Size-resolved sulfate and ammonium measurements in marine boundary layer over the North and South Pacific

Marine background levels of non-sea-salt- (nss-) SO₄²⁻ (5.0–9.7 neq m⁻³), NH₄⁺ (2.1–4.4 neq m⁻³) and elemental carbon (EC) (40–80 ngC m⁻³) in aerosol samples were measured over the equatorial and South Pacific during a cruise by the R/V Hakuho-maru from November 2001 to March 2002. High concentrations of nss-SO₄²⁻ (47–94 neq m⁻³), NH₄⁺ (35–94 neq m⁻³) and EC (130–460 ngC m⁻³) were found in the western North Pacific near the coast of the Asian continent under the influence of the Asian winter monsoon. Particle size distributions of ionic components showed that the equivalent concentrations of nss-SO₄²⁻ were balanced with those of NH₄⁺ in the size range of 0.06<D<0.22 μm, whereas the concentration ratios of NH₄⁺ to nss-SO₄²⁻ in the size range of D>0.22 μm were decreased with increase in particle size. We estimated the source contributions of those aerosol components in the marine background air over the equatorial and South Pacific. Biomass burning accounted for the large fraction (80–98% in weight) of EC and the minor fraction (2–4% in weight) of nss-SO₄²⁻. Marine biogenic source accounted for several tens percents of NH₄⁺ and nss-SO₄²⁻. In the accumulation mode, 70% of particle number existed in the size range of 0.1<D<0.2 μm. In the size rage of 0.06<D<0.22 μm, the dominant aerosol component of (NH₄)₂SO₄ would be mainly derived from the marine biogenic sources.     

Aerosol scattering properties in northern China

The aerosol scattering properties were investigated at two continental sites in northern China in 2004. Aerosol light scattering coefficient (σ_sp) at 525 nm, PM₁₀, and aerosol mass scattering efficiencies (α) at Dunhuang had a mean value of 165.1±148.8 M m⁻¹, 157.6±270.0 μg m⁻³, and 2.30±3.41 m² g⁻¹, respectively, while these values at Dongsheng were, respectively, 180.2±151.9 M m⁻¹, 119.0±112.9 μg m⁻³, and 1.87±1.41 m² g⁻¹. There existed a seasonal variability of aerosol scattering properties. In spring, at Dunhuang PM₁₀, σ_sp, and α were 184.1±211.548 μg m⁻³, 126.3±89.6 M m⁻¹, and 1.05±0.97 m² g⁻¹, respectively, and these values at Dongsheng were 146.4±142.1 μg m⁻³, 183.4±81.7 M m⁻¹, and 1.98±1.52 m² g⁻¹, respectively. However, in winter at Dunhuang PM₁₀, σ_sp, and α were 158.1±261.4 μg m⁻³, 303.3±165.2 M m⁻¹, and 3.17±1.93 m² g⁻¹, respectively, and these values at Dongsheng were 155.7±170.1 μg m⁻³, 304.4±158.1 M m⁻¹, and 2.90±1.72 m² g⁻¹, respectively. σ_sp and α in winter were higher than that in spring at both the sites, which coincides with the characteristics of dust aerosol and pollution aerosol. Overall, the dominant aerosol types in spring and winter at both sites in northern China are dust aerosol and pollution aerosol, respectively.     

Water-soluble organic nitrogen (WSON) in size-segregated atmospheric particles over the Eastern Mediterranean

Atmospheric water-soluble organic nitrogen (WSON) was determined on size-segregated aerosol particles collected during a two years period (2005–2006) in a remote marine location in the Eastern Mediterranean (Finokalia, Crete island). Average concentration of WSON was 5.5 ± 3.9 nmol m^?3 and 11.6 ± 14.0 nmol m^?3 for coarse (PM_1.3-10) and fine (PM_1.3) mode respectively, corresponding to 13% of Total Dissolved Nitrogen (TDN) in both modes. Air masses origin and correlation with tracers of natural and anthropogenic sources indicate that combustion process (biomass burning and fossil fuel) and African dust play an important role in regulating levels of WSON in both coarse and fine aerosol fractions. Chemical speciation of organic nitrogen pool was attempted by analyzing 47 fine aerosol samples (PM₁) for 17 free amino acids (N-FAA), dimethylamine (DMA) and trimethylamine (TMA). The average concentration of N-FAA was 0.5 ± 0.5 nmol m^?3, while the average concentration of DMA was 0.2 ± 0.8 nmol m^?3, TMA was below detection limit. The percentage contribution of N-FAA and DMA to WSON was 2.1 ± 2.3% and 0.9 ± 3.4%, respectively.     

Characterization of aerosol over the Northern South China Sea during two cruises in 2003

Atmospheric transport of trace elements has been found to be an important pathway for their input to the ocean. TSP, PM10, and PM2.5 aerosol samples were collected over the Northern South China Sea in two cruises in 2003 to estimate the input of aerosol from continent to the ocean. About 23 elements and 14 soluble ions in aerosol samples were measured. The average mass concentration of TSP in Cruise I in January (78 μg m⁻³) was ∼twice of that in Cruise II in April (37 μg m⁻³). Together with the crustal component, heavy metals from pollution sources over the land (especially from the industry and automobiles in Guangzhou) were transported to and deposited into the ocean. The atmospheric MSA concentrations in PM2.5 (0.048 μg m⁻³ in Cruise I and 0.043 μg m⁻³ in Cruise II) over Northern South China Sea were comparable to those over other coastal regions. The ratio of non-sea-salt (NSS)-sulfate to MSA is 103-655 for Cruise I and 15-440 for Cruise II in PM2.5 samples, which were much higher than those over remote oceans. The estimated anthropogenic sulfate accounts for 83–98% in Cruise I and 63–95% in Cruise II of the total NSS-sulfate. Fe (II) concentration in the aerosols collected over the ocean ranged from 0.1 to 0.9 μg m⁻³, accounting for 16–82% of the total iron in the aerosol, which could affect the marine biogeochemical cycle greatly.     

Multi-year hourly PM2.5 carbon measurements in New York: Diurnal,day of week and seasonal patterns

Multi-year hourly measurements of PM_2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m^?3 with peak hourly values of several μg m^?3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO_x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m^?3 with maximum hourly concentrations of 7–11 μg m^?3 predominantly in summer or winter months. OC concentrations generally correlated with PM_2.5 total mass and aerosol sulfate and with NO_x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO_x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.     

Quantification of Saharan dust contribution to PM10 concentrations over Italy during 2003–2005

Italy is frequently affected by Saharan dust intrusions, which result in high PM₁₀ concentrations in the atmosphere and can cause the exceedances of the PM₁₀ daily limits (50 μg m^?3) set by the European Union (EU/2008/50). The estimate of African dust contribution to PM₁₀ concentrations is therefore a key issue in air quality assessment and policy formulation. This study presents a first identification of Saharan dust outbreaks as well as an estimate of the African dust contribution to PM₁₀ concentrations during the period 2003–2005 over Italy. The identification of dust events has been carried out by looking at different sources of information such as monitoring network observations, satellite images, ground measurements of aerosol optical properties, dust model simulations and air mass backward trajectory analysis. The contribution of Saharan dust to PM₁₀ monthly concentrations has been estimated at seven Italian locations. The results are both spatially (with station) and temporally (with month and year) variable, as a consequence of the variability of the meteorological conditions. However, excluding the contribution of severe dust events (21st February 2004, 25th–28th September 2003, 23rd–27th March 2005), the monthly contribution of dust varies approximately between 1 μg m^?3 and 10 μg m^?3 throughout year 2005 and between 1 μg m^?3 and 8 μg m^?3 throughout year 2003. In 2004 the dust concentration is lower than 2003 and 2005 (<5 μg m^?3 at all sites). The reduction in the number of daily exceedances of the limit value (50 μg m^?3) after subtraction of the dust contribution is also calculated at each station: it varies with station between 20% and 50% in 2005 and between 5% and 25% in 2003 and 2004.     

Aqueous-phase reactive uptake of dicarbonyls as a source of organic aerosol over eastern North America

We use a global 3-D atmospheric chemistry model (GEOS-Chem) to simulate surface and aircraft measurements of organic carbon (OC) aerosol over eastern North America during summer 2004 (ICARTT aircraft campaign), with the goal of evaluating the potential importance of a new secondary organic aerosol (SOA) formation pathway via irreversible uptake of dicarbonyl gases (glyoxal and methylglyoxal) by aqueous particles. Both dicarbonyls are predominantly produced in the atmosphere by isoprene, with minor contributions from other biogenic and anthropogenic precursors. Dicarbonyl SOA formation is represented by a reactive uptake coefficient γ = 2.9 × 10^?3 and takes place mainly in clouds. Surface measurements of OC aerosol at the IMPROVE network in the eastern U.S. average 2.2 ± 0.7 μg C m^?3 for July–August 2004 with little regional structure. The corresponding model concentration is 2.8 ± 0.8 μg C m^?3, also with little regional structure due to compensating spatial patterns of biogenic, anthropogenic, and fire contributions. Aircraft measurements of water-soluble organic carbon (WSOC) aerosol average 2.2 ± 1.2 μg C m^?3 in the boundary layer (<2 km) and 0.9 ± 0.8 μg C m^?3 in the free troposphere (2–6 km), consistent with the model (2.0 ± 1.2 μg C m^?3 in the boundary layer and 1.1 ± 1.0 μg C m^?3 in the free troposphere). Source attribution for the WSOC aerosol in the model boundary layer is 27% anthropogenic, 18% fire, 28% semi-volatile SOA, and 27% dicarbonyl SOA. In the free troposphere it is 13% anthropogenic, 37% fire, 23% semi-volatile SOA, and 27% dicarbonyl SOA. Inclusion of dicarbonyl SOA doubles the SOA contribution to WSOC aerosol at all altitudes. Observed and simulated correlations of WSOC aerosol with other chemical variables measured aboard the aircraft suggest a major SOA source in the free troposphere compatible with the dicarbonyl mechanism.     

Absence of trends in relative risk estimates for the association between Black Smoke and daily mortality over a 34 years period in The Netherlands

A major issue in air pollution epidemiology is whether the associations that are found in the statistical analyses on the health effects of air pollution reflect real causal associations of single components or mixtures thereof, or just reflect statistical associations that are mainly the result of the high correlation between the separate components, one of them being the true causal factor.In a previous analysis on the relationship between daily SO₂ levels and daily mortality in The Netherlands [Buringh, E., Fischer, P., Hoek, G., 2000. Is SO₂ a causative factor for the PM-associated mortality risks in The Netherlands? Inhal. Toxicol. 12 (Suppl. 1), 55–60.], it was shown that the statistical significant association between daily variation in SO₂ and daily mortality did not reflect a causal relation. Black Smoke levels in The Netherlands have decreased 4-fold during the 34 years in the period 1972–2006 (annual average from 27 μg m^?3 to 6 μg m^?3). This large decrease in concentrations enabled us to use the same approach for this component as was done earlier for SO₂ to assess whether a decreasing trend in Black Smoke levels in The Netherlands is associated with an increasing trend in mortality relative risks or not.We used daily averaged Black Smoke (BS) data from 1972 to 2006. In the first two decades (1970–1990) only sparse data were available. Based on the availability of the data, we selected data from 1972 to 1974 and from 1982 to 1984 because during these two periods continuous daily measurement series were available. For the later years (1989–2006) data covering the whole of The Netherlands were available, giving a total of 24 years of daily data. Data on daily total mortality counts (excluding external causes), cardiovascular mortality and respiratory mortality for the whole population of The Netherlands were analyzed with regard to daily Black Smoke levels using generalized additive Poisson regression models (GAM). Period specific relative risk estimates were compared and differences in estimates between periods were evaluated.We found no consistent increase in relative risks for daily total and cause-specific mortality over time, despite the decreasing trend in the Black Smoke levels in The Netherlands. Average relative risks for total mortality varied over the different periods from 0.997 per 10 μg m^?3 daily Black Smoke to 1.010 per 10 μg m^?3. Average relative risks for cardiovascular mortality varied from 0.988 per 10 μg m^?3 to 1.010 per 10 μg m^?3 and for respiratory mortality from 1.000 to 1.010 per 10 μg m^?3. For weekly averaged concentrations the average relative risks for total mortality varied over the different periods from 1.004 per 10 μg m^?3 Black Smoke to 1.018 per 10 μg m^?3. Average relative risks for cardiovascular mortality varied from 1.003 per 10 μg m^?3 to 1.016 per 10 μg m^?3 and for respiratory mortality from 1.000 to 1.050 per 10 μg m^?3.The result of our analyses suggests that Black Smoke cannot be excluded as a potential causal agent because relative risks over time show no increasing trend despite the decreasing trend in Black Smoke concentrations.     

Concentration-dependent NH3 deposition processes for moorland plant species with and without stomata

Currently, in operational modelling of NH₃ deposition a fixed value of canopy resistance (R_c) is generally applied, irrespective of the plant species and NH₃ concentration. This study determined the effect of NH₃ concentration on deposition processes to individual moorland species. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to Deschampsia cespitosa (L.) Beauv., Calluna vulgaris (L.) Hull, Eriophorum vaginatum L., Cladonia spp., Sphagnum spp., and Pleurozium schreberi (Brid.) Mitt. Measurements were conducted across a wide range of NH₃ concentrations (1–140 μg m⁻³).NH₃ concentration directly affects the deposition processes to the vegetation canopy, with R_c, and cuticular resistance (R_w) increasing with increasing NH₃ concentration, for all the species and vegetation communities tested. For example, the R_c for C. vulgaris increased from 14 s m⁻¹ at 2 μg m⁻³ to 112 s m⁻¹ at 80 μg m⁻³. Diurnal variations in NH₃ uptake were observed for higher plants, due to stomatal uptake; however, no diurnal variations were shown for non-stomatal plants. R_c for C. vulgaris at 80 μg m⁻³ was 66 and 112 s m⁻¹ during day and night, respectively. Differences were found in NH₃ deposition between plant species and vegetation communities: Sphagnum had the lowest R_c (3 s m⁻¹ at 2 μg m⁻³ to 23 at 80 μg m⁻³), and D. cespitosa had the highest nighttime value (18 s m⁻¹ at 2 μg m⁻³ to 197 s m⁻¹ at 80 μg m⁻³).     

Carbon content of atmospheric aerosols in a residential area during the wood combustion season in Sweden

Carbonaceous aerosol particles were observed in a residential area with wood combustion during wintertime in Northern Sweden. Filter samples were analyzed for elemental carbon (EC) and organic carbon (OC) content by using a thermo-optical transmittance method. The light-absorbing carbon (LAC) content was determined by employing a commercial Aethalometer and a custom-built particle soot absorption photometer. Filter samples were used to convert the optical signals to LAC mass concentrations. Additional total PM₁₀ mass concentrations and meteorological parameters were measured. The mean and standard deviation mass concentrations were 4.4±3.6 μg m⁻³ for OC, and 1.4±1.2 μg m⁻³ for EC. On average, EC accounted for 10.7% of the total PM₁₀ and the contribution of OC to the total PM₁₀ was 35.4%. Aethalometer and custom-built PSAP measurements were highly correlated (R²=0.92). The hourly mean value of LAC mass concentration was 1.76 μg m⁻³ (median 0.88 μg m⁻³) for the winter 2005–2006. This study shows that the custom-built PSAP is a reliable alternative for the commercial Aethalometer with the advantage of being a low-cost instrument.     

Five years of formaldehyde and acetaldehyde monitoring in the Rio de Janeiro downtown area – Brazil

The fuel matrix used in Brazil is unique around the world. The intensive use of hydrated ethanol, gasohol (gasoline with 25% v/v of ethanol), compressed natural gas (CNG), and biodiesel leads to a peculiar composition of the urban atmosphere. From 1998 to 2002 an increase in formaldehyde levels was observed and since then, a reduction. This work presents a monitoring campaign that was executed from March 2004 to February 2009 by sampling at early morning on every sunny Wednesday for a total of 183 samples. The results indicate a strong reduction in formaldehyde levels from 2004 (average of 135.8 μg m^?3 with SD 28.4 μg m^?3) to 2009 (average of 49.3 μg m^?3 with SD 27.4 μg m^?3). The levels of acetaldehyde showed a slight reduction from 2004 (average of 34.9 μg m^?3 with SD 8.0 μg m^?3) to 2009 (average of 26.8 μg m^?3 with SD 11.5 μg m^?3). Comparing the results with the concurrent evolution of the fleet and of fuel composition indicates that the observed formaldehyde levels could be associated with the increase in ethanol use and in CNG use by engines with improved technology over the first converted CNG engines. Modelling studies using the OZIPR trajectory model and the SAPRC chemical mechanism indicate that formaldehyde is the main ozone precursor in Rio de Janeiro and acetaldehyde is the forth one.     

Air pollutants in rural homes in Guizhou,China – Concentrations,speciation, and size distribution

Several types of fuels, including coal, fuel wood, and biogas, are commonly used for cooking and heating in Chinese rural households, resulting in indoor air pollution and causing severe health impacts. In this paper, we report a study monitoring multiple pollutants including PM₁₀, PM_2.5, CO, CO₂, and volatile organic compounds (VOCs) from fuel combustion at households in Guizhou province of China. The results showed that most pollutants exhibited large variability for different type of fuels except for CO₂. Among these fuels, wood combustion caused the most serious indoor air pollution, with the highest concentrations of particulate matters (218～417 μg m^?3 for PM₁₀ and 201～304 μg m^?3 for PM_2.5), and higher concentrations of CO (10.8 ± 0.8 mg m^?3) and TVOC (about 466.7 ± 337.9 μg m^?3). Coal combustion also resulted in higher concentrations of particulate matters (220～250 μg m^?3 for PM₁₀ and 170～200 μg m^?3 for PM_2.5), but different levels for CO (respectively 14.5 ± 3.7 mg m^?3 for combustion in brick stove and 5.5 ± 0.7 mg m^?3 for combustion in metal stove) and TVOC (170 mg m^?3 for combustion in brick stove and 700 mg m^?3 for combustion in metal stove). Biogas was the cleanest fuel, which brought about the similar levels of various pollutants with the indoor case of non-combustion, and worth being promoted in more areas. Analysis of the chemical profiles of PM_2.5 indicated that OC and EC were dominant components for all fuels, with the proportions of 30～48%. A high fraction of SO₄^2? (31～34%) was detected for coal combustion. The cumulative percentages of these chemical species were within the range of 0.7～1.3, which was acceptable for the assessment of mass balance.     

Estimation and characterization of children’s ambient generated exposure to PM2.5 using sulphate and elemental carbon as tracers

Children’s exposures to ambient and non-ambient fine particulate matter (PM_2.5) were determined using the sulphate and elemental carbon components of the PM_2.5 mixture as tracers of the ambient contribution during a 6-week winter period in Prince George, British Columbia, Canada. Personal exposures to PM_2.5 were measured in children at 5 elementary schools located throughout the city and ambient samples were collected on school rooftops. Average ambient levels and personal exposures during this time period were 13.8 μg m^?3 and 16.4 μg m^?3 respectively. From the data pooled across individuals, use of the two different tracers indicated identical estimates of median exposure to ambient PM_2.5 (7.5 μg m^?3) and similar estimates of non-ambient generated exposure (6.4 and 5.0 μg m^?3) and infiltration (0.49 and 0.52) for the sulphate and elemental carbon approach, respectively. The median fraction of the ambient concentration resulting in exposure or exposure factors were 0.54 and 0.55 respectively, however lower values of 0.46 and 0.42 were determined from regression analysis. A strong association was found between exposure to ambient PM_2.5 and measured ambient concentrations at both the closest school monitor (median r = 0.92) and a central site (median r = 0.88) demonstrating that the central site monitor was suitable for assessing longitudinal ambient generated exposure throughout the city. These results support the use of elemental carbon as a tracer of ambient generated exposure and the use of ambient data as estimates of longitudinal changes in children’s exposure in this setting. The importance of both ambient and non-ambient sources of PM_2.5 is emphasized by their almost equal contribution to total personal exposures. Comparison with other studies suggests a limited influence of climate and the cold season in Prince George on exposure levels and found similar mean non-ambient generated exposures despite large variability across and within subjects in any given location.     

Spatial and chemical patterns of PM10 in road dust deposited in urban environment

Recent research interest has been focused on road dust resuspension as one of the major sources of atmospheric particulate matter in an urban environment. Given the dearth of studies on the variability of the PM₁₀ fraction of road deposited sediments, our understanding of the main factors controlling this pollutant is incomplete. In the present study a new sampling methodology was devised and applied to collect PM₁₀ deposited mass from 1 m² of road pavement. PM₁₀ road dust fraction was sampled directly from active traffic lanes at 23 sampling sites during a campaign in Barcelona (Spain) in June 2007. The aim of the study was to gain more insight into the variability of mass and chemistry of road dust in different urban environments, such as the city centre, ring roads, and locations nearby demolition/construction sites. The city centre showed values of PM₁₀ road dust within a range of 3–23 mg m^?2, whereas levels reached 24–80 mg m^?2 in locations affected by transport of uncovered heavy trucks. The largest dust loads were measured in the proximity of demolition/construction sites and the harbor entry with values up to 328 mg m^?2.The city centre road dust profiles (%) were enriched in OC, EC, Fe, S, Cu, Zn, Mn, Cr, Sb, Sn, Mo, Zr, Hf, Ge, Ba, Pb, Bi, SO₄^2?, NO₃^?, Cl^? and NH₄⁺, but several crustal components such as Ca, Ti, Na, and Mg were also considerably concentrated. Locations affected by construction and demolition activities had high levels of crustal components such as Ca, Li, Sc, Sr, Rb and also As whereas ring roads, characterized by a higher load of uncovered heavy trucks showed an intermediate composition.Levels of PM₁₀ components per area were also evaluated to quantify the resuspendable amount of each element from 1 m². In the inner city environment mean values of 1363 μg Ca m^?2, 816 μg OC m^?2, 239 μg EC m^?2, 13 μg Cu m^?2, 12 μg Zn m^?2, 1.9 μg Sb m^?2 and 2.0 μg Pb m^?2, in PM₁₀ in all cases, were registered.Moreover the deposited PM load at demolition/construction sites acts as a reservoir or trap for traffic-related particles, which gives rise to large amounts of hazardous pollutants, available for resuspension.     

Quantifying the sources of hazardous elements of suspended particulate matter aerosol collected in Yokohama,Japan

We analyzed metals (Mg, Al, Ca, V, Cr, Mn, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, Cs, Ba, Pb and Bi), water-soluble ions (Na⁺, NH₄⁺, K⁺, Ca²⁺, Cl^?, NO₃^? and SO₄^2?) and carbonaceous mass (EC and OC) in SPM aerosol samples using an ICP-MS, ion chromatograph and CHN corder, respectively. The SPM samples were collected from 1999 to 2005 at two locations (urban site A and industrial site B) of Yokohama, Japan with concentrations in mean and ranges of 34.2 and 19.7–50.3 μg m^?3 and 22.9 and 12.7–35.1 μg m^?3 for the respective location. Source apportionment of SPM aerosol was conducted appropriately for the first time to these locations employing PCA-APCS technique. Major sources of SPM at site A were a) crustal source, b) urban origin, c) undefined, and d) mineral rock. At site B, the sources were predicted as a) urban origin, b) undefined, c) crustal source, and d) secondarily formed aerosol. The tracers and nature of the source related to urban origin at both sites were similar but retaining different source strength. Secondarily formed aerosol was quite unique at site B. However, mineral rock was remarkable at site A.     

Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

Concentration-dependent NH3 deposition processes for mixed moorland semi-natural vegetation

Dry deposition modelling typically assumes that canopy resistance (R_c) is independent of ammonia (NH₃) concentration. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to a moorland composed of a mixture of Calluna vulgaris (L.) Hull, Eriophorum vaginatum L. and Sphagnum spp. Ammonia was applied at a wide range of concentrations (1–100 μg m⁻³). The physical and environmental properties and the testing of the chamber are described, as well as results for the moorland vegetation using the ‘canopy resistance’ and ‘canopy compensation point’ interpretations of the data.Results for moorland plant species demonstrate that NH₃ concentration directly affects the rate of NH₃ deposition to the vegetation canopy, with R_c and cuticular resistance (R_w) increasing with increasing NH₃ concentrations. Differences in R_c were found between night and day: during the night R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 95 s m⁻¹ at 80 μg m⁻³, whereas during the day R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 48 s m⁻¹ at 80 μg m⁻³. The lower resistance during the day is caused by the stomata being open and available as a deposition route to the plant. R_w increased with increasing NH₃ concentrations and was not significantly different between day and night (at 80 μg m⁻³ NH₃ day R_w=88 s m⁻¹ and night R_w=95 s m⁻¹). The results demonstrate that assessments using fixed R_c will over-estimate NH₃ deposition at high concentrations (over ∼15 μg m⁻³).     

Aerosol mass-size distributions at a tropical coastal environment: response to mesoscale and synoptic processes

Regular measurements of total mass concentration and mass-size distribution of near-surface aerosols, made using a ten-channel Quartz Crystal Microbalance (qcm) Impactor for the period October 1998–December 1999 at the tropical coastal station Trivandrum (8.5°N, 77°E), are used to study the response of aerosol characteristics to regional mesoscale and synoptic processes. Results reveal that aerosol mass concentrations are generally higher under land breeze conditions. The sea breeze generally has a cleansing effect, depleting the aerosol loading. The continental air (LB regime) is richer in accumulation mode (submicron) aerosols than the marine air. On a synoptic scale, aerosol mass concentration in the submicron mode decreased from an average high value of ∼86 μg m⁻³ during the dry months (January–March) to ∼11 μg m⁻³ during the monsoon season (June–September). On the contrary mass concentration in the supermicron mode increased from a low value of ∼15 μg m⁻³ during the dry months to reach a comparatively high value of ∼35 μg m⁻³ during April, May. Correspondingly, the effective radius (R_eff) increased from a low value of 0.15–0.17 μm to ∼0.3 μm indicating a seasonal change in the size distribution. The mass-size distribution shows mainly three modes, a fine mode (∼0.1 μm); a large mode (∼0.5 μm) and a coarse mode (∼3 μm). The fine mode dominates in winter. In summer the large mode becomes more conspicuous and the coarse mode builds up. The fine mode is highly reduced in monsoon and the large and coarse modes continue to remain high (replenished) so that their relative dominance increases. The size distribution tends to revert to the winter pattern in the post-monsoon season. Accumulation (submicron) aerosols account for ∼98% of the total surface area and ∼70% of the total volume of aerosols during winter. During monsoon, even though they still account for ∼90% of the area, their contribution to the volume is reduced to ∼50%; the coarse aerosols account for the rest.     

Behavioral and environmental determinants of personal exposures to PM2.5 in EXPOLIS – Helsinki,Finland

Behavioral and environmental determinants of PM_2.5 personal exposures were analyzed for 201 randomly selected adult participants (25–55 years old) of the EXPOLIS study in Helsinki, Finland. Personal exposure concentrations were higher than respective residential outdoor, residential indoor and workplace indoor concentrations for both smokers and non-smokers. Mean personal exposure concentrations of active smokers (31.0±31.4 μg m⁻³) were almost double those of participants exposed to environmental tobacco smoke (ETS) (16.6±11.8 μg m⁻³) and three times those of participants not exposed to tobacco smoke (9.9±6.2 μg m⁻³). Mean indoor concentrations of PM_2.5 when a member of the household smoked indoors (20.8±23.9 μg m⁻³) were approximately 2.5 times the concentrations of PM_2.5 when no smoking was reported (8.2±5.2 μg m⁻³). Interestingly, however, both mean (8.2 μg m⁻³) and median (6.9 μg m⁻³) residential indoor concentrations for non-ETS exposed participants were lower than residential outdoor concentrations (9.5 and 7.3 μg m⁻³, respectively). In simple linear regression models residential indoor concentrations were the best predictors of personal exposure concentrations. Correlations (r²) between PM_2.5 personal exposure concentrations of all participants, both smoking and non-smoking, and residential indoor, workplace indoor, residential outdoor and ambient fixed site concentrations were 0.53, 0.38, 0.17 and 0.16, respectively. Predictors for personal exposure concentrations of non-ETS exposed participants identified in multiple regression were residential indoor concentrations, workplace concentrations and traffic density in the nearest street from home, which accounted for 77% of the variance. Subsequently, step-wise regression not including residential and workplace indoor concentrations as input (as these are frequently not available), identified ambient PM_2.5 concentration and home location, as predictors of personal exposure, accounting for 47% of the variance. Ambient fixed site PM_2.5 concentrations were closely related to residential outdoor concentrations (r²=0.9, p=0.000) and PM_2.5 personal exposure concentrations were higher in summer than during other seasons. Personal exposure concentrations were significantly (p=0.040) higher for individuals living downtown compared with individuals in suburban family homes. Further analysis will focus on comparisons of determinants between Helsinki and other EXPOLIS centers.     

Fire and biofuel contributions to annual mean aerosol mass concentrations in the United States

We estimate the contributions from biomass burning (summer wildfires, other fires, residential biofuel, and industrial biofuel) to seasonal and annual aerosol concentrations in the United States. Our approach is to use total carbonaceous (TC) and non-soil potassium (ns-K) aerosol mass concentrations for 2001–2004 from the nationwide IMPROVE network of surface sites, together with satellite fire data. We find that summer wildfires largely drive the observed interannual variability of TC aerosol concentrations in the United States. TC/ns-K mass enhancement ratios from fires range from 10 for grassland and shrub fires in the south to 130 for forest fires in the north. The resulting summer wildfire contributions to annual TC aerosol concentrations for 2001–2004 are 0.26 μg C m⁻³ in the west and 0.14 μg C m⁻³ in the east; Canadian fires are a major contributor in the east. Non-summer wildfires and prescribed burns contribute on an annual mean basis 0.27 and 0.31 μg C m⁻³ in the west and the east, highest in the southeast because of prescribed burning. Residential biofuel is a large contributor in the northeast with annual mean concentration of up to 2.2 μg C m⁻³ in Maine. Industrial biofuel (mainly paper and pulp mills) contributes up to 0.3 μg C m⁻³ in the southeast. Total annual mean fine aerosol concentrations from biomass burning average 1.2 and 1.6 μg m⁻³ in the west and east, respectively, contributing about 50% of observed annual mean TC concentrations in both regions and accounting for 30% (west) and 20% (east) of total observed fine aerosol concentrations. Our analysis supports bottom-up source estimates for the contiguous United States of 0.7–0.9 Tg C yr⁻¹ from open fires (climatological) and 0.4 Tg C yr⁻¹ from biofuel use. Biomass burning is thus an important contributor to US air quality degradation, which is likely to grow in the future.