Keith N. Bower

Evolution of Organic Aerosols in the Atmosphere

Framework for Change Organic aerosols make up 20 to 90% of the particulate mass of the troposphere and are important factors in both climate and human heath. However, their sources and removal pathways are very uncertain, and their atmospheric evolution is poorly characterized. Jimenez et al. (p. 1525; see the Perspective by Andreae) present an integrated framework of organic aerosol compositional evolution in the atmosphere, based on model results and field and laboratory data that simulate the dynamic aging behavior of organic aerosols. Particles become more oxidized, more hygroscopic, and less volatile with age, as they become oxygenated organic aerosols. These results should lead to better predictions of climate and air quality. Organic aerosols are not compositionally static, but they evolve dramatically within hours to days of their formation. Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high–time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes

[1] Organic aerosol (OA) data acquired by the Aerosol Mass Spectrometer (AMS) in 37 field campaigns were deconvolved into hydrocarbon-like OA (HOA) and several types of oxygenated OA (OOA) components. HOA has been linked to primary combustion emissions (mainly from fossil fuel) and other primary sources such as meat cooking. OOA is ubiquitous in various atmospheric environments, on average accounting for 64%, 83% and 95% of the total OA in urban, urban downwind, and rural/remote sites, respectively. A case study analysis of a rural site shows that the OOA concentration is much greater than the advected HOA, indicating that HOA oxidation is not an important source of OOA, and that OOA increases are mainly due to SOA. Most global models lack an explicit representation of SOA which may lead to significant biases in the magnitude, spatial and temporal distributions of OA, and in aerosol hygroscopic properties.

Quantitative sampling using an Aerodyne aerosol mass spectrometer 1. Techniques of data interpretation and error analysis

Received 22 March 2002; revised 2 July 2002; accepted 5 August 2002; published 4 February 2003. [1] The aerosol mass spectrometer (AMS), manufactured by Aerodyne Research, Inc., has been shown to be capable of delivering quantitative information on the chemical composition and size of volatile and semivolatile fine airborne particulate matter with high time resolution. Analytical and software tools for interpreting the data from this instrument and generating meaningful, quantitative results have been developed and are presented here with a brief description of the instrument. These include the conversion of detected ion rates from the quadrupole mass spectrometer during the mass spectrum (MS) mode of operation to atmospheric mass concentrations of chemical species (in m gm � 3 ) by applying calibration data. It is also necessary to correct for variations in the electron multiplier performance, and a method involving the measurement of the instrument’s response to gas phase signals is also presented. The techniques for applying particle velocity calibration data and transforming signals from time of flight (TOF) mode to chemical mass distributions in terms of aerodynamic diameter (dM/dlog(Da) distributions) are also presented. It is also possible to quantify the uncertainties in both MS and TOF data by evaluating the ion counting statistics and variability of the background signal, respectively. This paper is accompanied by part 2 of this series, in which these methods are used to process and analyze AMS results on ambient aerosol from two U.K. cities at different times of the year. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0394 Atmospheric Composition and Structure: Instruments and techniques; 0399 Atmospheric Composition and Structure: General or miscellaneous; KEYWORDS: aerosols, chemical composition, mass spectrometry, analysis techniques

Submicron aerosol composition at Trinidad Head, California, during ITCT 2K2: Its relationship with gas phase volatile organic carbon and assessment of instrument performance

[1] Two Aerodyne aerosol mass spectrometers (AMSs) were deployed at Trinidad Head on the north Californian coast during the National Oceanographic and Atmospheric Administration Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) experiment, to study the physiochemical properties of submicron aerosol particles within the Pacific marine boundary layer. One AMS was modified to allow the study of sea salt-based particles, while the other used a temperature cycling system on its inlet. The reported loadings increased by a factor of 2 when the temperature approached the dew point, which is due to the inlet performance and has implications for other AMS experiments and applications. The processed data were compared with those of a particle into liquid sampler-ion chromatograph and showed that the ammonium, sulfate and organic fractions of the particles were consistently found within a single, normally acidic, accumulation mode at around 300 - 400 nm. However, when influenced by land-based sources, vehicle emissions and increased ammonium loadings were seen. The concentrations of nitrate in the accumulation mode were low, but it was also found within sea salt particles in the coarse mode and can be linked to the displacement of chloride. The organic fraction showed a high degree of chemical ageing and evidence of nitrogen-bearing organics was also observed. The particulate organic data were compared to the volatile organic carbon data derived from an in-situ gas chromatograph-mass spectrometer-flame ionization detector and relationships were found between the gas and particle phase chemicals in both the overall concentrations and the levels of oxidation.

A closure study of sub-micrometer aerosol particle hygroscopic behaviour

Abstract The hygroscopic properties of sub-micrometer aerosol particles were studied in connection with a ground-based cloud experiment at Great Dun Fell, in northern England in 1995. Hygroscopic diameter growth factors were measured with a Tandem Differential Mobility Analyser (TDMA) for dry particle diameters between 35 and 265 nm at one of the sites upwind of the orographic cloud. An external mixture consisting of three groups of particles, each with different hygroscopic properties, was observed. These particle groups were denoted less-hygroscopic, more-hygroscopic and sea spray particles and had average diameter growth factors of 1.11–1.15, 1.38–1.69 and 2.08–2.21 respectively when taken from a dry state to a relative humidity of 90%. Average growth factors increased with dry particle size. A bimodal hygroscopic behaviour was observed for 74–87% of the cases depending on particle size. Parallel measurements of dry sub-micrometer particle number size distributions were performed with a Differential Mobility Particle Sizer (DMPS). The inorganic ion aerosol composition was determined by means of ion chromatography analysis of samples collected with Berner-type low pressure cascade impactors at ambient conditions. The number of ions collected on each impactor stage was predicted from the size distribution and hygroscopic growth data by means of a model of hygroscopic behaviour assuming that only the inorganic substances interacted with the ambient water vapour. The predicted ion number concentration was compared with the actual number of all positive and negative ions collected on the various impactor stages. For the impactor stage which collected particles with aerodynamic diameters between 0.17–0.53 μm at ambient relative humidity, and for which all pertinent data was available for the hygroscopic closure study, the predicted ion concentrations agreed with the measured values within the combined measurement and model uncertainties for all cases but one. For this impactor sampling occasion, the predicted ion concentration was significantly higher than the measured. The air mass in which this sample was taken had undergone extensive photochemical activity which had probably produced hygroscopically active material other than inorganic ions, such as organic oxygenated substances.

Global temperature stabilization via controlled albedo enhancement of low-level maritime clouds

An assessment is made herein of the proposal that controlled global cooling sufficient to balance global warming resulting from increasing atmospheric CO2 concentrations might be achieved by seeding low-level, extensive maritime clouds with seawater particles that act as cloud condensation nuclei, thereby activating new droplets and increasing cloud albedo (and possibly longevity). This paper focuses on scientific and meteorological aspects of the scheme. Associated technological issues are addressed in a companion paper. Analytical calculations, cloud modelling and (particularly) GCM computations suggest that, if outstanding questions are satisfactorily resolved, the controllable, globally averaged negative forcing resulting from deployment of this scheme might be sufficient to balance the positive forcing associated with a doubling of CO2 concentration. This statement is supported quantitatively by recent observational evidence from three disparate sources. We conclude that this technique could thus be adequate to hold the Earths temperature constant for many decades. More work—especially assessments of possible meteorological and climatological ramifications—is required on several components of the scheme, which possesses the advantages that (i) it is ecologically benign—the only raw materials being wind and seawater, (ii) the degree of cooling could be controlled, and (iii) if unforeseen adverse effects occur, the system could be immediately switched off, with the forcing returning to normal within a few days (although the response would take a much longer time).

Direct measurements and parameterisation of aerosol flux, concentration and emission velocity above a city

Articles have recently been published on aerosol size distributions and number concentrations in cities, however there have been no studies on transport of these particles. Eddy covariance measurements of vertical transport of aerosol in the size range 11 nm<Dp<3 μm are presented here. The analysis shows that typical average aerosol number fluxes in this size range vary between 9000 and 90,000 cm−2 s−1. With concentrations between 3000 and 20,000 cm−3 this leads to estimates of particle emission velocity between 20 and 75 mm s−1. The relationships between number flux and traffic activity, along with emission velocity and boundary layer stability are demonstrated and parameterised. These are used to derive an empirical parameterisation for aerosol concentration in terms of traffic activity and stability. The main processes determining urban aerosol fluxes and concentrations are discussed and quantified where possible. The difficulties in parameterising urban activity are discussed

Cloud droplet nucleation scavenging in relation to the size and hygroscopic behaviour of aerosol particles

The size distributions and hygroscopic growth spectra of aerosol particles were measured during the GCE cloud experiment at Great Dun Fell in the Pennine Hills in northern England. Hygroscopic growth is defined as the particle diameter at 90% RH divided by the particle diameter at 10% RH. The fraction of the aerosol particles scavenged by cloud droplets as a function of particle size was also measured. The general aerosol type was a mixture of marine and aged anthropogenic aerosols. The Aitken and accumulation mode numbers (average ± 1 S.D.) were 1543 ± 1078 and 1023 ± 682 cm−3 respectively. The mean diameters were in the range 30–100 nm and 100–330 nm. The hygroscopic growth spectra were bimodal about half the time. The less-hygroscopic particles had average growth factors of 1.06, 1.06, 1.03, 1.03, and 1.03 for particle diameters of 50, 75, 110, 165, and 265 nm, respectively. For the more-hygroscopic particles of the same sizes, the average hygroscopic growth was 1.34, 1.37, 1.43, 1.47, and 1.53. The effects of ageing on the aerosol particle size distribution and on hygroscopic behaviour are discussed. The scavenged fraction of aerosol particles was a strong function of particle diameter. The diameter with 50% scavenging was in the range 90–220 nm. No tail of smaller particles activated to cloud drops was observed. A small tail of larger particles that remained in the interstitial aerosol can be explained by there being a small fraction of less-hygroscopic particles. A weak correlation between the integral dry particle diameter and the diameter with 50% scavenging was seen.

Marine Cloud Brightening

The idea behind the marine cloud-brightening (MCB) geoengineering technique is that seeding marine stratocumulus clouds with copious quantities of roughly monodisperse sub-micrometre sea water particles might significantly enhance the cloud droplet number concentration, and thereby the cloud albedo and possibly longevity. This would produce a cooling, which general circulation model (GCM) computations suggest could—subject to satisfactory resolution of technical and scientific problems identified herein—have the capacity to balance global warming up to the carbon dioxide-doubling point. We describe herein an account of our recent research on a number of critical issues associated with MCB. This involves (i) GCM studies, which are our primary tools for evaluating globally the effectiveness of MCB, and assessing its climate impacts on rainfall amounts and distribution, and also polar sea-ice cover and thickness; (ii) high-resolution modelling of the effects of seeding on marine stratocumulus, which are required to understand the complex array of interacting processes involved in cloud brightening; (iii) microphysical modelling sensitivity studies, examining the influence of seeding amount, seed-particle salt-mass, air-mass characteristics, updraught speed and other parameters on cloud–albedo change; (iv) sea water spray-production techniques; (v) computational fluid dynamics studies of possible large-scale periodicities in Flettner rotors; and (vi) the planning of a three-stage limited-area field research experiment, with the primary objectives of technology testing and determining to what extent, if any, cloud albedo might be enhanced by seeding marine stratocumulus clouds on a spatial scale of around 100×100 km. We stress that there would be no justification for deployment of MCB unless it was clearly established that no significant adverse consequences would result. There would also need to be an international agreement firmly in favour of such action.

SCOUT-O3/ACTIVE High-altitude Aircraft Measurements around Deep Tropical Convection

During November and December 2005, two consortia of mainly European groups conducted an aircraft campaign in Darwin, Australia, to measure the composition of the tropical upper-troposphere and tropopause regions, between 12 and 20 km, in order to investigate the transport and transformation in deep convection of water vapor, aerosols, and trace chemicals. The campaign used two high-altitude aircraft-the Russian M55 Geophysica and the Australian Grob 520 Egrett, which can reach 20 and 15 km, respectively-complemented by upward-pointing lidar measurements from the DLR Falcon and low-level aerosol and chemical measurements from the U.K. Dornier-228. The meteorology during the campaign was characterized mainly by premonsoon conditions-isolated afternoon thunderstorms with more organized convective systems in the evening and overnight. At the beginning of November pronounced pollution resulting from widespread biomass burning was measured by the Dornier, giving way gradually to cleaner conditions by December, thus affording the opportunity to study the influence of aerosols on convection. The Egrett was used mainly to sample in and around the outflow from isolated thunderstorms, with a couple of survey missions near the end. The Geophysica-Falcon pair spent about 40% of their flight hours on survey legs, prioritizing remote sensing of water vapor, cirrus, and trace gases, and the remainder on close encounters with storm systems, prioritizing in situ measurements. Two joint missions with all four aircraft were conducted: on 16 November, during the polluted period, sampling a detached anvil from a single-cell storm, and on 30 November, around a much larger multicellular storm.