Comparison of the levels of organic, elemental and inorganic carbon in particulate matter in six urban environments in Europe

International audienceA series of 7-week sampling campaigns were conducted in urban background sites in the six European cities as follows: Duisburg 4 October?21 November 2002 (autumn), Prague 29 November 2002?16 January 2003 (winter), Amsterdam 24 January?13 March 2003 (winter), Helsinki 21 March?12 May 2003 (spring), Barcelona 28 March?19 May 2003 (spring) and Athens 2 June?21 July 2003 (summer). The campaigns were scheduled to include seasons of local public health concern due to high PM concentrations or findings in previously conducted epidemiological studies. Aerosol samples were collected in parallel with two identical virtual impactors (VI), which divide air PM into two size fractions, PM2.5 and PM2.5-10. The filter samples were analysed with a microbalance, an energy dispersive X-ray fluorescence (ED-XRF), an ion chromatograph (IC) and a thermo-optical carbon analyser (TOA). The PM2.5 and PM2.5-10 campaign means ranged 8.3?29.6 µg m-3 and 5.4?28.7 µg m-3, respectively. The ''wet and cool'' seasons favoured low coarse PM concentration and high fine PM concentration, whereas the spring and summer led to low fine and high coarse PM concentrations. The contribution of particulate organic matter (POM) to PM2.5-10 was highest (27%) in Prague and the lowest (10%) in Barcelona, while those to PM2.5 were generally higher, ranging from 21% in Barcelona to 54% in Prague. The contribution of elemental carbon (EC) to PM2.5-10 were relatively low (1?6%) in all the six European cities but it contributed somewhat higher (5?9%) to PM2.5. The differences are most likely due to variable contributions of local emission sources and seasonal factors such as domestic heating, vehicle exhausts and photochemical reactions. Carbonate, which interferes with carbon analysis by evolving stage at 900°C, was detected in the coarse particles of Athens and Barcelona and it could be separated reliably from OC by a simple integrating method. The calcium carbonate in Athens and Barcelona accounted for 56% and 11% of coarse PM masses, respectively. Carbonate was not found in other cities or in PM2.5. The mean PM2.5 mass portions of five OC thermal fractions (OC1, OC2, OC3, OC4 and OCP) varied in the range 26?33%, 6?10%, 7?10%, 9?22% and 29?50%, respectively, in six cities. The differences in the mass portion profiles were relatively small between the cities

Organic, elemental and inorganic carbon in particulate matter of six urban environments in Europe

International audienceA series of 7-week sampling campaigns were conducted in urban background sites of six European cities as follows: Duisburg (autumn), Prague (winter), Amsterdam (winter), Helsinki (spring), Barcelona (spring) and Athens (summer). The campaigns were scheduled to include seasons of local public health concern due to high particulate concentrations or findings in previously conducted epidemiological studies. Aerosol samples were collected in parallel with two identical virtual impactors that divide air particles into fine (PM2.5) and coarse (PM2.5-10) size ranges. From the collected filter samples, elemental (EC) and organic (OC) carbon contents were analysed with a thermal-optical carbon analyser (TOA); total Ca, Ti, Fe, Si, Al and K by energy dispersive X-ray fluorescence (ED-XRF); As, Cu, Ni, V, and Zn by inductively coupled plasma mass spectrometry (ICP/MS); Ca2+, succinate, malonate and oxalate by ion chromatography (IC); and the sum of levoglucosan+galactosan+mannosan (?MA) by liquid chromatography mass spectrometry (LC/MS). The campaign means of PM2.5 and PM2.5-10 were 8.3-29.6 µg m-3 and 5.4-28.7 µg m-3, respectively. The contribution of particulate organic matter (POM) to PM2.5 ranged from 21% in Barcelona to 54% in Prague, while that to PM2.5-10 ranged from 10% in Barcelona to 27% in Prague. The contribution of EC was higher to PM2.5 (5-9%) than to PM2.5-10 (1-6%) in all the six campaigns. Carbonate (C(CO3), that interferes with the TOA analysis, was detected in PM2.5-10 of Athens and Barcelona but not elsewhere. It was subtracted from the OC by a simple integration method that was validated. The CaCO3 accounted for 55% and 11% of PM2.5-10 in Athens and Barcelona, respectively. It was anticipated that combustion emissions from vehicle engines affected the POM content in PM2.5 of all the six sampling campaigns, but a comparison of mass concentration ratios of the selected inorganic and organic tracers of common sources of organic material to POM suggested also interesting differences in source dominance during the campaign periods: Prague (biomass and coal combustion), Barcelona (fuel oil combustion, secondary photochemical organics) and Athens (secondary photochemical organics). The on-going toxicological studies will clarify the health significance of these findings

The contributions of snow, fog, and dry deposition to the summer flux of anions and cations at Summit, Greenland

Experiments were performed during the period May–July of 1993 at Summit, Greenland. Aerosol mass size distributions as well as daily average concentrations of several anionic and cationic species were measured. Dry deposition velocities for SO42− were estimated using surrogate surfaces (symmetric airfoils) as well as impactor data. Real-time concentrations of particles greater than 0.5 μm and greater than 0.01 μm were measured. Snow and fog samples from nearly all of the events occurring during the field season were collected. Filter sampler results indicate that SO42− is the dominant aerosol anion species, with Na+, NH4+, and Ca2+being the dominant cations. Impactor results indicate that MSA and SO42− have similar mass size distributions. Furthermore, MSA and SO42− have mass in both the accumulation and coarse modes. A limited number of samples for NH4+ indicate that it exists in the accumulation mode. Na, K, Mg, and Ca exist primarily in the coarse mode. Dry deposition velocities estimated from impactor samples and a theory for dry deposition to snow range from 0.017 cm/s +/− 0.011 cm/s for NH4+ to 0.110 cm/s +/− 0.021 cm/s for Ca. SO42− dry deposition velocity estimates using airfoils are in the range 0.023 cm/s to 0.062 cm/s, as much as 60% greater than values calculated using the airborne size distribution data. The rough agreement between the airfoil and impactor-estimated dry deposition velocities suggests that the airfoils may be used to approximate the dry deposition to the snow surface. Laser particle counter (LPC) results show that particles \u3e 0.5 μm in diameter efficiently serve as nuclei to form fog droplets. Condensation nuclei (CN) measurements indicate that particles \u3c 0.5 μm are not as greatly affected by fog. Furthermore, impactor measurements suggest that from 50% to 80% of the aerosol SO42−serves as nuclei for fog droplets. Snow deposition is the dominant mechanism transporting chemicals to the ice sheet. For NO3−, a species that apparently exists primarily in the gas phase as HNO3(g), 93% of the seasonal inventory (mass of a deposited chemical species per unit area during the season) is due to snow deposition, which suggests efficient scavenging of HNO3(g) by snowflakes. The contribution of snow deposition to the seasonal inventories of aerosols ranges from 45% for MSA to 76% for NH4+. The contribution of fog to the seasonal inventories ranges from 13% for Na+ and Ca2+ to 26% and 32% for SO42− and MSA. The dry deposition contribution to the seasonal inventories of the aerosol species is as low as 5% for NH4+ and as high as 23% for MSA. The seasonal inventory estimations do not take into consideration the spatial variability caused by blowing and drifting snow. Overall, results indicate that snow deposition of chemical species is the dominant flux mechanism during the summer at Summit and that all three deposition processes should be considered when estimating atmospheric concentrations based on ice core chemical signals

Size-segregated mass distributions of aerosols over Eastern Mediterranean: seasonal variability and comparison with AERONET columnar size-distributions

International audienceThis work provides long-term (2004?2006) size segregated measurements of aerosol mass at a remote coastal station in the southern Europe, with the use of size-selective samplings (SDI impactor). Seven distinct modes were identified in the range 0?10 µm and the dominant were the "Accumulation 1" (0.25?0.55 µm) and the "Coarse 2" (3?7 µm) modes. The seasonal characteristics of each mode were thoroughly studied and different sources for submicron and supermicron particles were identified, the first being related to local/regional and transported pollution with maximum in summer and the latter to dust from deserted areas in Northern Africa maximizing in spring. On average, PM2.5 and PM1 accounted for 60% and 40% of PM10 mass, respectively.The representativity of the ground-based measurements for the total column was also investigated by comparing the measured aerosol mass distributions with the AERONET volume size distribution data. Similar seasonal patterns were revealed and AERONET was found adequate for the estimation of background levels of both fine and coarse particles near surface, with certain limitations in the case of pollution or dust abrupt episodes due to its low temporal coverage

Black carbon concentration trends in Helsinki during 1996?2005

International audienceThe black carbon (BC) concentration trends were studied during ten years in Helsinki, Finland. Measurements were made in three campaigns between 1996 and 2005 at an urban area locating two kilometres from the centre of Helsinki. The first campaign was from November 1996 to June 1997, the second from September 2000 to May 2001 and the third from March 2004 to October 2005. In this study, only data from winter and spring months was analysed. The effect of traffic and meteorological variables on the measured BC concentrations was studied by means of a multiple regression analysis, where the meteorological data was obtained from a meteorological pre-processing model (MPP-FMI). During the ten years, the campaign median BC concentrations were found to decrease slightly from 1.11 to 1.00 ?g m?3. The lowest campaign median concentration (0.93 ?g m?3) was measured during the second campaign in 2000?2001, when also the lowest traffic rates were measured. The strongest decrease between campaigns 1 and 3 was observed during weekday daytimes, when the traffic rates are highest. The variables affecting the measured BC concentrations most were traffic, wind speed and mixing height. On weekdays, traffic had clearly the most important influence and on weekends the effect of wind speed diluted the effect of traffic. The affecting variables and their influence on the BC concentration were similar in winter and spring. The separate examination of the three campaigns showed that the effect of traffic on the BC concentrations had decreased during the studied years. This reduction was caused by cleaner emissions from vehicles, since between years 1996 and 2005 the traffic rates had increased. A rough estimate gave that vehicle number-scaled BC mass concentrations have decreased from 0.0028 to 0.0020 ?g m?3 between campaigns 1 and 3

Temporal variations in black carbon concentrations with different time scales in Helsinki during 1996?2005

International audienceVariations in black carbon (BC) concentrations over different timescales, including annual, weekly and diurnal changes, were studied during ten years in Helsinki, Finland. Measurements were made in three campaigns between 1996 and 2005 at an urban area locating two kilometres of the centre of Helsinki. The first campaign took place from November 1996 to June 1997, the second from September 2000 to May 2001 and the third from March 2004 to October 2005. A detailed comparison between the campaigns was only made for winter and spring months when data from all campaigns existed. The effect of traffic and meteorological variables on the measured BC concentrations was studied by means of a multiple regression analysis, where the meteorological data was obtained from a meteorological pre-processing model (MPP-FMI). The BC concentrations showed annual pattern with maxima in fall and late winter due to the weakened mixing and enhanced emissions. Between 1996 and 2005, the campaign median BC concentrations decreased slightly from 1.11 to 1.00 ?g m?3. The lowest campaign median concentration (0.93 ?g m?3) was measured during the second campaign in 2000?2001, when also the lowest traffic rates were measured. The strongest decrease between Campaigns 1 and 3 was observed on weekday daytimes, when also the traffic rates are highest. The variables affecting the measured BC concentrations most were traffic, wind speed and mixing height. On weekdays, traffic had clearly the most important influence before the wind speed and on weekends the effect of wind speed diluted the effect of traffic. The affecting variables and their influence on the BC concentrations were similar in winter and spring. The separate examination of the three campaigns showed that the effect of traffic on the BC concentrations had decreased during the studied years. This reduction was caused by lower emitting vehicles, since between years 1996 and 2005 the traffic rates had increased

Changes in background aerosol composition in Finland during polluted and clean periods studied by TEM/EDX individual particle analysis

Aerosol samples were collected at a rural background site in southern Finland in May 2004 during pollution episode ( PM1 similar to 16 mu g m(-3), backward air mass trajectories from south-east), intermediate period (PM1 similar to 5 mu g m(-3), backtrajectories from north-east) and clean period (PM1 similar to 2 mu g m(-3), backtrajectories from northwest/ north). The elemental composition, morphology and mixing state of individual aerosol particles in three size fractions were studied using transmission electron microscopy (TEM) coupled with energy dispersive X-ray (EDX) microanalyses. The TEM/EDX results were complemented with the size-segregated bulk chemical measurements of selected ions and organic and elemental carbon. Many of the particles in PM0.2-1 and PM1-3.3 size fractions were strongly internally mixed with S, C and/or N. The major particle types in PM0.2-1 samples were 1) soot and 2) ( ammonium) sulphates and their mixtures with variable amounts of C, K, soot and/or other inclusions. Number proportions of those two particle groups in PM0.2-1 samples were 0 - 12% and 83 - 97%, respectively. During the pollution episode, the proportion of Ca-rich particles was very high ( 26 - 48%) in the PM1- 3.3 and PM3.3-11 samples, while the PM0.2-1 and PM1- 3.3 samples contained elevated proportions of silicates ( 22 - 33%), metal oxides/hydroxides ( 1 - 9%) and tar balls ( 1 - 4%). These aerosols originated mainly from polluted areas of Eastern Europe, and some open biomass burning smoke was also brought by long-range transport. During the clean period, when air masses arrived from the Arctic Ocean, PM1- 3.3 samples contained mainly sea salt particles ( 67 - 89%) with a variable rate of Cl substitution ( mainly by NO3-). During the intermediate period, the PM1- 3.3 sample contained porous (sponge-like) Na-rich particles (35%) with abundant S, K and O. They might originate from the burning of wood pulp wastes of paper industry. The proportion of biological particles and C-rich fragments ( probably also biological origin) were highest in the PM3.3-11 samples ( 0 - 81% and 0 - 22%, respectively). The origin of different particle types and the effect of aging processes on particle composition and their hygroscopic and optical properties are discussed.Aerosol samples were collected at a rural background site in southern Finland in May 2004 during pollution episode ( PM1 similar to 16 mu g m(-3), backward air mass trajectories from south-east), intermediate period (PM1 similar to 5 mu g m(-3), backtrajectories from north-east) and clean period (PM1 similar to 2 mu g m(-3), backtrajectories from northwest/ north). The elemental composition, morphology and mixing state of individual aerosol particles in three size fractions were studied using transmission electron microscopy (TEM) coupled with energy dispersive X-ray (EDX) microanalyses. The TEM/EDX results were complemented with the size-segregated bulk chemical measurements of selected ions and organic and elemental carbon. Many of the particles in PM0.2-1 and PM1-3.3 size fractions were strongly internally mixed with S, C and/or N. The major particle types in PM0.2-1 samples were 1) soot and 2) ( ammonium) sulphates and their mixtures with variable amounts of C, K, soot and/or other inclusions. Number proportions of those two particle groups in PM0.2-1 samples were 0 - 12% and 83 - 97%, respectively. During the pollution episode, the proportion of Ca-rich particles was very high ( 26 - 48%) in the PM1- 3.3 and PM3.3-11 samples, while the PM0.2-1 and PM1- 3.3 samples contained elevated proportions of silicates ( 22 - 33%), metal oxides/hydroxides ( 1 - 9%) and tar balls ( 1 - 4%). These aerosols originated mainly from polluted areas of Eastern Europe, and some open biomass burning smoke was also brought by long-range transport. During the clean period, when air masses arrived from the Arctic Ocean, PM1- 3.3 samples contained mainly sea salt particles ( 67 - 89%) with a variable rate of Cl substitution ( mainly by NO3-). During the intermediate period, the PM1- 3.3 sample contained porous (sponge-like) Na-rich particles (35%) with abundant S, K and O. They might originate from the burning of wood pulp wastes of paper industry. The proportion of biological particles and C-rich fragments ( probably also biological origin) were highest in the PM3.3-11 samples ( 0 - 81% and 0 - 22%, respectively). The origin of different particle types and the effect of aging processes on particle composition and their hygroscopic and optical properties are discussed.Aerosol samples were collected at a rural background site in southern Finland in May 2004 during pollution episode ( PM1 similar to 16 mu g m(-3), backward air mass trajectories from south-east), intermediate period (PM1 similar to 5 mu g m(-3), backtrajectories from north-east) and clean period (PM1 similar to 2 mu g m(-3), backtrajectories from northwest/ north). The elemental composition, morphology and mixing state of individual aerosol particles in three size fractions were studied using transmission electron microscopy (TEM) coupled with energy dispersive X-ray (EDX) microanalyses. The TEM/EDX results were complemented with the size-segregated bulk chemical measurements of selected ions and organic and elemental carbon. Many of the particles in PM0.2-1 and PM1-3.3 size fractions were strongly internally mixed with S, C and/or N. The major particle types in PM0.2-1 samples were 1) soot and 2) ( ammonium) sulphates and their mixtures with variable amounts of C, K, soot and/or other inclusions. Number proportions of those two particle groups in PM0.2-1 samples were 0 - 12% and 83 - 97%, respectively. During the pollution episode, the proportion of Ca-rich particles was very high ( 26 - 48%) in the PM1- 3.3 and PM3.3-11 samples, while the PM0.2-1 and PM1- 3.3 samples contained elevated proportions of silicates ( 22 - 33%), metal oxides/hydroxides ( 1 - 9%) and tar balls ( 1 - 4%). These aerosols originated mainly from polluted areas of Eastern Europe, and some open biomass burning smoke was also brought by long-range transport. During the clean period, when air masses arrived from the Arctic Ocean, PM1- 3.3 samples contained mainly sea salt particles ( 67 - 89%) with a variable rate of Cl substitution ( mainly by NO3-). During the intermediate period, the PM1- 3.3 sample contained porous (sponge-like) Na-rich particles (35%) with abundant S, K and O. They might originate from the burning of wood pulp wastes of paper industry. The proportion of biological particles and C-rich fragments ( probably also biological origin) were highest in the PM3.3-11 samples ( 0 - 81% and 0 - 22%, respectively). The origin of different particle types and the effect of aging processes on particle composition and their hygroscopic and optical properties are discussed.Peer reviewe

Characterization of submicron aerosol chemical composition and sources in the coastal area of Central Chile

Chemical characteristics and the sources of submicron particles (<1 mu m in diameter) were investigated in Valle Alegre, the coastal area of Central Chile. The chemical composition of particles was studied by using a Soot particle Aerosol Mass Spectrometer and Multi-Angle Absorption Photometer. Submicron particles were dominated by organics (42% of mass) and sulfate (39% of mass) while the mass fractions of ammonium, nitrate and black carbon were much smaller (13, 2 and 4% of mass, respectively). Additionally, several metals (V, Zn, Fe, Cd, Cu, K, Na and Mg) were detected in submicron particles and also some of their inorganic salts (e.g. NaCl+, MgCl2+, CaCl2+, KCl+ and KNO3+). The sources of particles were examined by using Positive Matrix Factorization (PMF). Organic aerosol (OA) was divided into five factors by using PMF; hydrocarbon-like OA (HOA), biomass burning OA (BBOA), low-volatility oxygenated OA (LV-OOA), semi-volatile OA (SV-OOA) and marine oxygenated OOA (MOOA), Oxygenated factors (LV-OOA; SV-OOA and MOOA) comprised 75% of total OA with LV-OOA being the dominant factor (38% of OA). Sulfate had two major sources in Valle Alegre; similar to 70% of sulfate was related to anthropogenic sources through the oxidation of gas phase SO2 whereas similar to 24% of sulfate was associated with biogenic origin related to the oxidation of dimethyl sulfide in the marine environment. Regarding total submicron particle mass (campaign-average 9.5 mu g m(-3)), the contribution of anthropogenic sources was at least as large as that of biogenic origin.Peer reviewe

Chemical composition of boundary layer aerosol over the Atlantic Ocean and at an Antarctic site

International audienceAerosol chemical composition was measured over the Atlantic Ocean in November?December 1999 and at the Finnish Antarctic research station Aboa in January 2000. The concentrations of all anthropogenic aerosol compounds decreased clearly from north to south. An anthropogenic influence was still evident in the middle of the tropical South Atlantic, background values were reached south of Cape Town. Chemical mass balance was calculated for high volume filter samples (Dp80% in the Southern Ocean, and 10% in most samples, also at Aboa. The correlation of biomass-burning-related aerosol components with 210Pb was very high compared with that between nss calcium and 210Pb which suggests that 210Pb is a better tracer for biomass burning than for Saharan dust. The ratio of the two clear tracers for biomass burning, nss potassium and oxalate, was different in European and in African samples, suggesting that this ratio could be used as an indicator of biomass burning type. The concentrations of continent-related particles decreased exponentially with the distance from Africa. The shortest half-value distance, ~100 km, was for nss calcium. The half-value distance of particles that are mainly in the submicron particles was ~700±200 km. The MSA to nss sulfate ratio, R, increased faster than MSA concentration with decreasing anthropogenic influence, indicating that the R increase could largely be explained by the decrease of anthropogenic sulfate

Size distributions, sources and source areas of water-soluble organic carbon in urban background air

International audienceThis paper represents the results of one year long measurement period of the size distributions of water-soluble organic carbon (WSOC), inorganic ions and gravimetric mass of particulate matter. Measurements were done at an urban background station (SMEAR III) by using a micro-orifice uniform deposit impactor (MOUDI). The site is located in northern European boreal region in Helsinki, Finland. The WSOC size distribution measurements were completed with the chemical analysis of inorganic ions, organic carbon (OC) and monosaccharide anhydrides from the filter samples. During the measurements gravimetric mass in the MOUDI collections varied between 3.4 and 55.0 ?g m?3 and the WSOC concentration was between 0.3 and 7.4 ?g m?3. On average, water-soluble particulate organic matter (WSPOM, WSOC multiplied by 1.6) comprised 25±7.7% and 7.5±3.4% of aerosol PM1 mass and the PM1?10 mass, respectively. Inorganic ions contributed 33±12% and 28±19% of the analyzed PM1 and PM1?10 aerosol mass. Five different aerosol categories corresponding to different sources or source areas were identified (long-range transport aerosols, biomass burning aerosols from wild land fires and from small-scale wood combustion, aerosols originating from marine areas and from the clean arctic areas). Clear differences in WSOC concentrations and size distributions originating from different sources or source areas were observed, although there are also many other factors which might affect the results. E.g. the local conditions and sources of volatile organic compounds (VOCs) and aerosols as well as various transformation processes are likely to have an impact on the measured aerosol composition. Using the source categories, it was identified that especially the oxidation products of biogenic VOCs in summer had a clear effect on WSOC concentrations