Spectroscopic Characterization of Humic-Like Substances in Airborne Particulate Matter

In a standard reference air dust (NIST 1648 – urban particulate matter) as well as in airborne particulate matter collected in German urban and rural areas (Dortmund, Sauerland) 10% and more of the organic carbon can be attributed to macromolecular substances like humic and fulvic acids (HA, FA). Indirect evidence for the presence of humin was also obtained. HA and FA extracted from NIST 1648 and other urban and rural atmospheric particles using 0.1 m NaOH and isolated by ion-exchangers were characterized by their molecular-size distribution applying multistage ultrafiltration, their carbon content and their UV/VIS, Fourier-transformed infrared (FTIR) and nuclear magnetic resonance (¹H-NMR) spectra. Summarizing, the structural studies exhibit that these humic-like substances (HULIS) contained in air dust samples are small in their molecular size and rich in aliphatic and carbohydrate substructures compared to HA and FA from soils and aquatic systems.     

Effect of atmospheric humic-like substances on the enhanced dissolution of volatile organic compounds into dew water

Simultaneous sampling of chlorinated hydrocarbons (CHs) and monocyclic aromatic hydrocarbons (MAHs), potentially harmful to humans and/or responsible for the formation of ozone and secondary particles, in dew water and in the ambient air was carried out from August 2004 to July 2005 in Hino City, situated in the western part of Greater Tokyo, Japan. CHs were less contained in dew water than MAHs. Toluene (volume-weighted mean concentration, VWM: 4.77 nM) and m,p-Xylenes (VWM: 5.07 nM) except dichloromethane, which was abnormally high (VWM: 1.14 μM), were abundant among eleven VOCs determined in dew water. Chloroform, carbon tetrachloride, 1,2-dichloroethane, and benzene were not detected in dew water during the study period. Dew water contained higher amounts of VOCs than would have been expected from the ambient gas-phase concentrations and the temperature-corrected Henry's law constants. Following the determination method of humic substances in river water proposed by Hiraide et al. [Hiraide, M., Shima, T., Kawaguchi, H., 1994. Separation and determination of dissolved and particulate humic substances in river water. Mikrochim. Acta 113, 269–276], the VWM of soluble humic and fulvic acid fractions in dew water was found to be 1.00 mg/L and 0.87 mg/L (n = 20), respectively, while the VWM of particulate humic and fulvic acid fractions was found to be 0.61 mg/L and 0.42 mg/L (n = 20), respectively. Surface tension decreased with an increase in dissolved fulvic acid fraction in dew water, indicating that humic-like substances with relatively lower molecular weight, which is soluble in acid solution, could be an effective surface-active species within dew water. The enrichment factors, which were defined as the ratio of the observed VOCs concentration to the estimated, were over 10² for MAHs except for benzene and increased as the increment of total humic-like substances (HULIS) concentration (the sum of humic and fulvic acid fractions in both dissolved and particulate form) normalized by total inorganic ion concentration in dew water. Our results indicate that total HULIS in dew water could enhance the dissolution of atmospheric VOCs into dew droplets.     

Characterization of Water-Soluble Macromolecular Substances in Cloud Water

In this contribution we present to our knowledge the first investigations of macromolecular, often called humic-like substances (HULIS) in cloud water samples and compare them with water-soluble extracts from atmospheric PM_2.5, soils and waters to study its possible origin. Chemical analysis was done using high performance liquid chromatography (HPLC) coupled with UV and diode array detector, and HPLC coupled with ESI-MS (electrospray ionization mass spectrometer). The data have been treated by principle component analysis (PCA) and cluster analysis to state similarities and/or differences between different types of samples. Our results show that the content of organic and inorganic species is distinctly different in smaller and larger droplets suggesting varying origin. We conclude that smaller droplets are formed more from organic containing condensation nuclei (CCN) and larger droplets more from inorganic containing CCN organic compounds. Putting all experimental findings together we state that HULIS in cloud water—and consequently in particulate CCN precursors—are produced in an atmospheric polymerization process from low molecular weighted organics of different origin. Evidence is found that anthropogenic sources contribute to this pathway. Cloud drops may act as reactor in this HULIS formation process but more likely are gas-phase or gas-to-particle interactions.     

Organosulfates – A New Component of Humic-Like Substances in Atmospheric Aerosols?

Ion trap mass spectrometry (ITMS) was used to obtain further qualitative information about the chemical composition of humic-like substances (HULIS) in atmospheric particulate matter. Particles ≤10 μm (PM₁₀) were collected on quartz fiber filters for 24 h in the region of Basel (Switzerland) and extracted with water. HULIS were separated from inorganic salts by size exclusion chromatography (SEC) and detected by electrospray ionization in the negative ion mode (ESI(−)). Series of consecutive fragment ion spectra (MSⁿ) were recorded by ITMS. Full scan mass spectra of the extracts showed a mass distribution pattern characteristic for HULIS. Different molecular ions were selected from this pattern for further fragmentations. Among them the molecular ion m/z 299 was considered as representative and intensively studied. Many MS² and MS³ fragment spectra contained a fragment m/z 97 and a neutral loss of 80 u. Time-of-flight (TOF) MS and deuterium exchange experiments identified m/z 97 as hydrogen sulfate. MS² and MS³ fragment spectra supported the existence of sulfate covalently bound to HULIS. The fragmentation behavior of sulfated HULIS could be confirmed by model compounds.     

Theoretical Modeling of the Size-Dependent Influence of Surface Tension on the Absorptive Partitioning of Semi-Volatile Organic Compounds

The influence of surface tension on the formation of secondary organic aerosol (SOA) is investigated in this study using a size-dependent absorptive partitioning model. A theoretical framework is offered to estimate the surface tension of multi-component aerosols consisting of organic compounds and water. The size-dependent influence of surface tension on the absorptive partitioning of semi-volatile organic compounds is examined via numerical simulations of systems of representative pre-existing aerosol (PA) components and semi-volatile organic compounds that have been observed to constitute SOA. Results indicate that if nonpolar organic species constitute a significant fraction of the PA, the Kelvin effect on SOA formation may be negligible. However, if PA is dominated by polar organic compounds, the Kelvin effect on SOA formation is significant when the PA initial diameter is smaller than approximately 200 nm. If the PA is an aqueous aerosol, the Kelvin effect on SOA formation is most important. A simplified computational scheme for estimation of the Kelvin effect is developed in this study and feasibly could be coupled into three-dimensional air quality models that simulate SOA formation. Available observations also suggest that future modeling and analysis of SOA formation may need to consider the Kelvin effect. Concrete testing of the purely theoretical model presented here requires carefully designed observations that examine the phase distribution of secondary organic compounds between the gas phase and aerosol particles small enough to be affected by surface tension.     

Application of Non-Ionic Solid Sorbents (XAD Resins) for the Isolation and Fractionation of Water-Soluble Organic Compounds from Atmospheric Aerosols

A detailed procedure using non-ionic macropourous XAD-8 and XAD-4 resins is presented for the isolation and fractionation of aerosol water-soluble organic compounds (WSOC) from aerosol samples. The procedure entails adsorption of WSOC fraction onto XAD-8 and XAD-4 resins, desalting of the adsorbed organic material with ultra-pure water, elution of the retained organic matter with 40% MeOH solution and freeze-drying. Due to resin’s different properties and to certain hydrophobic/hydrophilic interactions between the resin polymers and the organic matter, two major fractions were obtained; namely the XAD-8 and the XAD-4 eluates. The XAD-8 eluate, which accounts for 55–60% of total aerosol WSOC, is represented by partially acidic compounds with significant hydrophobic moieties. The XAD-4 fraction holds few conjugated systems and a higher content of hydrophilic structures with low molecular size, and accounts for 9% of total WSOC. The isolated WSOC sub-fractions were nearly free from inorganic species, and successful recoveries of organic matter from the resins were accomplished. With this procedure the XAD-8 eluate yields a mixture representative of those WSOC that are highly conjugated compounds in atmospheric aerosols. It also allows a successful characterisation of the organic material by advanced analytical techniques without the interference of inorganic species present in the original sample of atmospheric particles.     

Characterization of atmospheric surfactants in the bulk precipitation by electrochemical tools

Characterization of atmospheric surfactants in bulk precipitations was carried out by adsorption study at the mercury electrode/solution interface using phase sensitive AC voltammetry. The structure and permeability of the adsorbed organic films at the mercury electrode was tested using the redox processes of lead and cadmium ions as electrochemical tools. The effects of organic matter from the bulk precipitations (rainwater and melted snow) were compared to those obtained for aqueous solutions of model substances: aromatic hydrocarbon (naphtalene), anionic surfactant (sodium dodecylbenzene sulfonate, NDBS), protein (albumine) and selected model substances suggested to be representative of water soluble organic compounds (WSOC) in atmospheric water (monocarboxylic, dicarboxylic, and polyacidic compounds and levoglucosan). It was found that substances like humic acid and 3-hydroxybutanoic acid may play an important role in atmospheric heterogeneous chemistry because of their surface active potential.     

The effect of clouds on aerosol growth in the rural atmosphere

Measurements of accumulation mode aerosol in the atmospheric boundary layer under cloudy and cloud-free conditions, and in the lower free troposphere under cloud-free conditions, were conducted over the rural northwest of England. Normalised size distributions in the cloud-free boundary layer (CFBL) and the cloud-free free troposphere (CFFT) exhibited almost identical spectral similarities with both size distributions possessing a concentration peak mode-radius of ≈0.05 μm or less. By comparison, aerosol distributions observed in cloudy air exhibited a distinctive log-normal distribution with mode-radii occurring at ≈0.1 μm concomitant with a local minimum at ≈0.05 μm. The consistent and noticeable difference in spectral features observed between cloudy and cloud-free conditions suggest that a greater amount of gas-to-particle conversion occurs on cloudy days, presumably through in-cloud aqueous phase oxidation processes, leading to larger sized accumulation mode particles. Apart from the distinct difference between cloudy and cloud-free aerosol spectra on cloudy days, aerosol concentration and mass were observed to be significantly enhanced above that of the ambient background in the vicinity of clouds. Volatility analysis during one case of cloud processing indicated an increase in the relative contribution of aerosol mass volatile at temperatures characteristic of sulphuric acid, along with a smaller fraction of more volatile material (possibly nitric acid and/or organic aerosol). Growth-law analysis of possible growth mechanisms point to aqueous phase oxidation of aerosol precursors in cloud droplets as being the only feasible mechanism capable of producing the observed growth. The effect of cloud processing is to alter the cloud condensation nuclei (CCN) supersaturation spectrum in a manner which increases the availability of CCN at lower cloud supersaturations.     

Study on the Chemical Character of Water Soluble Organic Compounds in Fine Atmospheric Aerosol at the Jungfraujoch

In this study the chemical nature of the bulk of water soluble organic compounds in fine atmospheric aerosol collected during summer 1998 at the Jungfraujoch, Switzerland (3580 m asl) is characterised. The mass concentration of water soluble organic substances was similar to those of major inorganic ions, and the water soluble organic matter was found to be composed of two main fractions: (i) highly polyconjugated, acidic compounds with a varying degree of hydrophobicity and (ii) slightly polyconjugated, neutral and very hydrophilic compounds. The contribution of both fractions to the total water soluble organic carbon was about 50%. Separation into individual components was impossible either by HPLC or capillary electrophoresis which indicates the presence of a high number of chemically similar but not identical species. Results obtained by ultrafiltration and HPLC-MS have shown that the molecular weights are of the order of several hundreds. Most of the protonation constants for the acidic compounds determined by capillary electrophoresis were in the range 10⁴–10⁷.     

In-situ Formation of Light-Absorbing Organic Matter in Cloud Water

Current climate models seem to underestimate the flux of solar energy absorbed by the global troposphere. All of these models are constrained with the assumption that cloud droplets consist of pure water. Here we demonstrate in a simple laboratory experiment that aromatic hydroxy-acids which are found in continental fine aerosol can react with hydroxyl radicals under typical conditions prevalent in cloud water influenced by biomass burning. The reactions yield colored organic species which do absorb solar radiation. We also suggest that the products of such reactions may be humic-like substances whose presence in continental aerosol has been confirmed but their source mechanisms are still much sought after. We also attempt to give a first order estimate of the enhancement of water absorption at a visible wavelength under atmospheric conditions.     

Absorption and fluorescence properties of rainwater during the cold season at a town in Western Portugal

This study aims at evaluating the variability of the optical properties of chromophoric dissolved organic matter (CDOM) of rainwater during the cold season, specifically between Autumn and Winter periods. The spectroscopic characteristics of rainwater samples collected at a town (Aveiro) in western Portugal were assessed by UV-Vis absorbance and three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopies. Rainwater samples showed similar characteristics to those of natural humic substances when analysed by UV-Vis absorbance spectroscopy, but a significant difference was observed in the volume weight average (VWA) of absorbances between Autumn and Winter. In general, the EEM fluorescence spectra of the Autumn and Winter samples disclosed the presence of six fluorophores with different VWA specific fluorescence intensities: three humic-like (λ _excitation/λ _emission ≈ 230/415 nm; 290/415 nm; and 340/415 nm) and three protein-like (λ _excitation/λ _emission ≈ 230/350 nm; 280/340 nm; and 225/300 nm), but one of the humic-like peaks (≈340/415 nm) does not always appear in the EEM fluorescence spectra of the Winter samples. During the cold season, chromophoric compounds are important constituents of rainwater dissolved organic matter and the presence of these highly absorbing and fluorescing compounds may exert a determining effect in atmospheric absorption of solar radiation.     

Lidar depolarization measurements for aerosol source and property studies over Chungli (24.58° N, 121.1° E)

Aerosol depolarization ratio and aerosol optical depth (AOD) were measured at Chungli (24.58° N, 121.1° E), Taiwan during the period from 2002–2004. The depolarization ratios of background aerosol have values mostly less than 0.06. The maximum AOD in the altitude range of 0.7 to 2km occurs in the summer (June–August) while between 2 and 5km, the spring (March–May) shows the maximum. The former is mainly related to strong convection and humidity; however the latter is due to anthropogenic aerosols transported from East China and Southeast Asia based on calculations of backward trajectories. This seasonal variation of AOD inferred from different transport mechanisms and aerosol compositions which are supported by the height distributions of aerosol extinction and origins.     

The influence of the organic aerosol component on CCN supersaturation spectra for different aerosol types

Abstract This paper describes the effect of the presence of water-soluble organic compounds (WSOC) in aerosol particles on the aerosol critical supersaturation as defined by the Köhler theory and on cloud condensation nuclei (CCN) number concentration. Taking into account both the soluble mass increase and the surface tension depression due to WSOC, we calculated a substantial decrease of the aerosol critical supersaturation, which results in a large increase in CCN number concentration. CCN supersaturation spectra were computed for three different aerosol types: marine, rural and urban. The increase of CCN number concentration in the presence of WSOC (with respect to the case when only the inorganic aerosol compounds are considered) varies with aerosol type, with an increase up to 13% in the marine case, up to 97% in the rural case, and up to 110% in the urban case, for the supersaturation range typical of atmospheric conditions.     

Microphysical, chemical and optical aerosol properties in the Baltic Sea region

The microphysical structure, chemical composition and prehistory of aerosol are related to the aerosol optical properties and radiative effect in the UV spectral range. The aim of this work is the statistical mapping of typical aerosol scenarios and adjustment of regional aerosol parameters. The investigation is based on the in situ measurements in Preila (55.55° N, 21.00° E), Lithuania, and the AERONET data from the Gustav Dalen Tower (58 N, 17 E), Sweden.Clustering of multiple characteristics enabled to distinguish three aerosol types for clear-sky periods: 1) clean maritime–continental aerosol; 2) moderately polluted maritime–continental aerosol; 3) polluted continental aerosol. Differences between these types are due to significant differences in aerosol number and volume concentration, effective radius of volume distribution, content of SO₄⁻ ions and Black Carbon, as well as different vertical profiles of atmospheric relative humidity. The UV extinction, aerosol optical depth (AOD) and the Ångstrom coefficient α increased with the increasing pollution. The value α = 1.96 was observed in the polluted continental aerosol that has passed over central and eastern Europe and southern Russia. Reduction of the clear-sky UV index against the aerosol-free atmosphere was of 4.5%, 27% and 41% for the aerosol types 1, 2 and 3, respectively.     

The effects of aerosols on the response of a two-dimensional zonally-averaged climate model

Summary The response of climate processes to changes in aerosols is investigated using a two-dimensional zonally-averaged climate model. To account for the spatial and temporal heterogeneities of aerosol distributions, a strongly scattering maritime aerosol over ocean and a strongly absorbing rural aerosol over land are used in the layer between the surface and the 700 mb level. The effects of aerosols, gases and clouds on the radiative transfer are computed concurrently using a parameterized form of a two-stream approximation. Aerosols induce a reduction of the solar absorption at the surface and an enhancement of atmospheric absorption. The resulting changes in the climate model parameters are not only a function of the radiatively-active atmospheric constituents, but also of the amplifying or dampening effects of feedback processes employed in the model calculations. For the specified aerosol types and the optical thickness distribution given by Potter and Cess, the annual temperature change at the surface is –2.1 °C with ice-albedo feedback. Without ice-albedo feedback the corresponding value is –1.4 °C. In the present study aerosols produce a cooling effect in the atmosphere at all latitudes.

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Zusammenfassung Der Einfluß von unterschiedlichen Aerosolen auf Klimaprozesse wird mit Hilfe eines zweidimensionalen Klimamodells untersucht. Um die zeitliche und räumliche Variabilität von Aerosolverteilungen zu berücksichtigen, wird über dem Meer ein überwiegend streuendes Aerosol und über Land ein überwiegend absorbierendes Aerosol in der Schicht zwischen dem Erdboden und dem 700 mb Niveau betrachtet. Der Einfluß von Aerosolen, Gasen und Wolken auf den Strahlungstransport wird mit Hilfe einer parametrisierten Zweistromapproximation berechnet. Aerosole verursachen eine Reduzierung der solaren Absorption an der Erdoberfläche und eine Verstärkung der atmosphärischen Absorption. Resultierende Änderungen der Klimamodellparameter sind nicht nur eine Funktion der strahlungsaktiven atmosphärischen Bestandteile, sondern auch von verstärkenden oder dämpfenden Rückkopplungsprozessen. Für die hier benutzten speziellen Aerosoltypen und die Verteilung der optischen Dicke nach Potter and Cess ergibt sich eine Änderung in der Jahresmitteltemperatur von –2,1 °C unter Berücksichtigung des Eis-Albedo-Rückkopplungseffekts. Ohne diesen Mechanismus beträgt die entsprechende Temperaturänderung –1,4 °C. In der Atmosphäre ergibt sich ebenfalls eine Temperaturabnahme in allen Breiten.

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With 7 Figures     

The effects of below-cloud aerosol on the acidification process of rain

Using a model of the acidification process of rain, we calculate and analyze the effects and contributions of a below-cloud aerosol in its different concentrations and acidities on the pH and ion components of rain (SO ₄ ^2– , H⁺, NO ₃ ^– , NH ₄ ⁺ , etc.) under the conditions of different concentrations of pollution gases. The results show that the aerosol has an acidification or alkalization effect on the rain which changes the pHs of rain and aerosol. As acidifying pollution gas concentrations (SO₂, HNO₃) are low, the acid aerosol has important effects on the pH and H⁺ of rain, but as the gas concentrations are high, the acid aerosol has very little effect. The alkalizing aerosol makes the pH of rain increase by between 0.3 and 0.5 and neutralizes about 60% of H⁺ in the rain. As alkalizing pollution gas NH₃ exists, the acid aerosol has important effects on the pH and H⁺ of rain. But the alkalizing aerosol has very little effect, especially as the NH₃ concentration is high. The percentage contribution of the aerosol to SO ₄ ^2– in rain is generally 7–15%, the contribution of the aerosol to NO ₃ ^– is nearly the same as that of HNO₃=1 ppb, and the contribution of the aerosol to NH ₄ ⁺ is nearly the same as that of NH₃, from 5 to 7 ppb, and is an important source of NH ₄ ⁺ in rain. Finally, according to the actual conditions of typical regions in the south and north of China (Chongqing and Beijing), we analyze the effects of aerosol and pollution gases on the ion components of rain.     

A closure study of sub-micrometer aerosol particle hygroscopic behaviour

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.     

One year measurements of aerosol optical properties over an urban coastal site: Effect on local direct radiative forcing

We present results of direct aerosol radiative forcing over a French Mediterranean coastal zone based on one year of continuous observations of aerosol optical properties during 2005–2006. Monthly-mean aerosol optical depth at 440 nm ranged between 0.1 and 0.34, with high Angstrom coefficient (α > 1.2). The single scattering albedo (at 525 nm) estimated at the surface ranged between 0.7 and 0.8, indicating significant absorption. The presence of aerosols over the Mediterranean zone during summer decreases the shortwave radiation reaching the surface by as much as 26 ± 3.9 W m^− 2, and increases the top of the atmosphere reflected radiation by as much as 5.2 ± 1.0 W m^− 2. The shortwave atmospheric absorption translates to an atmospheric heating of 2.5 to 4.6 K day^− 1. Concerted efforts are needed for investigating the possible impact of the increase in heating rate on the maintenance of heat-waves frequently occurring over this coastal region during summer time.     

Impacts of greenhouse gases and aerosol direct and indirect effects on clouds and radiation in atmospheric GCM simulations of the 1930–1989 period

Among anthropogenic perturbations of the Earths atmosphere, greenhouse gases and aerosols are considered to have a major impact on the energy budget through their impact on radiative fluxes. We use three ensembles of simulations with the LMDZ general circulation model to investigate the radiative impacts of five species of greenhouse gases (CO₂, CH₄, N₂O, CFC-11 and CFC-12) and sulfate aerosols for the period 1930–1989. Since our focus is on the atmospheric changes in clouds and radiation from greenhouse gases and aerosols, we prescribed sea-surface temperatures in these simulations. Besides the direct impact on radiation through the greenhouse effect and scattering of sunlight by aerosols, strong radiative impacts of both perturbations through changes in cloudiness are analysed. The increase in greenhouse gas concentration leads to a reduction of clouds at all atmospheric levels, thus decreasing the total greenhouse effect in the longwave spectrum and increasing absorption of solar radiation by reduction of cloud albedo. Increasing anthropogenic aerosol burden results in a decrease in high-level cloud cover through a cooling of the atmosphere, and an increase in the low-level cloud cover through the second aerosol indirect effect. The trend in low-level cloud lifetime due to aerosols is quantified to 0.5 min day^–1 decade^–1 for the simulation period. The different changes in high (decrease) and low-level (increase) cloudiness due to the response of cloud processes to aerosols impact shortwave radiation in a contrariwise manner, and the net effect is slightly positive. The total aerosol effect including the aerosol direct and first indirect effects remains strongly negative.     

Carbonaceous materials in size-segregated atmospheric aerosols from urban and coastal-rural areas at the Western European Coast

A high-volume cascade impactor, equipped with a PM10 inlet, was used to collect size-segregated aerosol samples during the summer of 2004 at two Portuguese locations: a coastal-rural area (Moitinhos) and an urban area (Oporto). Concentrations of airborne particulate matter (PM), total carbon (TC), organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were determined for the following particle size ranges: < 0.49, 0.49–0.95, 0.95–3.0, and 3.0–10 µm. The total PM mass concentrations at the urban and coastal-rural sites ranged from 22.8 to 79.6 μg m^− 3 and 19.9 to 28.2 μg m^− 3, respectively, and more than 56% of the total aerosol mass was found in the fractions below 3.0 μm. At both locations the highest concentrations of OC and EC were found in the submicrometer size range. The regional variability for the OC and EC concentrations, with the highest concentrations being found in the urban area, was related to the contribution of local primary sources (mostly traffic emissions). It was also verified an enrichment of the small size particles in WSOC, representing on average 37.3(± 12.4)% and 59.7(± 18.0)% of OC in the very fine aerosol at the coastal-rural and urban areas, respectively. The amount of secondary OC calculated by the minimum OC/EC ratio method indicates that secondary organic aerosol formation was important throughout the study at both sites. The obtained results suggest that long-range transport and favourable summer conditions for photochemical oxidation are key factors determining secondary OC formation in the coastal-rural and urban areas. The ultraviolet absorption properties of the chromophoric constituents of the WSOC fractions were also different among the different particle size ranges and also between the two sampling locations, thus suggesting the strong impact of the diverse emission sources into the composition of the size-segregated organic aerosol.