The composition and sources of PM2.5 organic aerosol in two urban areas of Chile

Fine particle (PM_2.5) samples were collected, using a charcoal diffusion denuder, in two urban areas of Chile, Santiago and Temuco, during the winter and spring season of 1998. Molecular markers of the organic aerosol were determined using GC/MS. Diagnostic ratios and molecular tracers were used to investigate the origin of carbonaceous aerosols. As main sources, road and non-road engine emissions in Santiago, and wood burning in Temuco were identified. Cluster analysis was used to compare the chemical characteristics of carbonaceous aerosols between the two urban environments. Distinct differences between Santiago and Temuco samples were observed. High concentrations of isoprenoid (30–69 ng m⁻³) and unresolved complex mixture (UCM) of hydrocarbons (839–1369 ng m⁻³) were found in Santiago. High concentrations of polynuclear aromatic hydrocarbons (751±304 ng m⁻³) and their oxygenated derivatives (4±2 ng m⁻³), and of n-alk-1-enes (16±13 ng m⁻³) were observed in Temuco.     

Water-soluble organic compounds at a mountain-top site in Colorado,USA

Water extracts of atmospheric particulate matter (PM_2.5) collected at the Storm Peak Laboratory (SPL) (3210 MSL, 40.45° N, 106.74° W) were analyzed for a wide variety of polar organic compounds. The unique geographical character of SPL allows for extended observations/sampling of the free tropospheric interface. Under variable meteorological conditions between January 9th and January14th 2007, the most abundant compounds were levoglucosan (9–72 ng m^?3), palmitic acid (10–40 ng m^?3) and succinic acid (18–27 ng m^?3). Of 84 analytes included in the GC–MS method, over 50 individual water extractable polar organic compounds (POC) were present at concentrations greater than 0.1 ng m^?3. During a snow event (Jan. 11th–13th), the concentrations of several presumed atmospheric transformation compounds (dicarboxylic acids) were reduced. Lower actinic flux, reduced transport distance, and ice crystal scavenging may explain this variability. Diurnal averages over the sampling period revealed a higher total concentration of water extractable POC at night, 211 ng m^?3 (105–265 ng m^?3), versus day, 160 ng m^?3 (137–205 ng m^?3), which suggests a more aged nighttime aerosol character. This may be due to the increased daytime convective mixing of local primary emissions from the Yampa Valley. XAD resin extracts revealed a gas-phase partitioning of several compounds, and analysis of cloud water collected at this site in 2002 revealed a similar compound abundance trend. Levoglucosan, a wood smoke tracer was generally found to be the most abundant compound in both aerosol and cloud water samples. Variations in meteorological parameters and local/regional transport analysis play an important interpretive role in understanding these results.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Long-range transport episodes of fine particles in southern Finland during 1999–2007

The frequency, strength and sources of long-range transport (LRT) episodes of fine particles (PM_2.5) were studied in southern Finland using air quality monitoring results, backward air mass trajectories, remote sensing of fire hot spots, transport and dispersion modelling of smoke and chemical analysis of particle samples (black carbon, monosaccharide anhydrides, oxalate, succinate, malonate, SO₄^2?, NO₃^?, K⁺ and NH₄⁺). At an urban background site in Helsinki, the daily WHO guideline value (24-h PM_2.5 mean 25 μg m^?3) was exceeded during 1–7 LRT episodes per year in 1999–2007. The 24-h mean maximum concentrations varied between 25 and 49 μg m^?3 during the episodes, which was 3–6 times higher than the local mean concentration (8.7 μg m^?3) in 1999–2007. The highest particle concentrations (max. 1-h mean 163 μg m^?3) and the longest episodes (max. 9 days) were mainly caused by the emissions from open biomass burning, especially during springs and late-summers in 2002 and 2006. During the period 2001–2007, the satellite remote sensing of active fire hot spots and transport and dispersion modelling of smoke indicated that approximately half of the episodes were caused partly by the emissions from wildfires and/or agricultural waste burning in fields in Eastern Europe, especially in Russia, Belarus and Ukraine. Other episodes were mainly caused by the LRT of ordinary anthropogenic pollutants, e.g. from energy production, traffic, industry and wood combustion. During those ‘other episodes’, air masses also arrived from Eastern Europe, including Poland. The highest concentrations of biomass-burning tracers, such as monosaccharide anhydrides (levoglucosan + mannosan + galactosan) and K⁺, were observed during open biomass-burning episodes, but quite high values were also measured during some winter episodes due to wood combustion emissions. Our results indicate that open biomass burning in Eastern Europe causes high fine particle concentration peaks in large areas of Europe almost every year.     

Partial dissolution of ACQ-treated wood in lithium chloride/N-methyl-2-pyrrolidinone: separation of copper from potential lignocellulosic feedstocks

A cellulose solvent system based on lithium chloride (LiCl) in N-methyl-2-pyrrolidinone (NMP) was used to assess the merits of partial dissolutions of coarsely ground wood samples. Alkaline Copper Quaternary (ACQ)-treated pine wood was of particular interest for treatment given the potential to generate a copper-rich stream apart from solid and/or liquid lignocellulosic feedstocks. Treatment with NMP alone gave yields of soluble materials that were higher than typical extractives contents thereby suggesting a limited degree of wood dissolution. Inclusion of LiCl, which disrupts hydrogen bonding, gave lower wood residue recoveries (i.e., higher dissolution) with higher LiCl concentration. Lower wood residue recoveries coincided with lower Klason lignin and hemicellulose-derived sugar contents in the wood residues. After treatment with 8% LiCl in NMP, subsequent filtration afforded 34% of the ACQ-treated sapwood as a wood residue retaining only 2% of the original copper. Pouring the filtrate over an excess of water resulted in the recovery of 30% of the solids and 50% of the copper together as a copper-enriched lignocellulosic precipitate. Results demonstrate a solvent system showing potential as a means to separate heavy metals from preservative-treated wood and to recover lignocellulosic feedstocks that may be suitable for use in a biorefinery.     

Assessment of the temporal and spatial distribution of atmospheric PCNs and their air–soil exchange using passive air samplers in Shanghai,East China

A total of 47 passive air samples and 25 soil samples were collected to study the temporal trend, distribution, and air–soil exchange of polychlorinated naphthalenes (PCNs) in Shanghai, China. Atmospheric PCNs ranged from 3.44 to 44.1 pg/m³ (average of 21.9 pg/m³) in summer and 13.6 to 153 pg/m³ (average of 40.0 pg/m³) in winter. In the soil samples, PCN concentrations were 54.7–1382 pg/g dry weight (average of 319 pg/g). Tri-CNs and tetra-CNs were two dominant homolog groups in air samples, while di-CNs were also found at comparable proportions to tri-CNs and tetra-CNs in soil samples. Most air and soil samples from the industrial and urban areas showed higher PCN concentrations than those from suburban areas. However, some soil samples in urban centers presented higher PCN concentrations than industrial areas. Analysis of PCN sources indicated that both industrial thermal process and historical usage of commercial PCN mixtures contributed to the PCN burden in most areas. The fugacity fraction results indicated a strong tendency of volatilization for lighter PCNs (tri- to hexa-CNs) in both seasons, and air–soil deposition for octa-CNs. Moreover, air–soil exchange fluxes indicate that soil was an important source of atmospheric PCNs in some areas. The results of this study provide information for use in the evaluation of the potential impact and human health risk of PCNs around the study areas.

     

Source contributions to carbonaceous aerosols in the Tennessee Valley Region

Sources of carbonaceous aerosols collected from three sites of Chattanooga, TN (CH), Muscle Shoals, AL (MS), and Look Rock, TN (LR) in the Tennessee Valley Region (TVR) were apportioned using both organic tracer-based chemical mass balance (CMB) modeling and radiocarbon (¹⁴C) measurement and the results were compared. Eight sources were resolved by CMB, among which wood combustion (averaging 0.92 μg m⁻³) was the largest contributor to primary organic carbon (OC) concentrations, followed by gasoline exhaust (0.35 μg m⁻³), and diesel exhaust (0.18 μg m⁻³). The identified primary sources accounted for 43%, 71%, and 14% of measured OC at CH, MS, and LR, respectively. Contributions from the eight primary sources resolved by CMB could explain 107±10% of ambient elemental carbon (EC) concentrations, with diesel exhaust (66±32%) and wood combustion (37±33%) as the most important contributors. The fossil fractions in total carbon determined by ¹⁴C measurements were in reasonably good agreement with that in primary (OC+EC) carbon apportioned by CMB in the MS winter samples. The comparison between the ¹⁴C and CMB results revealed that contemporary sources dominated other OC in the TVR, especially in summertime (84% contemporary).     

Atmospheric concentrations and dry deposition fluxes of particulate trace metals in Salvador,Bahia, Brazil

Respiratory system is the major route of entry for airborne particulates, being the effect on the human organism dependent on chemical composition of the particles, exposure time and individual susceptibility. Airborne particulate trace metals are considered to represent a health hazard since they may be absorbed into human lung tissues during breathing. Fossil fuel and wood combustion, as well as waste incineration and industrial processes, are the main anthropic sources of metals to the atmosphere. In urban areas, vehicular emissions—and dust resuspension associated to road traffic—become the most important manmade source.This work investigated the atmospheric concentrations of TSP, PM₁₀ and elements such as iron, manganese, copper and zinc, from three different sites around Salvador Region (Bahia, Brazil), namely: (i) Lapa Bus Station, strongly impacted by heavy-duty diesel vehicles; (ii) Aratu harbor, impacted by an intense movement of goods, including metal ores and concentrates and near industrial centers and; (iii) Bananeira Village located on Maré Island, a non-vehicle-influenced site, with activities such as handcraft work and fishery, although placed near the port. Results have pointed out that TSP concentrations ranged between 16.9 (Bananeira) and 354.0 μg m⁻³ (Aratu#1), while for PM₁₀ they ranged between 30.9 and 393.0 μg m⁻³, both in the Lapa Bus Station. Iron was the major element in both Lapa Station and Aratu (#1 and #2), with average concentrations in the PM₁₀ samples of 148.9, 79.6 and 205.0 ng m⁻³, respectively. Zinc, on the other hand, was predominant in samples from Bananeira, with an average concentration of 145.0 ng m⁻³ in TSP samples, since no PM₁₀ sample was taken from this site. The main sources of iron in the Lapa Station and Aratu harbor were, respectively, soil resuspension by buses and discharge of solid granaries, as fertilizers and metal ores. On the other hand, zinc and copper in the bus station were mainly from anthropic contributions, probably heavy-duty vehicle ageing and wearing actions releasing off Zn from tires and Cu from brake linings. In the Aratu harbor, the high copper concentrations found were probably due to the port's activities, as discharges of copper concentrate on its terminal, although other sources could be possible, as burning of diesel fuel on ships and heavy oil in heaters. Finally, the Bananeira site has been presented as a different profile, since this remote site has shown zinc as the most abundant element, demonstrating to have an unexpected anthropic contribution. On a mass-to-mass basis, both zinc and manganese were in high levels in the Bananeira site and their presence strongly suggest the impact of other sources, such as the Industrial Center of Aratu and/or a siderurgy plant, not far away from that location.     

Food contamination by C20–C50 mineral paraffins from the atmosphere

Most foods from plant origin usually contain 1–10 mg/kg (dry weight) of non-resolved isomeric alkanes in the range of the n-alkanes C₂₀–C₅₀ which are assumed to be residues from mineral oil products (in addition to the natural paraffins). In edible vegetable oils, concentrations may exceed 100 mg/kg. Since it was suspected that this contamination was mostly of environmental origin, particulate matter from air was analysed for the same range of paraffins. In a road tunnel, around 5 μg/m³ of such paraffins were found, corresponding to about 3% of the fine dust (PM10). The composition corresponded to that found in the particulate matter from the exhaust of diesel engines, which in turn largely corresponded to engine (lubricating) oil. In Swiss cities, the C₂₀–C₅₀ mineral paraffins in the PM10 from ambient air amounted to 0.1–1.5 μg/m³ (about 1% of the dust) and seemed to primarily originate from incomplete combustion of heating and diesel oil, lubricating oil, and road tar debris. On the countryside, the concentrations were around 0.03 μg/m³ (0.3% of the dust). Soil contained 0.5–10 mg/kg of these paraffins. The similarity of the molecular weight (volatility) distribution suggests that the food contamination with paraffins, is mostly from the air. A substantial proportion probably consists of lubricating oil. If this hypothesis is confirmed, measures should be investigated to reduce this contamination.     

Concentrations,seasonal variations,and transport of carbonaceous aerosols at a remote Mountainous region in western China

Carbonaceous aerosol concentrations were determined for total suspended particle samples collected from Muztagh Ata Mountain in western China from December 2003 to February 2006. Elemental carbon (EC) varied from 0.004 to 0.174 μg m^?3 (average = 0.055 μg m^?3) while organic carbon (OC) ranged from 0.12 to 2.17 μg m^?3 and carbonate carbon (CC) from below detection to 3.57 μg m^?3. Overall, EC was the least abundant fraction of carbonaceous species, and the EC concentrations approached those in some remote polar areas, possibly representing a regional background. Low EC and OC concentrations occurred in winter and spring while high CC in spring and summer was presumably due to dust from the Taklimakan desert, China. OC/EC ratios averaged 10.0, and strong correlations between OC and EC in spring–winter suggest their cycles are coupled, but lower correlations in summer–autumn suggest influences from biogenic OC emissions and secondary OC formation. Trajectory analyses indicate that air transported from outside of China brings ～0.05 μg m^?3 EC, ～0.42 μg m^?3 OC, and ～0.10 μg m^?3 CC to the site, with higher levels coming from inside China. The observed EC was within the range of loadings estimated from a glacial ice core, and implications of EC-induced warming for regional climate and glacial ice dynamics are discussed.     

A four-year size-segregated characterization study of particles PM10, PM2.5 and PM1 depending on air mass origin at Melpitz

PM₁₀ measurements were started in November 1992 at Melpitz site. The mean PM₁₀ concentration in 1993 was 38 μg m^?3 in the summer season (May until October) and about 44 μg m^?3 in the winter season (November until April). The mean PM₁₀ level decreased until 1999 and varies now in ranges from 20–34 μg m^?3 to 17–24 μg m^?3 (minimum and maximum mean values for 1999–2008) in winter and summer seasons, respectively. High volume filter samples of particles PM₁₀, PM_2.5 and PM₁ were characterized for mass, water-soluble ions, organic and elemental carbon from 2004 until 2008. The percentage of PM_2.5 in PM₁₀ varies between summer (71.6%) and winter seasons (81.9%). Mean concentrations of PM₁₀, PM_2.5 and PM₁ in Melpitz were 20, 15, and 13 μg m^?3 in 2004, 22, 18, and 13 μg m^?3 in 2005, 24, 19, and 12 μg m^?3 in 2006 and 22, 17, and 12 μg m^?3 in 2007, respectively. In the four winters the rural background concentration PM₁₀ at Melpitz exceeded the daily 50 μg m^?3 limit for Europe on 8, 8, 7 and 6 days, respectively.Findings for a simple two-sector-classification of the samples (May 2004 until April 2008) using 96-h backward trajectories for the identification of source regions are: Air masses were transported most of time (60%) from the western sector and secondly (17%) from the eastern sector. The lowest daily mean mass concentration PM₁₀ were found during western inflow in summer (17 μg m^?3) containing low amounts of sulphate (2.4 μg m^?3), nitrate (1.7 μg m^?3), ammonium (1.1 μg m^?3) and TC (3.7 μg m^?3). In opposite the highest mean mass concentration PM₁₀ was found during eastern inflow in winter (35 μg m^?3) with high amounts of sulphate (6.1 μg m^?3), nitrate (5.4 μg m^?3), ammonium (3.8 μg m^?3) and TC (9.4 μg m^?3). An estimation of secondary formed OC (SOA) shows 0.8–0.9 μg m^?3 for air masses from West and 2.1–2.2 μg m^?3 from East. The seasonal difference can be neglected.The half-hourly measurements of the particle mass concentration PM₁₀ evaluated as mean daily courses using a TEOM^® show low values (14–21 μg m^?3) in summer and winter for air masses transported from West and the highest concentrations (31–38 μg m^?3) in winter for air masses from East.The results demonstrate the influence of meteorological parameters on long-range transport, secondary particle mass formation and re-emission which modify mass concentration and composition of PM₁₀, PM_2.5 and PM₁. Melpitz site is located in the East of Germany faraway from strong local anthropogenic emissions (rural background). Therefore, this site is suitable for investigation of the influence of long-range transport of air pollution in continental air masses from the East with source regions inside and outside of the European Union.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.     

Wood-Specific Polycyclic Aromatic Hydrocarbon (PAH) Patterns in Soot Using Gas Chromatography-Atmospheric Pressure Laser Ionization-Mass Spectrometry (GC-APLI-MS)

If organic matter is burnt, the combustion of wood produces the highest amounts of polycyclic aromatic hydrocarbons (PAHs) compared with other fossil energy sources such as oil, coal, or gas. Emissions from wood combustion are increasingly of special interest due to the rising use of wood as a renewable energy source in residential heating in Europe. To the authors' knowledge, reproducible wood-specific PAH patterns in soot were identified for the first time by use of a sampling interval of only 5 min in this study. The short sampling interval was enabled by the very sensitive analytical method of gas chromatography–atmospheric pressure laser ionization–mass spectrometry (GC-APLI-MS) applied. The analysis of 40 PAH of soot from wood logs of spruce, pine, larch (softwood) and beech, birch, oak (hardwood), and wood pellets, as well as wood briquettes, showed 13.46–250.62 mg/kg for ∑40 PAH and 10.75–177.94 mg/kg for the U.S. Environmental Protection Agency PAH standard (without acenaphthylene and anthracene). Highest concentrations occurred in the samples from birch with bark, beech, and wood briquettes. Indeno[1,2,3-cd]pyrene, naphthalene, and alkylated naphthalenes were also detected. Significant concentrations of the very toxic dibenzopyrenes (up to 11.30 mg/kg) are reported. Softwood soot contained highest amounts of 2–4-ring PAH, followed by hardwood which is in accordance with the presence of highest amounts of abietic acid in softwood, a known precursor of retene and phenanthrene. PAH in soot from five spruce samples from different locations show a mean ∑40 PAH concentration of 13.46 mg/kg (n = 5, minimum 8.03, maximum 23.32 mg/kg, SD = 5.65) and exhibited a typical pattern that differed from all other wood soot samples. The distributions of alkylated naphthalenes of the spruce samples show a bell-shape distribution in contrast to the alkylated phenanthrenes/anthracenes of all samples (except the wood pellets), showing a slope distribution. The data indicate that wood-specific PAH patterns exist and under the applied conditions, spruce logs produced the least toxic soot.     

Survey of polyfluorinated chemicals (PFCs) in the atmosphere over the northeast Atlantic Ocean

High volume air sampling in Bermuda, Sable Island (Nova Scotia) and along a cruise track from the Gulf of Mexico to northeast coast of the USA, was carried out to assess air concentrations, particle-gas partitioning and transport of polyfluorinated chemicals (PFCs) in this region. Samples were collected in the summer of 2007. Targeted compounds included the neutral PFCs: fluorotelomer alcohols (FTOHs), perfluoroalkyl sulfonamides (FOSAs) and perfluoroalkyl sulfonamido ethanols (FOSEs).Among the FTOHs, 8:2 FTOH was dominant in all samples. Sum of the concentration of FTOHs (gas+particle phase) were higher in Bermuda (mean, 34 pg m^?3) compared to Sable Island (mean, 16 pg m^?3). In cruise samples, sum of FTOHs were highly variable (mean, 81 pg m^?3) reflecting contributions from land-based sources in the northeast USA with concentrations reaching as high as 156 pg m^?3.Among the FOSAs and FOSEs, MeFOSE was dominant in all samples. In Bermuda, levels of MeFOSE were exceptionally high (mean, 62 pg m^?3), exceeding the FTOHs. Sable Island samples also exhibited the dominance of MeFOSE but at a lower concentration (mean, 15 pg m^?3). MeFOSE air concentrations (pg m^?3) in cruise samples ranged from 1.6 to 73 and were not linked to land-based sources. In fact high concentrations of MeFOSE observed in Bermuda were associated with air masses that originated over the Atlantic Ocean.The partitioning to particles for 8:2 FTOH, 10:2 FTOH, MeFOSE and EtFOSE ranged from as high as 15 to 42% for cruise samples to 0.9 to 14% in Bermuda. This study provides key information for validating and developing partitioning and transport models for the PFCs.     

Fine particulate (PM2.5) composition in Atlanta, USA: assessment of the particle concentrator-Brigham Young University organic sampling system, PC-BOSS, during the EPA supersite study

Aerosol concentrations of carbonaceous material, sulfate, and nitrate for samples obtained using a newly designed PC-BOSS are reported. The results indicated that PM_2.5 composition in Atlanta was dominated by sulfate and organic material, with low concentrations of particulate nitrate. Observed average particulate component concentrations for the 26-day study period were: sulfate, 12.2 μg/m³ (17.0 μg/m³ as ammonium sulfate); non-volatile organic material, 11.4 μg OM/m³ (assumes organic material, OM, is 61% C); semi-volatile organic compounds (SVOC) lost from particles during sampling, 5.3 μg OM/m³; filter retained nitrate, 0.1 μg/m³ (0.2 μg/m³ as ammonium nitrate); nitrate lost from particles, 0.3 μg/m³ (0.4 μg/m³ as ammonium nitrate); and soot (elemental carbon), 1.5 μg/m³. The PC-BOSS particle concentrator efficiency was obtained by comparison of the PC-BOSS sulfate data with sulfate data obtained from the Federal Reference Method (FRM) sampler. A modification of the PC-BOSS design to allow independent determination of this parameter is recommended.     

Mercury deposition/accumulation rates in the vicinity of a lead smelter as recorded by a peat deposit

Mercury (Hg) concentration profiles and historical accumulation rates were determined in three ²¹⁰Pb-dated cores from a peat deposit in the vicinity of a lead (Pb) smelter at Příbram, Czech Republic. The Hg concentrations in peat samples ranged from 66 to 701 μg kg⁻¹. Cumulative Hg inventories from each core (for the past 150 yr) varied by a factor of 1.4 (13.6–18.5 mg Hg m⁻²), indicating variations of net Hg accumulation rate within the peat deposit. Historical changes in vegetation cover (leading to variable interception by trees) are probably responsible for this variation in space and time. The uncorrected Hg accumulation rates peaked between the 1960s and 1980s (up to 226 μg m⁻² yr⁻¹). Recent findings show that Hg records from peat tend to overestimate historical levels of Hg deposition. Therefore we used the mass loss compensation factor (MLCF) to normalize Hg accumulation rates. These corrected Hg accumulation rates were significantly lower (maximum 129 μg m⁻² yr⁻¹) and better corresponded to changes in historical smelter emissions, which were highest in the 1960s. The agreement between the corrected Hg accumulation rates in the uppermost peat sections (2–38 μg m⁻² yr⁻¹) and biomonitoring of atmospheric deposition by mosses in several recent years (4.7–34.4 μg m⁻² yr⁻¹) shows the usefulness of MLCF application on Hg accumulation in peat archives. However, the MLCF correction was unsuitable for Pb. The recent Pb deposition rates obtained by an independent biomonitoring study using mosses (0.5–127 mg m⁻² yr⁻¹) were better correlated with net Pb accumulation rates recorded in peat (7–145 mg m⁻² yr⁻¹) than with corrected rates obtained by the MLCF approach (1–28 mg m⁻² yr⁻¹).     

Atmospheric distribution of polycyclic aromatic hydrocarbons and deposition to Galveston Bay,Texas, USA

Estimates of the atmospheric deposition to Galveston Bay of polycyclic aromatic hydrocarbons (PAHs) are made using precipitation and meteorological data that were collected continuously from 2 February 1995 to 6 August 1996 at Seabrook, TX, USA. Particulate and vapor phase PAHs in ambient air and particulate and dissolved phases in rain samples were collected and analyzed. More than 95% of atmospheric PAHs were in the vapor phase and about 73% of PAHs in the rain were in the dissolved phase. Phenanthrene and napthalene were the dominant compounds in air vapor and rain dissolved phases, respectively, while 5 and 6 ring PAH were predominant in the particulate phase of both air and rain samples. Total PAH concentrations ranged from 4 to 161 ng m⁻³ in air samples and from 50 to 312 ng l⁻¹ in rain samples. Temporal variability in total PAH air concentrations were observed, with lower concentrations in the spring and fall (4–34 ng m ⁻³) compared to the summer and winter (37–161 ng m⁻³). PAHs in the air near Galveston Bay are derived from both combustion and petroleum vaporization. Gas exchange from the atmosphere to the surface water is estimated to be the major deposition process for PAHs (1211 μg m^{− 2} yr^{− 1}), relative to wet deposition (130 μg m⁻² yr^{− 1}) and dry deposition (99 μg m⁻² yr^{− 1}). Annual deposition of PAHs directly to Galveston Bay from the atmosphere is estimated as 2  t yr⁻¹.     

Particle size distributions and health-related exposures of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of sinter plant workers

This study measured particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in two workplace atmospheres of the sintering grate and rough roll shredder in a sintering plant, and to assess their workers’ health-related exposures. We found that the PCDD/F concentration of the sintering grate (site A = 14.47 pg m⁻³) was lower than that of the rough roll shredder (site B = 17.20 pg m⁻³). Particle size distributions of PCDD/Fs were in the form of the unimodal with the mass median aerodynamic diameter (MMAD) of 4.74 μm and 5.23 μm, and geometric standard deviation (σ_g) of 3.15 and 2.15 for the site A and B, respectively. The above results suggest that the workplace of the site A had a less fraction of coarse particles than that of the site B. The estimated PCDD/F concentrations of the inhalable fraction (11.0 pg m⁻³) and thoracic fraction (8.89 pg m⁻³) of the site A were lower than those of the site B (12.4 and 9.39 pg m⁻³, respectively). But to the contrary the estimated respirable fraction of the site A (5.05 pg m⁻³) was slightly higher than that of the site B (4.93 pg m⁻³). Our results clearly indicate the importance to conduct particle size segregating samplings for assessing human PCDD/F exposures.     

Urban and rural ultrafine (PM0.1) particles in the Helsinki area

In June 1996–June 1997 Berner low-pressure impactors were used at an urban and at a rural site in the Helsinki area for sampling ultrafine particles (UFP, PM_0.1). Ten sample pairs, each pair measured simultaneously, were collected in the size range of 0.03–15 μm of particle aerodynamic diameter. More than 40 chemical components were measured. Surprisingly, the average UFP mass concentration was higher at the rural site (520 ng/m³) than at the urban site (490 ng/m³). The average chemical composition of UFP was similar at the two sites. The most abundant of the measured components were sulphate (32 and 40 ng/m³ for the urban and rural sites, respectively), ammonium (22 and 25 ng/m³), nitrate (4 and 11 ng/m³) and the Ca²⁺ ion (5 and 7 ng/m³). The most important metals at both sites were Ca, Na, Fe, K and Zn with concentrations between 0.7 and 5 ng/m³. Of the heavy metals, Ni, V, Cu, and Pb were important with average ultrafine concentrations between about 0.1 and 0.2 ng/m³. Also the organic anions oxalate (urban 2.1 ng/m³ and rural 1.9 ng/m³) and methanesulphonate (1.3 and 1.7 ng/m³) contributed similarly at both sites. The measured species accounted for only about 15–20% of the total ultrafine mass. The fraction that was not measured includes mainly carbonaceous material and water. It was estimated that the amount of water was about 10% (50 ng/m³) and that of carbonaceous material about 70% (350 ng/m³) at both sites. Aitken modes were observed for most components with the average mass mean mode diameters being between about 0.06 and 0.12 μm. The average concentrations in the Aitken mode differed clearly from those in the UFP for several components.The average contribution of ultrafine mass to the fine particle mass (PM_2.5) was about 7% at the urban site and 8.5% at the rural site. At both sites the contribution of ultrafine to fine was especially high for Se, Ag, B, and Ni (10–20%) and at the rural site also for Co (20%), Ca²⁺ (16%) and Mo (11%). Enrichment in the ultrafine particles suggests that local sources may exist for these elements.Aitken modes turned out to be useful indicators of local sources for several components. The Aitken modes of Ba, Ca, Mg and Sr were similar in several samples, suggesting a common local combustion source for these elements, possibly traffic exhaust. Co, Fe, Mo and Ni formed another group of elements often having similar Aitken modes, the likely source being combustion of heavy fuel oil.     

Contribution of residential wood combustion to PM10 levels in Portugal

Wood is commonly used in residential combustion for heating purposes; however, it can be a major source of air pollutants, namely fine particles, volatile organic compounds and carbon monoxide. Since 2004, the PM10 daily limit value has been surpassed in Portugal, and the European Commission has stated that plans and programs must be designed in order to reduce these levels. In Portugal, 18% of PM10 emissions are due to residential wood combustion, which may deeply impact the PM10 levels in the atmosphere. The main aim of this study is to investigate the impact of residential wood combustion on the air quality in Portugal. The air quality modelling system MM5/CHIMERE was applied over Portugal for a winter month, for the following three scenarios: the reference scenario, considering the actual emissions of PM10; scenario 1, where residential wood combustion emissions are not considered; and scenario 2, which takes into account a complete conversion from traditional fireplaces to certified appliances (with a 90% reduction in PM emissions). The residential wood combustion contribution to PM10 air quality concentration values during January 2007 ranges from 0 to 14 μg m^?3, with a mean contribution of 10 μg m^?3 in the Lisboa area and 6 μg m^?3 in the Porto region. Concerning the legislated values, the area where the daily average limit value (50 μg m^?3) is exceeded decreases by 46% in the simulation when residential combustion is not considered. The modelling results for scenario 2 are not significantly different from those for scenario 1. In summary, the regulation of the residential wood combustion sector is as an effective way to reduce the PM10 levels in the atmosphere as regards air quality plans and programs.