Erik Swietlicki

Hygroscopic properties of submicrometer atmospheric aerosol particles measured with H-TDMA instruments in various environments—a review

The hygroscopic properties play a vital role for the direct and indirect effects of aerosols on climate, as well as the health effects of particulate matter (PM) by modifying the deposition pattern of inhaled particles in the humid human respiratory tract. Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA) instruments have been used in field campaigns in various environments globally over the last 25 yr to determine the water uptake on submicrometre particles at subsaturated conditions. These investigations have yielded valuable and comprehensive information regarding the particle hygroscopic properties of the atmospheric aerosol, including state of mixing. These properties determine the equilibrium particle size at ambient relative humidities and have successfully been used to calculate the activation of particles at water vapour supersaturation. This paper summarizes the existing published H-TDMA results on the sizeresolved submicrometre aerosol particle hygroscopic properties obtained from ground-based measurements at multiple marine, rural, urban and free tropospheric measurement sites. The data is classified into groups of hygroscopic growth indicating the external mixture, and providing clues to the sources and processes controlling the aerosol. An evaluation is given on how different chemical and physical properties affect the hygroscopic growth.

Chemical and physical characterization of emissions from birch wood combustion in a wood stove.

The purpose of this study was to characterize the emissions of a large number of chemical compounds emitted from birch wood combustion in a wood stove. Birch wood is widely used as fuel in Swedish household appliances. The fuel load was held constant during six experiments. Particles < 2.5 mum diameter were collected and the size distribution of the particles was measured. The results were compared to the size distribution in road traffic emissions. It could be seen that the number distribution differed between the sources. In traffic exhaust, the number of particles maximized at 20 nm, while the number distribution from wood burning ranged from 20 to 300 nm. The ratio K/Ca on particles was found. to be significantly different in wood burning compared to road dust, range 30-330 for the former and 0.8+/-0.15 for the latter. The source profile of common elements emitted from wood-burning differed from that found on particles at a street-level site or in long-distance transported particles. The ratio toluene/benzene in this study was found to be in the range 0.2-0.7, which is much lower than the ratio 3.6+/-0.5 in traffic exhaust emissions. Formaldehyde and acetone were the most abundant compounds among the volatile ketones and aldehydes. The emission factor varied between 180-710mg/kg wood for formaldehyde and 5-1300mg/kg wood for acetone. Of the organic acids analyzed (3,4,5)-trimethoxy benzoic acid was the most abundant compound. Of the PAHs reported, fluorene, phenanthrene, anthracene, fluoranthene and pyrene contribute to more than 70% of the mass of PAH. Of the elements analyzed, K and Si were the most abundant elements, having emission factors of 27 and 9mg/kg wood, respectively. Although fluoranthene has a toxic equivalence factor of 5% of benzo(a)pyrene (B(a)P), it can be seen that the toxic potency of fluoranthene in wood burning emissions is of the same size as B(a)P. This indicates that the relative carcinogenic potency contribution of fluoranthene in wood smoke would be about 40% of B(a)P

Sources and properties of Amazonian aerosol particles

This review provides a comprehensive account of what is known presently about Amazonian aerosol particles and concludes by formulating outlook and priorities for further research. The review is organized to follow the life cycle of Amazonian aerosol particles. It begins with a discussion of the primary and secondary sources relevant to the Amazonian particle burden, followed by a presentation of the particle properties that characterize the mixed populations present over the Amazon Basin at different times and places. These properties include number and mass concentrations and distributions, chemical composition, hygroscopicity, and cloud nucleation ability. The review presents Amazonian aerosol particles in the context of natural compared to anthropogenic sources as well as variability with season and meteorology. This review is intended to facilitate an understanding of the current state of knowledge on Amazonian aerosol particles specifically and tropical continental aerosol particles in general and thereby to enhance future research in this area. Copyright

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.

Sensitivity of CCN spectra on chemical and physical properties of aerosol: A case study from the Amazon Basin

Organic material, about half of which is water soluble, constitutes nearly 80% of the wet-season aerosol mass in the Amazon Basin, while soluble inorganic salts (predominantly ammonium bisulfate) represent about 15%. A detailed analysis of number distributions and the size-dependent chemical composition of the aerosol indicates that, in principle, the sulfate fraction could account for most of the cloud condensation nuclei (CCN) activity. Uncertainty about the chemical speciation of the water-soluble organic component precludes a rigorous analysis of its contribution to nucleation activity. Within reasonable assumptions, we can, however, predict a similar contribution of the organic component to CCN activity as that from sulfate. Because of the nonlinear dependence of droplet nucleation behavior on solute amount, the nucleation activity cannot be attributed uniquely to the inorganic or organic fractions. The role of water-soluble organic compounds as surfactants, however, may be significant (especially in the case of biomass-burning aerosol) and more field measurements are needed to quantify their effects on the surface tension of ambient aerosols. The parametric dependence of the CCN spectra on the physical and chemical properties of the aerosol show that the number distribution, soluble content of the aerosol, and surface tension effects all play an important role in determining CCN spectra. (Less)

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

Chemical composition of aerosol during particle formation events in boreal forest

Size-segregated chemical aerosol analysis of a total 5 integrated samples has been performed for the atmospheric aerosol during events of new particle formation. The experiments were conducted during the BIOFOR 3 measurement campaign at a boreal forest site in southern Finland in spring 1999. Aerosol samples collected by a cascade low-pressure impactor were taken selectively to distinguish particle formation event aerosol from non-event aerosol. The division into “event” and “non-event” cases was done “in situ” at field, based on the on-line submicron number size distribution. The results on the chemical ionic composition of the particles show only small differences between the event and non-event sample sets. The event samples show lower concentrations of total sulfate and ammonium as well as light dicarboxylic acids such as oxalate, malonate and succinate. In the event samples, nucleation mode particle MSA (methanesulphonic acid) was found to be present exceeding the concentrations found in the non-event samples, but at larger particle sizes the sample sets contained rather similar concentrations of MSA. The most significant difference between the event and non-event sets was found for dimethylammonium, ionic component of dimethylamine ((CH3)2NH), which seems to be present in the particle phase during the particle formation periods and/or during the subsequent particle growth. The absolute event sample dimethylamine concentrations were more than 30-fold greater than the non-event concentrations in the accumulation mode size range. On the other hand, the non-event back-up filter stage for sub-30 nm particles contained more dimethylamine than the event samples. This fractionation is probably a condensation artifact of the impactor sampling. A simple mass balance estimate is performed to evaluate the quality and consistency of the results for the overall mass concentration.

Urban air pollution source apportionment using a combination of aerosol and gas monitoring techniques

The dominating local and regional sources of gaseous and particulate air pollution in the city of Lund (69,000 inhabitants) in southern Sweden were characterized using a combination of aerosol and gas-phase monitoring techniques. Twelve-hour samples were taken at two stations of both fine and coarse fraction urban aerosols with a stacked filter unit during the four-week measurement campaign in March/April 1993. The aerosol samples were analysed with PIXE for 14 major and trace elements. In addition, gaseous species (SO2, NO2, O-3) were measured simultaneously with the DOAS technique over two stretches, crossing each other only 300 m from the downtown aerosol sampling site. The combined results obtained by the analytical techniques PIXE and DOAS for aerosol and gas measurements, respectively, were used in an absolute receptor model in order to identify the major sources affecting the measurement sites and to apportion the measured air pollutants to the identified sources. The gases (SO2, NO2, O-3) could also be attributed to specific sources by combining the trace elemental concentration data for the fine fraction aerosol with that of the gaseous species in the receptor model. According to the absolute principal component analysis (APCA) model, the dominant sources for the measured species were resuspended road dust, automobile and diesel emissions, combustion of oil and coal, ferrous and non-ferrous smelters and sea spray. Of these, the sources related to traffic are mainly local in character while the others constitute a regional background. For a small city in southern Scandinavia like Lund with only light industry, the long-range transported air pollutants make up a significant part of the fine fraction aerosol

Turbulent aerosol fluxes over the Arctic Ocean: 2. Wind-driven sources from the sea

An eddy-covariance flux system was successfully applied over open sea, leads and ice floes during the Arctic Ocean Expedition in July-August 1996. Wind-driven upward aerosol number fluxes were observed over open sea and leads in the pack ice. These particles must originate from droplets ejected into the air at the bursting of small air bubbles at the water surface. The source flux F (in 106 m−2 s−1) had a strong dependency on wind speed, log(F)=0.20U¯-1.71 and 0.11U¯-1.93, over the open sea and leads, respectively (where U¯ is the local wind speed at about 10 m height). Over the open sea the wind-driven aerosol source flux consisted of a film drop mode centered at ∼100 nm diameter and a jet drop mode centered at ∼1 μm diameter. Over the leads in the pack ice, a jet drop mode at ∼2 μm diameter dominated. The jet drop mode consisted of sea-salt, but oxalate indicated an organic contribution, and bacterias and other biogenic particles were identified by single particle analysis. Particles with diameters less than −100 nm appear to have contributed to the flux, but their chemical composition is unknown. Whitecaps were probably the bubble source at open sea and on the leads at high wind speed, but a different bubble source is needed in the leads owing to their small fetch. Melting of ice in the leads is probably the best candidate. The flux over the open sea was of such a magnitude that it could give a significant contribution to the condensation nuclei (CCN) population. Although the flux from the leads were roughly an order of magnitude smaller and the leads cover only a small fraction of the pack ice, the local source may till be important for the CCN population in Arctic fogs. The primary marine aerosol source will increase both with increased wind speed and with decreased ice fraction and extent. The local CCN production may therefore increase and influence cloud or fog albedo and lifetime in response to greenhouse warming in the Arctic Ocean region.