The driving factors of new particle formation and growth in the polluted boundary layer

New particle formation (NPF) is a significant source of atmospheric particles, affecting climate and air quality. Understanding the mechanisms involved in urban aerosols is important to develop effective mitigation strategies. However, NPF rates reported in the polluted boundary layer span more than 4 orders of magnitude, and the reasons behind this variability are the subject of intense scientific debate. Multiple atmospheric vapours have been postulated to participate in NPF, including sulfuric acid, ammonia, amines and organics, but their relative roles remain unclear. We investigated NPF in the CLOUD chamber using mixtures of anthropogenic vapours that simulate polluted boundary layer conditions. We demonstrate that NPF in polluted environments is largely driven by the formation of sulfuric acid&ndash;base clusters, stabilized by the presence of amines, high ammonia concentrations and lower temperatures. Aromatic oxidation products, despite their extremely low volatility, play a minor role in NPF in the chosen urban environment but can be important for particle growth and hence for the survival of newly formed particles. Our measurements quantitatively account for NPF in highly diverse urban environments and explain its large observed variability. Such quantitative information obtained under controlled laboratory conditions will help the interpretation of future ambient observations of NPF rates in polluted atmospheres. Full List of Authors: Mao Xiao1, Christopher R. Hoyle1,2, Lubna Dada3, Dominik Stolzenburg4, Andreas K&uuml;rten5, Mingyi Wang6, Houssni Lamkaddam1, Olga Garmash3, Bernhard Mentler7, Ugo Molteni1, Andrea Baccarini1, Mario Simon5, Xu-Cheng He3, Katrianne Lehtipalo3,8, Lauri R. Ahonen3, Rima Baalbaki3, Paulus S. Bauer4, Lisa Beck3, David Bell1, Federico Bianchi3, Sophia Brilke4, Dexian Chen6, Randall Chiu9, Ant&oacute;nio Dias10, Jonathan Duplissy3,11, Henning Finkenzeller9, Hamish Gordon6, Victoria Hofbauer6, Changhyuk Kim13,14, Theodore K. Koenig9,a, Janne Lampilahti3, Chuan Ping Lee1, Zijun Li15, Huajun Mai13, Vladimir Makhmutov16, Hanna E. Manninen17, Ruby Marten1, Serge Mathot17, Roy L. Mauldin18,19, Wei Nie20, Antti Onnela17, Eva Partoll7, Tuukka Pet&auml;j&auml;3, Joschka Pfeifer5,17, Veronika Pospisilova1, Lauriane L. J. Qu&eacute;l&eacute;ver3, Matti Rissanen3,b, Siegfried Schobesberger15, Simone Schuchmann17,c, Yuri Stozhkov16, Christian Tauber4, Yee Jun Tham3, Ant&oacute;nio Tom&eacute;21, Miguel Vazquez-Pufleau4, Andrea C. Wagner5,9,d, Robert Wagner3, Yonghong Wang3, Lena Weitz5, Daniela Wimmer3,4, Yusheng Wu3, Chao Yan3, Penglin Ye6,22, Qing Ye6, Qiaozhi Zha3, Xueqin Zhou5, Antonio Amorim10, Ken Carslaw12, Joachim Curtius5, Armin Hansel7, Rainer Volkamer9,19, Paul M. Winkler4, Richard C. Flagan13, Markku Kulmala3,11,20,23, Douglas R. Worsnop3,22, Jasper Kirkby5,17, Neil M. Donahue6, Urs Baltensperger1, Imad El Haddad1, and Josef Dommen1 1Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland 2Institute for Atmospheric and Climate Science, ETH Zurich, 8092 Zurich, Switzerland 3Institute for Atmospheric and Earth System Research (INAR)/Physics, University of Helsinki, 00014 Helsinki, Finland 4Faculty of Physics, University of Vienna, 1090 Vienna, Austria 5Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt, 60438 Frankfurt am Main, Germany 6Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, PA 15213, USA 7Institute of Ion Physics and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria 8Atmospheric Composition Research Unit, Finnish Meteorological Institute, 00560 Helsinki, Finland 9Department of Chemistry &amp; CIRES, University of Colorado Boulder, Boulder, CO 80309, USA 10CENTRA and FCUL, University of Lisbon, 1749-016 Lisbon, Portugal 11Helsinki Institute of Physics, University of Helsinki, 00014 Helsinki, Finland 12School of Earth and Environment, University of Leeds, LS2 9JT Leeds, United Kingdom 13Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA 14School of Civil and Environmental Engineering, Pusan National University, 46241 Busan, Republic of Korea 15Department of Applied Physics, University of Eastern Finland, 70211 Kuopio, Finland 16Solar and Cosmic Ray Physics Laboratory, P.N. Lebedev Physical Institute of the Russian Academy of Sciences, 119991 Moscow, Russian Federation 17CERN, 1211 Geneva, Switzerland 18Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA 19Department of Oceanic and Atmospheric Sciences, University of Colorado Boulder, Boulder, CO 80309, USA 20Joint International Research Laboratory of Atmospheric and Earth System Sciences, School of Atmospheric Sciences, Nanjing University, Nanjing, Jiangsu Province, China 21IDL-Universidade da Beira Interior, Covilh&atilde;, Portugal 22Aerodyne Research Inc., Billerica, MA 01821-3976, USA 23Aerosol and Haze Laboratory, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, China anow at: College of Environmental Sciences and Engineering, Peking University, 100871 Beijing, China bnow at: Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33720 Tampere, Finland cnow at: Experimentelle Teilchen- und Astroteilchenphysik, Johannes Gutenberg University Mainz, 55128 Mainz, Germany dnow at: Department of Chemistry &amp; CIRES, University of Colorado Boulder, Boulder, CO 80305, USA Correspondence: Urs Baltensperger ([email protected]) and Imad El Haddad ([email protected])</p

Oxidation of SO2 by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations

The effect of increased reaction rates of stabilized Criegee intermediates (sCIs) with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012) increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO) with SO2 according to the values recommended by Welz et al. (2012) increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.Peer reviewe

New instrument for measuring atmospheric concentrations of non-OH oxidants of SO2

Peer reviewe

Sources and characteristics of summertime organic aerosol in the Colorado Front Range: perspective from measurements and WRF-Chem modeling

Abstract. The evolution of organic aerosols (OAs) and their precursors in the boundary layer (BL) of the Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.085±0.003 µg m−3 ppbv−1. At background mixing ratios of CO, up to  ∼  1.8 µg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&amp;G) emissions was  ∼  40 % higher than in urban-influenced plumes. Positive matrix factorization (PMF) confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&amp;G sector were used in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including top-down modified O&amp;G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high-O&amp;G-influenced plumes. By including emissions from the O&amp;G sector using the top-down approach, it was estimated that the O&amp;G sector contributed to  &lt;  5 % of total OA, but up to 38 % of anthropogenic SOA (aSOA) in the region. The best agreement between the measured and simulated median OA was achieved by limiting the extent of biogenic hydrocarbon aging and consequently biogenic SOA (bSOA) production. Despite a lower production of bSOA in this scenario, contribution of bSOA to total SOA remained high at 40–54 %. Future studies aiming at a better emissions characterization of POA and intermediate-volatility organic compounds (IVOCs) from the O&amp;G sector are valuable

Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

Sulfuric acid is known to be a key component for atmospheric nucleation. Precise determination of sulfuric-acid concentration is a crucial factor for prediction of nucleation rates and subsequent growth. In our study, we have noticed a substantial discrepancy between sulfuric-acid monomer concentrations and total-sulfate concentrations measured from the same source of sulfuric-acid vapor. The discrepancy of about 1-2 orders of magnitude was found with similar particle-formation rates. To investigate this discrepancy, and its effect on nucleation, a method of thermally controlled saturator filled with pure sulfuric acid (97% wt.) for production of sulfuric-acid vapor is applied and rigorously tested. The saturator provided an independent vapor-production method, compared to our previous method of the furnace (Brus et al., 2010, 2011), to find out if the discrepancy is caused by the production method itself. The saturator was used in a H2SO4-H2O nucleation experiment, using a laminar flow tube to check reproducibility of the nucleation results with the saturator method, compared to the furnace. Two independent methods of mass spectrometry and online ion chromatography were used for detecting sulfuric-acid or sulfate concentrations. Measured sulfuric-acid or total-sulfate concentrations are compared to theoretical predictions calculated using vapor pressure and a mixing law. The calculated prediction of sulfuric-acid concentrations agrees very well with the measured values when total sulfate is considered. Sulfuric-acid monomer concentration was found to be about 2 orders of magnitude lower than theoretical predictions, but with a temperature dependency similar to the predictions and the results obtained with the ion-chromatograph method. Formation rates are reproducible when compared to our previous results with both sulfuric-acid or total-sulfate detection and sulfuric-acid production methods separately, removing any doubts that the vapor-production method would cause the discrepancy. Possible reasons for the discrepancy are discussed and some suggestions include that the missing sulfuric acid is in clusters, formed with contaminants found in most laboratory experiments. One-to-two-order-of-magnitude higher sulfuric-acid concentrations (measured as total sulfate in this study) would contribute to a higher fraction of particle growth rate than assumed from the measurements by mass spectrometers (i.e. sulfuric-acid monomer). However, the observed growth rates by sulfate-containing vapor in this study does not directly imply a similar situation in the field, where sources of sulfate are much more diverse.Peer reviewe

Ambient observations of dimers from terpene oxidation in the gas phase : Implications for new particle formation and growth

We present ambient observations of dimeric monoterpene oxidation products (C16-20HyO6-9) in gas and particle phases in the boreal forest in Finland in spring 2013 and 2014, detected with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols employing acetate and iodide as reagent ions. These are among the first online dual-phase observations of such dimers in the atmosphere. Estimated saturation concentrations of 10(-15) to 10(-6)mu gm(-3) (based on observed thermal desorptions and group-contribution methods) and measured gas-phase concentrations of 10(-3) to 10(-2)mu gm(-3) (similar to 10(6)-10(7)moleculescm(-3)) corroborate a gas-phase formation mechanism. Regular new particle formation (NPF) events allowed insights into the potential role dimers may play for atmospheric NPF and growth. The observationally constrained Model for Acid-Base chemistry in NAnoparticle Growth indicates a contribution of similar to 5% to early stage particle growth from the similar to 60 gaseous dimer compounds. Plain Language Summary Atmospheric aerosol particles influence climate and air quality. We present new insights into how emissions of volatile organic compounds from trees are transformed in the atmosphere to contribute to the formation and growth of aerosol particles. We detected for the first time over a forest, a group of organic molecules, known to grow particles, in the gas phase at levels far higher than expected. Previous measurements had only measured them in the particles. This finding provides guidance on how models of aerosol formation and growth should describe their appearance and fate in the atmosphere.Peer reviewe

Constraints from observations and modeling on atmosphere-surface exchange of mercury in eastern North America

Atmosphere-surface exchange of mercury, although a critical component of its global cycle, is currently poorly constrained. Here we use the GEOS-Chem chemical transport model to interpret atmospheric Hg-0 (gaseous elemental mercury) data collected during the 2013 summer Nitrogen, Oxidants, Mercury and Aerosol Distributions, Sources and Sinks (NOMADSS) aircraft campaign as well as ground-and ship-based observations in terms of their constraints on the atmosphere-surface exchange of Hg-0 over eastern North America. Model-observation comparison suggests that the Northwest Atlantic may be a net source of Hg-0, with high evasion fluxes in summer (our best sensitivity simulation shows an average oceanic Hg-0 flux of 3.3 ng m(-2) h(-1) over the Northwest Atlantic), while the terrestrial ecosystem in the summer of the eastern United States is likely a net sink of Hg-0 (our best sensitivity simulation shows an average terrestrial Hg-0 flux of -0.6 ng m(-2) h(-1) over the eastern United States). The inferred high Hg-0 fluxes from the Northwest Atlantic may result from high wet deposition fluxes of oxidized Hg, which are in turn related to high precipitation rates in this region. We also find that increasing simulated terrestrial fluxes of Hg-0 in spring compared to other seasons can better reproduce observed seasonal variability of Hg-0 concentration at ground-based sites in eastern North America.Peer reviewe

The Hausdorff and dynamical dimensions of self-affine sponges : a dimension gap result

We construct a self-affine sponge in R 3 whose dynamical dimension, i.e. the supremum of the Hausdorff dimensions of its invariant measures, is strictly less than its Hausdorff dimension. This resolves a long-standing open problem in the dimension theory of dynamical systems, namely whether every expanding repeller has an ergodic invariant measure of full Hausdorff dimension. More generally we compute the Hausdorff and dynamical dimensions of a large class of self-affine sponges, a problem that previous techniques could only solve in two dimensions. The Hausdorff and dynamical dimensions depend continuously on the iterated function system defining the sponge, implying that sponges with a dimension gap represent a nonempty open subset of the parameter space

Ambient Measurements of Highly Oxidized Gas-Phase Molecules during the Southern Oxidant and Aerosol Study (SOAS) 2013

We present measurements of highly oxidized multifunctional molecules (HOMs) detected in the gas phase using a high-resolution time-of flight chemical ionization mass spectrometer with nitrate reagent ion (NO3- CIMS). The measurements took place during the 2013 Southern Oxidant and Aerosol Study (SOAS 2013) at a forest site in Alabama, where emissions were dominated by biogenic volatile organic compounds (BVOCs). Primary BVOC emissions were represented by isoprene mixed with various terpenes, making it a unique sampling location compared to previous NO3- CIMS deployments in monoterpene-dominated environments. During SOAS 2013, the NO3- CIMS detected HOMs with oxygen-to-carbon (O:C) ratios between 0.5 and 1.4 originating from both isoprene (C-5) and monoterpenes (C-10) as well as hundreds of additional HOMs with carbon numbers between C-3 and C-20. We used positive matrix factorization (PMF) to deconvolve the complex data set and extract information about classes of HOMs with similar temporal trends. This analysis revealed three isoprene-dominated and three monoterpene-dominated PMF factors. We observed significant amounts of isoprene- and monoterpene-derived organic nitrates (ONs) in most factors. The abundant presence of ONs was consistent with previous studies that have highlighted the importance of NOx-driven chemistry at the site. One of the isoprene-dominated factors had a strong correlation with SO2 plumes likely advected from nearby coal-fired power plants and was dominated by an isoprene derived ON (C5H10N2O8). These results indicate that anthropogenic emissions played a significant role in the formation of low volatility compounds from BVOC emissions in the region.Peer reviewe