Olle H. Berg

Chemical mass closure and assessment of the origin of the submicron aerosol in the marine boundary layer and the free troposphere at Tenerife during ACE-2

The organic, inorganic, mineral content and mass concentration of the submicron aerosol were measured in June−July 1997 on Tenerife in the marine boundary layer (MBL) and the free troposphere (FT). Aerosol size distributions were measured simultaneously at the same sites. The submicron aerosol mass concentrations derived from the chemical composition and calculated from the number size distributions agreed within the experimental uncertainties both in the MBL (±47%) and the FT (±75%). However, the analytical uncertainties in the concentration of organic compounds (OC) for the average sample collected in the MBL (-97, +77%) and the FT (±74%) were high. The average contribution of aerosol various components to the submicron aerosol mass were calculated for different air masses. The absolute uncertainties in these contributions were calculated by adding random uncertainties quadratically and possibly systematic errors in a conservative way. In the unperturbed MBL, the aerosol average composition (± the absolute uncertainty in the contribution) was 37 (-3, +9)% for non-sea-salt SO42-+ NH4+, 21 (-2, +10)% for sea-salt, and 20 (-7, +11)% OC (N=19). In the unperturbed FT, OC and SO42- accounted for 43 (±20)% and 32 (-5, +3)% of the submicron aerosol mass, respectively (N=15). Considering these aerosol compositions, we suggest that the source for the FT aerosol could be the transport of continental aerosol through precipitating convective clouds. A simple budget calculation shows, that in background conditions, the MBL and FT aerosol compositions are consistent with the hypothesis that the MBL aerosol is formed by the dilution of continental aerosol by FT air, modified by deposition and condensation of species of oceanic origin. Dramatic continental aerosol outbreaks were observed in both the MBL and the FT. The aerosol outbreaks in the MBL were due to transport of polluted air masses from Europe. They were characterized mainly by increases in SO42-+ NH4+, making up 75 (-5, +19)% of the submicron aerosol mass. The aerosol outbreaks in the FT were due to advection of desert dust, probably mixed with pollution aerosol.

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.

Hygroscopic properties of aerosol particles in the north-eastern Atlantic during ACE-2

Measurements of the hygroscopic properties of sub-micrometer atmospheric aerosol particles were performed with hygroscopic tandem differential mobility analysers (H-TDMA) at 5 sites in the subtropical north-eastern Atlantic during the second Aerosol Characterization Experiment (ACE-2) from 16 June to 25 July 1997. Four of the sites were in the marine boundary layer and one was, at least occasionally, in the lower free troposphere. The hygroscopic diameter growth factors of individual aerosol particles in the dry particle diameter range 10−440 nm were generally measured for changes in relative humidity (RH) from <10% to 90%. In the marine boundary layer, growth factors at 90% RH were dependent on location, air mass type and particle size. The data was dominated by a unimodal growth distribution of more-hygroscopic particles, although a bimodal growth distribution including less-hygroscopic particles was observed at times, most often in the more polluted air masses. In clean marine air masses the more-hygroscopic growth factors ranged from about 1.6 to 1.8 with a consistent increase in growth factor with increasing particle size. There was also a tendency toward higher growth factors as sodium to sulphate molar ratio increased with increasing sea-salt contribution at higher wind speeds. During outbreaks of European pollution in the ACE-2 region, the growth factors of the largest particles were reduced, but only slightly. Growth factors at all sizes in both clean and polluted air masses were markedly lower at the Sagres, Portugal site due to more proximate continental influences. The frequency of occurrence of less-hygroscopic particles with a growth factor of ca. 1.15 was greatest during polluted conditions at Sagres. The free tropospheric 50 nm particles were predominately less-hygroscopic, with an intermediate growth factor of 1.4, but more-hygroscopic particles with growth factors of about 1.6 were also frequent. While these particles probably originate from within the marine boundary layer, the less-hygroscopic particles are probably more characteristic of lower free tropospheric air masses. For those occasions when measurements were made at 90% and an intermediate 60% or 70% RH, the growth factor G(RH) of the more-hygroscopic particles could be modelled empirically by a power law expression. For the ubiquitous more-hygroscopic particles, the expressions G(RH)=(1-RH/100)-0.210 for 50 nm Aitken mode particles and G(RH)=(1-RH/100)-0.233 for 166 nm accumulation mode particles are recommended for clean marine air masses in the north-eastern Atlantic within the range 0

Hygroscopic growth of aerosol particles in the marine boundary layer over the Pacific and Southern Oceans during the First Aerosol Characterization Experiment (ACE 1)

The hygroscopic properties of submicrometer aerosol particles were studied with a Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) in the remote marine tropospheric boundary layer (MBL) over the Pacific and Southern Oceans in connection with the southern hemisphere marine First Aerosol Characterization Experiment (ACE 1) in October–December 1995. The H-TDMA was placed on board the ship R/V NOAA Discoverer and measured the hygroscopic diameter growth of individual aerosol particles when taken from a dry state to a relative humidity (RH) of 89–90%. Measurements were performed for the particles with dry diameters of 35, 50, 75, and 150 (or 165) nm. The natural aerosol present in the remote MBL largely consists of two types, a sea-salt component and a non-sea-salt (nss) sulfate component. Since their hygroscopic behavior is significantly different, the H-TDMA could clearly distinguish between these two types and thus make in situ measurements of the mixing state of the MBL aerosol. During the ACE 1 intensive campaign in the Southern Ocean south of Australia, the hygroscopic diameter growth factors at RH = 90% for the nss-sulfate aerosol particles were 1.62, 1.66, and 1.78 at dry particle diameters of 35, 50, and 150 nm, respectively, and for time periods with remote marine air masses. These values exceed those normally found in continental polluted environments. The growth factors for the externally mixed sea-salt particles were even higher (2.12 and 2.14 for 50 and 150 nm). The corresponding values for the Pacific Ocean (at RH = 89%) for the nss-sulfate particles were 1.56, 1.59, 1.61, and 1.63 for 35, 50, 75, and 165 nm. Particle deliquescence and RH hysteresis between RH = 68–90% was only observed in air masses north of the South Pacific Gyre, and then only for the Aitken mode particles (particle diameters ∼20–80 nm). The occurrence of externally mixed sea-salt particles could be linked to conditions with high wind speeds in connection with frontal passages or low pressure systems. Nevertheless, the number of externally mixed 150 nm sea-salt particles was found to be poorly correlated with local wind speed, probably due to a rather long life-time of these submicrometer particles. Particles with hygroscopic growth factors significantly less than those of the nsssulfate particles (denoted less hygroscopic particles) were only present during periods with anthropogenic influence.

Determination of Differential Mobility Analyzer Transfer Functions Using Identical Instruments in Series

The differential mobility analyzer (DMA) is an important tool for determining particle size distributions. The physical performance of a DMA is quantified by the concept of the transfer function. Therefore, knowledge of the transfer function is important to interpret the mobility distributions recorded by a DMA. During a calibration workshop in preparation for the Aerosol Characterization Experiment 1 (ACE1) field campaign, the transfer functions of five types of different mobility analyzers (Vienna-type DMA short, medium, and long, CIT radial, and TSI long; CIT = California Institute of Technology, Pasadena, CA; TST = TSI Inc., St. Paul, MN) were experimentally characterized by height, width, and area of their transfer functions. Different particles size ranges between 3 and 200 nm were investigated. The transfer function was determined by scanning a DMA across the mobility distribution produced by another, identical DMA. Subsequently, the data were processed by a deconvolution algorithm assuming a triangular shape for the transfer function. For all DMA types, the area of the transfer function decreased with particle size, especially for ultrafine particles (d_p < 20 nm). The gradient with which this area decreases with particle size, however, is different for each of the DMA types investigated. The calibration provides an improved description of the performance of each DMA, particularly in the ultrafine size range.

Hygroscopic properties of aerosol particles over the central Arctic Ocean during summer

The hygroscopic properties of submicrometer aerosol particles in the Arctic summer marine boundary layer (MBL) were observed on board the icebreaker Oden during the Arctic Ocean Expedition 1996 (AOE-96). The measurements were performed between July 15 and August 25 1996 and covered the region between longitudes 16°-147°E and latitudes 70°-87.5°N, mostly over melting pack ice. The hygroscopic tandem differential mobility analyzer (H-TDMA) was used to determine the hygroscopic diameter growth of aerosol particles at four dry diameters (15, 35, 50, and 165 nm) and three relative humidities (50%, 70%, and 90% RH). The hygroscopic behavior of the aerosol particles over the pack ice showed large temporal variations, in contrast to previous observations in marine boundary layers over warmer oceans. These variations were mostly due to the high degree of vertical atmospheric stratification often observed over the pack ice. However, when comparing the average diameter growth factors of the more hygroscopic particle group, representing an aged aerosol with growth factors between 1.4–1.9 at 90% RH and present in 81–86% of all cases, the agreement between the measurements over the Arctic and the warmer oceans was very good and depended on the average wind speed. The average diameter growth factors of the more hygroscopic particles as a function of relative humidity were modeled empirically by power law expressions. The concentration of cloud condensation nuclei (CCN) estimated from aerosol number size distribution and hygroscopic growth data correlated well with direct measurements but overpredicted the CCN concentrations by about 30%. In 43 cases when the sampled air mass had undergone processing in Arctic Ocean MBL clouds, the minimum CCN diameter was estimated to be 76±15 nm, corresponding to effective water vapor supersaturations of 0.28±0.08%.

Droplet nucleation and growth in orographic clouds in relation to the aerosol population

Abstract The formation and development of orographic clouds was studied in a field experiment comprising several measurement sites at a mountain ridge. The influence of the aerosol population present on the cloud microstructure was studied in relation to the dynamics in the cloud formation. Droplet nucleation scavenging was investigated by the introduction of a non-dimensional particle diameter related to the process, and it was found that the scavenging rose rapidly in a relatively narrow particle size interval. The size dependency of the scavenging could partly be explained by external mixture of the aerosol. The large particles in the cloud interstitial aerosol was found to be of a chemical nature which allows for only a very weak uptake of water, implying that the chemical composition of these particles rather than entrainment of dry air prevented the droplet nucleation. The aerosol particle number concentration was found to strongly influence the cloud microstructure. Droplet number concentrations up to approximately 2000 cm −3 were observed together with a substantially reduced effective droplet diameter. The observed effect of elevated particle number concentrations in orographic clouds was generalised to the climatologically more important stratiform clouds by the use of a cloud model. It was found that the microstructure of stratiform clouds was strongly dependent on the aerosol population present as well on the dynamics in the cloud formation.

The Great Dun Fell Experiment 1995: an overview

Abstract During March and April of 1995 a major international field project was conducted at the UMIST field station site on Great Dun Fell in Cumbria, Northern England. The hill cap cloud which frequently envelopes this site was used as a natural flow through reactor to examine the sensitivity of the cloud microphysics to the aerosol entering the cloud and also to investigate the effects of the cloud in changing the aerosol size distribution, chemical composition and associated optical properties. To investigate these processes, detailed measurements of the cloud water chemistry (including the chemistry of sulphur compounds, organic and inorganic oxidised nitrogen and ammonia), cloud microphysics and properties of the aerosol and trace gas concentrations upwind and downwind of the cap cloud were undertaken. It was found that the cloud droplet number was generally strongly correlated to aerosol number concentration, with up to 2000 activated droplets cm−3 being observed in the most polluted conditions. In such conditions it was inferred that hygroscopic organic compounds were important in the activation process. Often, the size distribution of the aerosol was substantially modified by the cloud processing, largely due to the aqueous phase oxidation of S(IV) to sulphate by hydrogen peroxide, but also through the uptake and fixing of gas phase nitric acid as nitrate, increasing the calculated optical scattering of the aerosol substantially (by up to 24%). New particle formation was also observed in the ultrafine aerosol mode (at about 5 nm) downwind of the cap cloud, particularly in conditions of low total aerosol surface area and in the presence of ammonia and HCl gases. This was seen to occur at night as well as during the day via a mechanism which is not yet understood. The implications of these results for parameterising aerosol growth in Global Climate Models are explored.

The effects of in-cloud mass production on atmospheric light scatter

Direct physical measurements of particle mass and number concentration indicate an increase in overall aerosol mass resulting from cloud processing, most likely through aqueous-phase chemistry (e.g., SO2 oxidation). Measurements conducted in the Pennines of Northern England reveal an average increase of 14 to 20% in dry aerosol mass (0.003<particle diameter<0.9 μm) after aerosol passage through an orographic cloud. The rate of in-cloud mass production is most sensitive to changes in upwind particle size distributions, SO2 concentration, and cloud water acidity. Newly-formed mass appears in size range between 200 and 600 nm and enhances the bimodality of the particle number distribution after cloud processing. Furthermore, the cloud-produced mass is estimated to increase total light scattering, bsp, by 18 to 24%. The scattering efficiency of the dry, cloud-generated aerosol is 5.0±0.3 m2 g−1 and increases to 7.4±0.7 m2 g−1 when adjusted to 90% relative humidity by incorporating particle hygroscopicity data.

Changes in hygroscopic growth of atmospheric submicrometer particles during air mass subsidence events in remote marine environments

Publisher Summary This chapter discusses the changes in hygroscopic growth of atmospheric submicrometer particles during air mass subsidence events in remote marine environments. Sea-level measurements of the hygroscopic growth of submicrometer aerosol particles were performed during the ACE-1 field experiment in the South Tasmanian Sea, and on a north–south transect across the Pacific Ocean preceding the ACE-1 intensive campaign. A Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) was used to measure the hygroscopic diameter growth of submicrometer aerosol particles, when taken from a dry state to a humid state with a relative humidity of 90%. A substantial lowering of the hygroscopic growth factors was seen during events with air mass subsidence resulting in increased sea-level particle concentrations in the ultrafine (