. Rastogi, N., McWhinney, R. D., Akhtar, U. S., Urch, B., Fila, M., Abbatt, J. P. D., Scott, J. A., Silverman, F., Brook, J. R., and Evans, G. J.: Physical characterization of the University of Toronto Coarse, Fine and Ultrafine High-Volume Particle Concentrator Systems, Aerosol Sci. Technol., 46, 1015–1024, 2012. Saarikoski, S., Timonen, H., Saarnio, K., Aurela, M., Järvi, L., Keronen, P., Kerminen, V.-M., and Hillamo, R.: Sources of organic carbon in fine particulate matter in northern European urban air, Atmos. Chem. Phys., 8, 6281–6295, <a href="http://dx.doi.org/10.5194/acp-8-6281-2008">https://doi.org/10.5194/acp-8-6281-2008</a>, 2008. Saarnio, K., Aurela, M., Timonen, H., Saarikoski, S., Teinilä, K., Mäkelä, T., Sofiev, M., Koskinen, J., Aalto, P. P., Kulmala, M., Kukkonen, J., and Hillamo, R.: Chemical composition of fine particles in fresh smoke plumes from boreal wild-land fires in Europe, Sci. Total Environ., 408, 2527–2542, 2010. Salcedo, D., Onasch, T. B., Aiken, A. C., Williams, L. R., de Foy, B., Cubison, M. J., Worsnop, D. R., Molina, L. T., and Jimenez, J. L.: Determination of particulate lead using aerosol mass spectrometry: MILAGRO/MCMA-2006 observations, Atmos. Chem. Phys., 10, 5371–5389, <a href="http://dx.doi.org/10.5194/acp-10-5371-2010">https://doi.org/10.5194/acp-10-5371-2010</a>, 2010. Salcedo, D., Laskin, A., Shutthanandan, V., and Jimenez, J.-L.: Feasibility of the Detection of Trace Elements in Particulate Matter Using Online High-Resolution Aerosol Mass Spectrometry, Aerosol Sci. Technol., 46, 1187–1200, 2012. Sioutas, C., Koutrakis, P., Godleski, J. J., Ferguson, S. T., Kim, C. S., and Burton, R. M.: Fine particle concentrators for inhalation exposures – effect of particle size and composition, J. Aerosol Sci., 28, 1057–1071, 1997. Smith, J. N., Barsanti, K. C., Friedli, H. R., Ehn, M., Kulmala, M., Collins, D. R., Scheckman, J. H., Williams, B. J., and McMurry, P. H.: Observations of aminium salts in atmospheric nanoparticles and possible climatic implications, Proc. Natl. Aca. Sci., 107, 6634–6639, 2010. Su, Y., Sipin, M. F., Spencer, M. T., Qin, X., Moffet, R. C., Shields, L. G., Prather, K. A., Venkatachari, P., Jeong, C.-H., Kim, E., Hopke, P. K., Gelein, R. M., Utell, M. J., Oberdörster, G., Berntsen, J., Devlin, R. B., and Chen, L. C.: Real-Time Characterization of the Composition of Individual Particles Emitted From Ultrafine Particle Concentrators, Aerosol Sci. Technol., 40, 437–455, 2006. Sun, Y., Zhang, Q., Macdonald, A. M., Hayden, K., Li, S. M., Liggio, J., Liu, P. S. K., Anlauf, K. G., Leaitch, W. R., Steffen, A., Cubison, M., Worsnop, D. R., van Donkelaar, A., and Martin, R. V.: Size-resolved aerosol chemistry on Whistler Mountain, Canada with a high-resolution aerosol mass spectrometer during INTEX-B, Atmos. Chem. Phys., 9, 3095–3111, <a href="http://dx.doi.org/10.5194/acp-9-3095-2009">https://doi.org/10.5194/acp-9-3095-2009</a>, 2009. Timonen, H., Saarikoski, S., Tolonen-Kivimäki, O., Aurela, M., Saarnio, K., Petäjä, T., Aalto, P. P., Kulmala, M., Pakkanen, T., and Hillamo, R.: Size distributions, sources and source areas of water-soluble organic carbon in urban background air, Atmos. Chem. Phys., 8, 5635–5647, <a href="http://dx.doi.org/10.5194/acp-8-5635-2008">https://doi.org/10.5194/acp-8-5635-2008</a>, 2008. Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.: Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data, Atmos. Chem. Phys., 9, 2891–2918, <a href="http://dx.doi.org/10.5194/acp-9-2891-2009">https://doi.org/10.5194/acp-9-2891-2009</a>, 2009. Wang, D., Pakbin, P, Saffari, A., Shafer, M. M., Schauer, J. J., and Sioutas, C.: Development and Evaluation of a High-Volume Aerosol-into-Liquid Collector for Fine and Ultrafine Particulate Matter, Aerosol Sci. Technol., 47, 1226–1238, <a href="http://dx.doi.org/10.1080/02786826.2013.830693">https://doi.org/10.1080/02786826.2013.830693</a>, 2013. Willeke, K. and Baron, P. A.: Aerosol measurement: principles, techniques, and applications, New York, Van Nostrand Reinhold, 1993. Zhao, Y., Bein, K. J., Wexler, A. S., Misra, C., Fine, P. M., and Sioutas, C.: Field evaluation of the versatile aerosol concentration enrichment system (VACES) particle concentrator coupled to the rapid single-particle mass spectrometer (RSMS-3), J. Geophys. Res., 110, D07S02, <a href="http://dx.doi.org/10.1029/2004JD004644">https://doi.org/10.1029/2004JD004644</a>, 2005.