Characterization of Fine Particulate Matter (PM) and Secondary PM Precursor Gases in Mexico City

This project was one of three collaborating grants designed to understand the atmospheric chemistry and aerosol particle microphysics impacting air quality in the Mexico City Metropolitan Area (MCMA) and its urban plume. The overall effort, titled MCMA- 2006, focused on: 1) the primary emissions of fine particles and precursor gases leading to photochemical production of atmospheric oxidants and secondary aerosol particles and 2) the measurement and analysis of secondary oxidants and secondary fine particular matter (PM) production, with particular emphasis on secondary organic aerosol (SOA). MCAM-2006 pursued it goals through three main activities: 1) performance and publication of detailed analyses of extensive MCMA trace gas and fine PM measurements made by the collaborating groups and others during earlier MCMA field campaigns in 2002 and 2003; 2) deployment and utilization of extensive real-time trace gas and fine PM instrumentation at urban and downwind MCMA sites in support of the MAX-Mex/MILAGRO field measurements in March, 2006; and, 3) analyses of the 2006 MCMA data sets leading to further publications that are based on new data as well as insights from analysis and publication of the 2002/2003 field data. Thirteen archival publications were coauthored with other MCMA-2003 participants. Documented findings included a significantly improved speciated emissions inventory from on-road vehicles, a greatly enhanced understanding of the sources and atmospheric loadings of volatile organic compounds, a unique analysis of the high fraction of ambient formaldehyde from primary emission sources, a much more extensive knowledge of the composition, size distributions and atmospheric mass loadings of both primary and secondary fine PM, including the fact that the rate of MCMA SOA production greatly exceeded that predicted by current atmospheric models, and evaluations of significant errors that can arise from standard air quality monitors for ozone and nitrogen dioxide. Deployment of the Aerodyne mobile laboratory, equipped with instruments from five collaborating laboratories, at the T0 urban supersite, four downwind sites and the Tula industrial area yielded unique trace gas and fine PM data sets during the March 2006 MAXMex/MILAGRO campaign. In addition, on-road measurements as the mobile laboratory moved between sites provided extensive data on 2006 MCMA fleet averaged vehicle emissions. Analyses of 2006 data sets have yielded the identification of a close correlation between the rate of production of SOA and “Odd Oxygen” (O3 + NO2) and primary organic PM with CO in the MCMA urban plume, a more sophisticated understanding of the interplay between nitrogen oxide speciation and ozone production, the identification of significant vehicular emission sources of HCN and CH3CN (usually associated with biomass burning), characterization of the aging of primary carbonaceous PM, and updated 2006 MCMA fleet on-road trace gas and fine PM emissions. Results from analyses of 2002/2003 and 2006 emissions and ambient measurements have conveyed to Mexican air quality managers who are using these data to devise and assess air quality management strategies. All data sets and published analyses are available to DOE/ASP researchers evaluating the impact of urban emissions on regional climate

Microphysical explanation of the RH-dependent water affinity of biogenic organic aerosol and its importance for climate

This is the final version of the article. Available from American Geophysical Union via the DOI in this record.A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH-dependent SOA water-uptake with solubility and phase separation; (2) show that laboratory data on IP- and MT-SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single-parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.The data presented in the paper will be available through the Bolin Centre database (http://bolin.su.se/data/). The EC H2020 European Research Council ERC (ERC-StGATMOGAIN-278277 and ERC-StG-QAPPA-335478) and integrated project 641816 CRESCENDO Svenska Forskningsrådet Formas (Swedish Research Council Formas) (2015-749), Knut och Alice Wallenbergs Stiftelse (Knut and Alice Wallenberg Foundation Wallenberg Fellowship AtmoRemove), Academy of Finland (grants 272041 and 259005), Natural Environment Research Council (NERC grants NE/M003531/1 and NE/J02175X/1), Norwegian Research Council (EVA grant 229771), Natural Sciences and Engineering Research Council of Canada (NSERC, grant RGPIN/04315-2014), National Science Foundation (NSF, grants ATM-1242258, AGS-1242932, and AGS-1360834), U.S. Environmental Protection Agency (EPA, STAR grant R835410), National Oceanic and Atmospheric Administration (NOAA, CPO award 538NA10OAR4310102), Electric Power Research Institute (EPRI, grant 10004734), U.S. Department of Energy (DOE, grants BER/ASR DE-SC0016559 and DE-SC0012792), Georgia Institute of Technology, and NordForsk (Nordic Centre of Excellence eSTICC) are gratefully acknowledged for funding. The climate model simulations were performed on resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputing Centre. Benjamin Murphy is acknowledged for useful discussions

Global atmospheric particle formation from CERN CLOUD measurements

Fundamental questions remain about the origin of newly formed atmospheric aerosol particles because data from laboratory measurements have been insufficient to build global models. In contrast, gas-phase chemistry models have been based on laboratory kinetics measurements for decades. Here we build a global model of aerosol formation using extensive laboratory-measured nucleation rates involving sulfuric acid, ammonia, ions and organic compounds. The simulations and a comparison with atmospheric observations show that nearly all nucleation throughout the present-day atmosphere involves ammonia or biogenic organic compounds in addition to sulfuric acid. A significant fraction of nucleation involves ions, but the relatively weak dependence on ion concentrations indicates that for the processes studied variations in cosmic ray intensity do not significantly affect climate via nucleation in the present-day atmosphere

The role of low-volatility organic compounds in initial particle growth in the atmosphere

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday1. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres2, 3. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles4, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth5, 6, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer7, 8, 9, 10. Although recent studies11, 12, 13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon2, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory)2, 14, has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown15 that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10−4.5 to 10−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

4 pages 359-363 in the print version, additional 7 pages online.Peer reviewe

Multicomponent new particle formation from sulfuric acid, ammonia, and biogenic vapors

A major fraction of atmospheric aerosol particles, which affect both air quality and climate, form from gaseous precursors in the atmosphere. Highly oxygenated organic molecules (HOMs), formed by oxidation of biogenic volatile organic compounds, are known to participate in particle formation and growth. However, it is not well understood how they interact with atmospheric pollutants, such as nitrogen oxides (NOx) and sulfur oxides (SOx) from fossil fuel combustion, as well as ammonia (NH3) from livestock and fertilizers. Here, we show how NOx suppresses particle formation, while HOMs, sulfuric acid, and NH3 have a synergistic enhancing effect on particle formation. We postulate a novel mechanism, involving HOMs, sulfuric acid, and ammonia, which is able to closely reproduce observations of particle formation and growth in daytime boreal forest and similar environments. The findings elucidate the complex interactions between biogenic and anthropogenic vapors in the atmospheric aerosol system

Aerosol mass spectrometer constraint on the global secondary organic aerosol budget

The budget of atmospheric secondary organic aerosol (SOA) is very uncertain, with recent estimates suggesting a global source of between 12 and 1820 Tg (SOA) a−1. We used a dataset of aerosol mass spectrometer (AMS) observations from 34 different surface locations to evaluate the GLOMAP global chemical transport model. The standard model simulation (which included SOA from monoterpenes only) underpredicted organic aerosol (OA) observed by the AMS and had little skill reproducing the variability in the dataset. We simulated SOA formation from biogenic (monoterpenes and isoprene), lumped anthropogenic and lumped biomass burning volatile organic compounds (VOCs) and varied the SOA yield from each precursor source to produce the best overall match between model and observations. We assumed that SOA is essentially non-volatile and condenses irreversibly onto existing aerosol. Our best estimate of the SOA source is 140 Tg (SOA) a−1 but with a large uncertainty range which we estimate to be 50–380 Tg (SOA) a−1. We found the minimum in normalised mean error (NME) between model and the AMS dataset when we assumed a large SOA source (100 Tg (SOA) a−1) from sources that spatially matched anthropogenic pollution (which we term antropogenically controlled SOA). We used organic carbon observations compiled by Bahadur et al. (2009) to evaluate our estimated SOA sources. We found that the model with a large anthropogenic SOA source was the most consistent with these observations, however improvement over the model with a large biogenic SOA source (250 Tg (SOA) a−1) was small. We used a dataset of 14C observations from rural locations to evaluate our estimated SOA sources. We estimated a maximum of 10 Tg (SOA) a−1 (10 %) of the anthropogenically controlled SOA source could be from fossil (urban/industrial) sources. We suggest that an additional anthropogenic source is most likely due to an anthropogenic pollution enhancement of SOA formation from biogenic VOCs. Such an anthropogenically controlled SOA source would result in substantial climate forcing. We estimated a global mean aerosol direct effect of −0.26 ± 0.15 Wm−2 and indirect (cloud albedo) effect of −0.6+0.24−0.14 Wm−2 from anthropogenically controlled SOA. The biogenic and biomass SOA sources are not well constrained with this analysis due to the limited number of OA observations in regions and periods strongly impacted by these sources. To further improve the constraints by this method, additional OA observations are needed in the tropics and the Southern Hemisphere

An Eddy-Covariance System for the Measurement of Surface/Atmosphere Exchange Fluxes of Submicron Aerosol Chemical Species—First Application Above an Urban Area

Until now, micrometeorological measurements of surface/ atmosphere exchange fluxes of submicron aerosol chemical components such as nitrate, sulfate or organics could only be made with gradient techniques. This paper describes a novel setup to measure speciated aerosol fluxes by the more direct eddy covariance technique. The system is based on the Aerodyne quadrupole-based Aerosol Mass Spectrometer (Q-AMS), providing a quantitative measurement of aerosol constituents of environmental concern at a time resolution sufficient for eddy-covariance. The Q-AMS control software was modified to maximize duty cycle and statistics and enable fast data acquisition, synchronized with that of an ultrasonic anemometer. The detection limit of the Q-AMS based system for flux measurements ranges from 0.2 for NO−3 to 15 ng m−2 s−1 for hydrocarbon-like organic aerosol (HOA), with an estimated precision of around 6 ng m−2 s−1, depending on aerosol loading. At common ambient concentrations the system is capable of resolving deposition velocity values < 1 mm s−1, sufficient for measurements of dry deposition to vegetation. First tests of the system in the urban environment (6 to 20 June 2003) in Boulder, CO, USA, reveal clear diurnal, presumably traffic related, patterns in the emission of HOA and NO−3 , with indication of fast production of moderately oxygenated organic aerosol below the measurement height, averaging about 15% of the HOA emission. The average emission factor for HOA was 0.5 g (kg fuel)−1, similar to those found in previous studies. For NO−3 an emission factor of 0.09 g (kg fuel)−1 was estimated, implying oxidation of 0.5% of the traffic derived NOx below the measurement height of 45 m. By contrast, SO2− 4 fluxes were on average downward, with deposition velocities that increase with friction velocity from 0.4 to 4 mm s−1

An eddy-covariance system for the measurement of surface/atmosphere exchange fluxes of submicron aerosol chemical species - First application above an urban area

Until now, micrometeorological measurements of surface/ atmosphere exchange fluxes of submicron aerosol chemical components such as nitrate, sulfate or organics could only be made with gradient techniques. This article describes a novel setup to measure speciated aerosol fluxes by the more direct eddy covariance technique. The system is based on the Aerodyne quadrupole-based Aerosol Mass Spectrometer (Q-AMS), providing a quantitative measurement of aerosol constituents of environmental concern at a time resolution sufficient for eddy-covariance. The Q-AMS control software was modified to maximize duty cycle and statistics and enable fast data acquisition, synchronized with that of an ultrasonic anemometer. The detection limit of the Q-AMS based system for flux measurements ranges from 0.2 for NO3- to 15 ng m-2 s-1 for hydrocarbon-like organic aerosol (HOA), with an estimated precision of around 6 ng m-2 s-1, depending on aerosol loading. At common ambient concentrations the system is capable of resolving deposition velocity values &lt; 1 mm s-1, sufficient for measurements of dry deposition to vegetation. First tests of the system in the urban environment (6 to 20 June 2003) in Boulder, CO, USA, reveal clear diurnal, presumably traffic related, patterns in the emission of HOA and NO3-, with indication of fast production of moderately oxygenated organic aerosol below the measurement height, averaging about 15% of the HOA emission. The average emission factor for HOA was 0.5 g (kg fuel)-1, similar to those found in previous studies. For NO3- an emission factor of 0.09 g (kg fuel)-1 was estimated, implying oxidation of 0.5% of the traffic derived NOx below the measurement height of 45 m. By contrast, SO42- fluxes were on average downward, with deposition velocities that increase with friction velocity from 0.4 to 4 mm s-1. Copyright © American Association for Aerosol Research