Delphine K. Farmer

Rainforest aerosols as biogenic nuclei of clouds and precipitation in the Amazon.

Clean or Dirty Aerosols strongly affect atmospheric properties and processes—including visibility, cloud formation, and radiative behavior. Knowing their effects in both clean and polluted air is necessary in order to understand their influence (see the Perspective by Baltensperger). Clarke and Kapustin (p. 1488) examine vertical atmospheric profiles collected above the Pacific Ocean, where air quality is affected by the transport of polluted air from the west, and find significant regional enhancements in light scattering, aerosol mass, and aerosol number associated with combustion. Aerosol particle concentrations in this region can exceed values in clean, unperturbed regions by over an order of magnitude. Thus combustion affects hemispheric aerosol optical depth and the distribution of cloud condensation nuclei. Pöschl et al. (p. 1513) discuss the composition of aerosols above the Amazon Basin, in the pristine conditions of the rainy season. The aerosols in this region are derived mostly from gaseous biogenic precursors, plants, and microorganisms, and particle concentration is orders of magnitude lower than in polluted continental regions. The majority of cloud condensation nuclei in the Amazon during the wet season are derived from biogenic precursors. The Amazon is one of the few continental regions where atmospheric aerosol particles and their effects on climate are not dominated by anthropogenic sources. During the wet season, the ambient conditions approach those of the pristine pre-industrial era. We show that the fine submicrometer particles accounting for most cloud condensation nuclei are predominantly composed of secondary organic material formed by oxidation of gaseous biogenic precursors. Supermicrometer particles, which are relevant as ice nuclei, consist mostly of primary biological material directly released from rainforest biota. The Amazon Basin appears to be a biogeochemical reactor, in which the biosphere and atmospheric photochemistry produce nuclei for clouds and precipitation sustaining the hydrological cycle. The prevailing regime of aerosol-cloud interactions in this natural environment is distinctly different from polluted regions.

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ON-nitrogen appears as ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using fragment ratios, organonitrogen ions, ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species.

Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin

Submicron atmospheric particles in the Amazon Basin were characterized by a high-resolution aerosol mass spectrometer during the wet season of 2008. Patterns in the mass spectra closely resembled those of secondary-organic-aerosol (SOA) particles formed in environmental chambers from biogenic precursor gases. In contrast, mass spectral indicators of primary biological aerosol particles (PBAPs) were insignificant, suggesting that PBAPs contributed negligibly to the submicron fraction of particles during the period of study. For 40% of the measurement periods, the mass spectra indicate that in-Basin biogenic SOA production was the dominant source of the submicron mass fraction, contrasted to other periods (30%) during which out-of-Basin organic-carbon sources were significant on top of the baseline in-Basin processes. The in-Basin periods had an average organic-particle loading of 0.6 mu g m(-3) and an average elemental oxygen-to-carbon (O:C) ratio of 0.42, compared to 0.9 mu g m(-3) and 0.49, respectively, during periods of out-of-Basin influence. On the basis of the data, we conclude that most of the organic material composing submicron particles over the Basin derived from biogenic SOA production, a finding that is consistent with microscopy observations made in a concurrent study. This source was augmented during some periods by aged organic material delivered by long-range transport. Citation: Chen, Q., et al. (2009), Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin, Geophys. Res. Lett., 36, L20806, doi: 10.1029/2009GL039880.

Atmospheric Processes and Their Controlling Influence on Cloud Condensation Nuclei Activity

Atmospheric Processes and their Controlling Influence on Cloud Condensation Nuclei Activity Delphine K. Farmer 1 , Christopher D. Cappa 2 , Sonia M. Kreidenweis 3 Department of Chemistry, Colorado State University, Fort Collins, CO Department of Civil and Environmental Engineering, University of California, Davis, CA Department of Atmospheric Science, Colorado State University, Fort Collins, CO Table of Contents Introduction 2 Fundamentals of Water Uptake by Particles 4 Particle Activation 5 Water Activity 10 Water absorption 10 Solubility Limitations 12 Water adsorption 13 Surface tension 15 Particle Size, Composition and CCN Activity 16 Influence of Atmospheric Processes on CCN Activity and Number Concentration .... 17 Chemistry 17 Gas-particle phase partitioning 18 Heterogeneous chemistry 19 Multiphase chemistry 20 Condensational growth 23 Coagulation 24 Mixing state 26 Timescales 27 Summary 28 Suggested Future Research 29 Acknowledgements 29 References 29

Observational insights into aerosol formation from isoprene.

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.

Real-time atmospheric chemistry field instrumentation.

Quantifying the concentrations of trace atmospheric species in complex, reactive, and constantly changing gas and particle mixtures is challenging. This article provides a broad overview of recent advances in instrumentation used for analyzing ambient gases and particles continuously and with fast time resolution during field campaigns.

A controlling role for the air−sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer

Significance Reactions occurring at the air−sea interface have the potential to alter the chemical composition of the atmosphere. However, our knowledge of the extent to which these reactions impact the concentration of oxidants and their precursors is derived from laboratory measurements using systems that mimic the chemical, biological, and physical complexity of the surface ocean. Here, we present direct measurements of the vertical fluxes of a reactant−product pair using eddy covariance coupled with chemical ionization time-of-flight mass spectrometry to directly assess the role of the ocean surface in the exchange of reactive nitrogen and halogens. Our observations suggest that the ocean surface plays a critical role in controlling the lifetime of N2O5, a primary nocturnal reservoir for tropospheric reactive nitrogen. The lifetime of reactive nitrogen and the production rate of reactive halogens in the marine boundary layer are strongly impacted by reactions occurring at aqueous interfaces. Despite the potential importance of the air−sea interface in serving as a reactive surface, few direct field observations are available to assess its impact on reactive nitrogen deposition and halogen activation. Here, we present direct measurements of the vertical fluxes of the reactant−product pair N2O5 and ClNO2 to assess the role of the ocean surface in the exchange of reactive nitrogen and halogens. We measure nocturnal N2O5 exchange velocities (Vex = −1.66 ± 0.60 cm s−1) that are limited by atmospheric transport of N2O5 to the air−sea interface. Surprisingly, vertical fluxes of ClNO2, the product of N2O5 reactive uptake to concentrated chloride containing surfaces, display net deposition, suggesting that elevated ClNO2 mixing ratios found in the marine boundary layer are sustained primarily by N2O5 reactions with aerosol particles. Comparison of measured deposition rates and in situ observations of N2O5 reactive uptake to aerosol particles indicates that N2O5 deposition to the ocean surface accounts for between 26% and 42% of the total loss rate. The combination of large Vex, N2O5 and net deposition of ClNO2 acts to limit NOx recycling rates and the production of Cl atoms by shortening the nocturnal lifetime of N2O5. These results indicate that air−sea exchange processes account for as much as 15% of nocturnal NOx removal in polluted coastal regions and can serve to reduce ClNO2 concentrations at sunrise by over 20%.

The Formation of Sulfate and Elemental Sulfur Aerosols under Varying Laboratory Conditions: Implications for Early Earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.

Chemically Resolved Particle Fluxes Over Tropical and Temperate Forests

Chemically resolved submicron (PM1) particle mass fluxes were measured by eddy covariance with a high resolution time-of-flight aerosol mass spectrometer over temperate and tropical forests during the BEARPEX-07 and AMAZE-08 campaigns. Fluxes during AMAZE-08 were small and close to the detection limit (<1 ng m−2 s−1) due to low particle mass concentrations (<1 μg m−3). During BEARPEX-07, concentrations were five times larger, with mean mid-day deposition fluxes of −4.8 ng m−2 s−1 for total nonrefractory PM1 (Vex,PM1 = −1 mm s−1) and emission fluxes of +2.6 ng m−2 s−1 for organic PM1 (Vex,org = +1 mm s−1). Biosphere–atmosphere fluxes of different chemical components are affected by in-canopy chemistry, vertical gradients in gas-particle partitioning due to canopy temperature gradients, emission of primary biological aerosol particles, and wet and dry deposition. As a result of these competing processes, individual chemical components had fluxes of varying magnitude and direction during both campaigns. Oxygenated organic components representing regionally aged aerosol deposited, while components of fresh secondary organic aerosol (SOA) emitted. During BEARPEX-07, rapid in-canopy oxidation caused rapid SOA growth on the timescale of biosphere-atmosphere exchange. In-canopy SOA mass yields were 0.5–4%. During AMAZE-08, the net organic aerosol flux was influenced by deposition, in-canopy SOA formation, and thermal shifts in gas-particle partitioning. Wet deposition was estimated to be an order of magnitude larger than dry deposition during AMAZE-08. Small shifts in organic aerosol concentrations from anthropogenic sources such as urban pollution or biomass burning alters the balance between flux terms. The semivolatile nature of the Amazonian organic aerosol suggests a feedback in which warmer temperatures will partition SOA to the gas-phase, reducing their light scattering and thus potential to cool the region. Copyright 2013 American Association for Aerosol Research

Anthropogenic Sulfur Perturbations on Biogenic Oxidation: SO2 Additions Impact Gas-Phase OH Oxidation Products of α- and β-Pinene

In order to probe how anthropogenic pollutants can impact the atmospheric oxidation of biogenic emissions, we investigated how sulfur dioxide (SO2) perturbations impact the oxidation of two monoterpenes, α-and β-pinene. We used chemical ionization mass spectrometry to examine changes in both individual molecules and gas-phase bulk properties of oxidation products as a function of SO2 addition. SO2 perturbations impacted the oxidation systems of α-and β-pinene, leading to an ensemble of products with a lesser degree of oxygenation than unperturbed systems. These changes may be due to shifts in the OH:HO2 ratio from SO2 oxidation and/or to SO3 reacting directly with organic molecules. Van Krevelen diagrams suggest a shift from gas-phase functionalization by alcohol/peroxide groups to functionalization by carboxylic acid or carbonyl groups, consistent with a decreased OH:HO2 ratio. Increasing relative humidity dampens the impact of the perturbation. This decrease in oxygenation may impact secondary organic aerosol formation in regions dominated by biogenic emissions with nearby SO2 sources. We observed sulfur-containing organic compounds following SO2 perturbations of monoterpene oxidation; whether these are the result of photochemistry or an instrumental artifact from ion-molecule clustering remains uncertain. However, our results demonstrate that the two monoterpene isomers produce unique suites of oxidation products.