X-ray Spectroscopic Quantification of Phosphorus Transformation in Saharan Dust during Trans-Atlantic Dust Transport.

Saharan dust is an important phosphorus (P) supply to remote and oligotrophic parts of the oceans and American lowland tropical rainforests. Phosphorus speciation in aeolian dust ultimately controls the release and bioavailability of P after dust deposition, but the speciation in Saharan dust and its change during the trans-Atlantic transport remains unclear. Using P K-edge X-ray absorption near edge structure (XANES) spectroscopy, we showed that with increasing dust traveling distance from the Sahara Desert to Cape Verde and to Puerto Rico, about 570 and 4000 km, respectively, the proportion of Ca-bound P (Ca-P), including both apatite and non-apatite forms, decreased from 68-73% to 50-71% and to 21-37%. The changes were accompanied by increased iron/aluminum-bound P proportion from 14-25% to 23-46% and to 44-73%, correspondingly. Laboratory simulation experiments suggest that the changes in P speciation can be ascribed to increasing degrees of particle sorting and atmospheric acidification during dust transport. The presence of relatively soluble non-apatite Ca-P in the Cape Verde dust but not in the Puerto Rico dust is consistent with the higher P water solubility of the former than the latter. Our findings provide insights into the controls of atmospheric processes on P speciation, solubility, and stability in Saharan dust.

Polycyclic aromatic hydrocarbons and their derivatives (nitro-PAHs, oxygenated PAHs, and azaarenes) in PM2.5 from Southern European cities.

Atmospheric particulate matter (PM2.5) samples were collected over two one month periods during winter and summer in three Southern European cities (Oporto - traffic site, Florence - urban background, Athens - suburban). Concentrations of 27 polycyclic aromatic hydrocarbons (PAHs), 15 nitro-PAHs (NPAHs), 15 oxygenated-PAHs (OPAHs) and 4 azaarenes (AZAs) were determined. On average, the winter-summer concentrations of ΣPAHs were 16.3-5.60, 7.75-3.02 and 3.44-0.658ngm-3 in Oporto, Florence and Athens, respectively. The corresponding concentrations of ΣNPAHs were 15.8-9.15, 10.9-3.36 and 15.9-2.73ngm-3, whilst ΣOPAHs varied in the ranges 41.8-19.0, 11.3-3.10 and 12.6-0.704ngm-3. Concentrations of ΣAZAs were always below 0.5ngm-3. Irrespective of the city, the dominant PAHs were benzo[b+j+k]fluoranthene, retene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene. The most abundant OPAH in all cities was 1,8-naphthalic anhydride, whereas 5-nitroacenaphthene was the prevailing NPAH. The ΣOPAHs/ΣPAHs and ΣNPAHs/ΣPAHs were higher in summer than in winter, suggesting increasing formation of derivatives by photochemical degradation of PAHs. Molecular diagnostic ratios suggested that, after traffic, biomass burning was the dominant emission source. Apart from being influenced by seasonal sources, the marked differences between winter and summer may indicate that these diagnostic ratios are particularly sensitive to photodegradation, and thus should be applied and interpreted cautiously. The lifetime excess cancer risk from inhalation was, in part, attributable to PAH derivatives, acclaiming the need to include these compounds in regular monitoring programmes. On average, 206, 88 and 26 cancer cases per million people were estimated, by the World Health Organisation method, for the traffic-impacted, urban background and suburban atmospheres of Oporto, Florence and Athens, respectively.

Hydrocarbons in particulate samples from wildfire events in central Portugal in summer 2010.

In summer 2010, twenty eight (14 PM2.5 samples plus 14 samples PM2.5-10) smoke samples were collected during wildfires that occurred in central Portugal. A portable high-volume sampler was used to perform the sampling, on quartz fibre filters of coarse (PM2.5-10) and fine (PM2.5) smoke samples. The carbonaceous content (elemental and organic carbon) of particulate matter was analysed by a thermal-optical technique. Subsequently, the particulate samples were solvent extracted and fractionated by vacuum flash chromatography into three different classes of organic compounds (aliphatics, polycyclic aromatic hydrocarbons (PAHs) and carbonyl compounds). The organic speciation was performed by gas chromatography-mass spectrometry (GC-MS). Emissions were dominated by the fine particles, which represented around 92% of the PM10. A clear predominance of carbonaceous constituents was observed, with organic to elemental carbon (OC/EC) ratios ranging between 1.69 and 245 in both size fractions. The isoprenoid ketone 6,10,14-trimethyl-2-pentadecanone, a tracer for secondary organic aerosol formation, was one of the dominant constituents in both fine and coarse particles. Retene was the most abundant compound in all samples. Good correlations were obtained between OC and both aliphatic and PAH compounds. Pyrogenic processes, thermal release of biogenic compounds and secondary processing accounted for 97% of the apportioned PM2.5 levels.

A one-year record of carbonaceous components and major ions in aerosols from an urban kerbside location in Oporto, Portugal.

PM2.5 aerosol samples were collected from January 2013 to January 2014 on the kerbside of a major arterial route in the city of Oporto, Portugal, and later analyzed for carbonaceous fractions and water soluble ions. The average concentrations of organic carbon (OC), elemental carbon (EC) and water soluble organic carbon (WSOC) in the aerosol were 6.2µg/m(3), 5.0µg/m(3) and 3.8µg/m(3), respectively, and fit within the range of values that have been observed close to major roads in Europe, Asia and North America. On average, carbonaceous matter accounted for 56% of the gravimetrically measured PM2.5 mass. The three carbon fractions exhibited a similar seasonal variation, with high concentrations in late autumn and in winter, and low concentrations in spring. SO4(2-) was the dominant water soluble ion, followed by NO3(-), NH4(+), Cl(-), Na(+), K(+), oxalate, Ca(2+), Mg(2+), formate, methanesulfonate and acetate. Some of these ions exhibited a clear seasonal trend during the study period. The average OC/EC ratio for the entire set of samples was 1.28±0.61, which was consistent with a significant influence of vehicle exhaust emissions on aerosol composition. On the other hand, the average WSOC/OC ratio was 0.67±0.23, reflecting the influence of other emitting sources. WSOC was highly correlated with nssK(+), a tracer of biomass combustion, and was not correlated with nssSO4(2-), a species associated with secondary processes, suggesting that the main source of WSOC was biomass burning. Most of the SO4(2-) was anthropogenic in origin and was closely associated with NH4(+), pointing to the formation of secondary aerosols. Na(+), Cl(-) and methanesulfonate were clearly associated with marine sources while NO3(-) was related with combustion of both fossil and non-fossil fuels. Mixed sources explained the occurrence of the other water soluble ions.

Elements and polycyclic aromatic hydrocarbons in exhaust particles emitted by light-duty vehicles.

The main purpose of this work was to evaluate the chemical composition of particulate matter (PM) emitted by eight different light-duty vehicles. Exhaust samples from petrol and diesel cars (Euro 3 to Euro 5) were collected in a chassis dynamometer facility. To simulate the real-world driving conditions, three ARTEMIS cycles were followed: road, to simulate a fluid traffic flow and urban with hot and cold starts, to simulate driving conditions in cities. Samples were analysed for the water-soluble ions, for the elemental composition and for polycyclic aromatic hydrocarbons (PAHs), respectively, by ion chromatography, inductively coupled plasma atomic emission spectroscopy (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and gas chromatography-mass spectrometry (GC-MS). Nitrate and phosphate were the major water-soluble ions in the exhaust particles emitted from diesel and petrol vehicles, respectively. The amount of material emitted is affected by the vehicle age. For vehicles ≥Euro 4, most elements were below the detection limits. Sodium, with emission factors in the ranges 23.5-62.4 and 78.2-227µg km(-1), for petrol and diesel Euro 3 vehicles, respectively, was the major element. The emission factors of metallic elements indicated that diesel vehicles release three to five times more than petrol automobiles. Element emissions under urban cycles are higher than those found for on-road driving, being three or four times higher, for petrol vehicles, and two or three times, for diesel vehicles. The difference between cycles is mainly due to the high emissions for the urban cycle with hot start-up. As registered for elements, most of the PAH emissions for vehicles ≥Euro 4 were also below the detection limits. Regardless of the vehicle models or driving cycles, the two- to four-ring PAHs were always dominant. Naphthalene, with emission factors up to 925 µg km(-1), was always the most abundant PAH. The relative cancer risk associated with naphthalene was estimated to be up to several orders of magnitude higher than any of the chemical species found in the PM phase. The highest PAH emission factors were registered for diesel-powered vehicles. The condition of the vehicle can exert a decisive influence on both element and PAH emissions.

Wet deposition of particulate carbon to the Central North Atlantic Ocean.

Elemental carbon (EC) and water-insoluble organic carbon (WIOC) concentrations were measured in wet-only precipitation samples collected on Terceira Island (Azores, Portugal) between December 2009 and October 2010, to investigate temporal variations, source regions and wet deposition fluxes. The global volume-weighted average (vwa) concentrations were 134 ± 19 µgC L(-1) for WIOC and 15.0 ± 1.6 µgC L(-1) for EC, which fall within the range of values that have been found in the European background atmosphere. The WIOC concentration exhibited a temporal variation over the study period with a minimum in winter (vwa 88 ± 16 µgC L(-1)) and a maximum in summer (vwa 477 ± 86 µgC L(-1)). This trend was due to the higher dilution effect of winter rains and possibly to an increase of biogenic particulate carbon incorporation during the growing season. A different temporal variation was observed for the EC concentration with a minimum in summer (vwa 4.2 ± 3.3 µgC L(-1)) and a maximum in spring (vwa 17.5 ± 2.2 µgC L(-1)). The observed trend was mainly related to changes in atmospheric circulation patterns over the Azores. A backward trajectory analysis was applied to identify possible source regions of particulate carbon. The highest WIOC and EC concentrations were associated with air masses that persisted for more than four days over the Central North Atlantic Ocean and with air masses arriving from Europe, respectively. Lower concentrations were observed in samples collected under the influence of back-trajectories from North America. Despite the lower abundance of particulate carbon, the wet deposition fluxes were higher for this group of samples, which reflects the higher amount of precipitation that is normally associated with air masses arriving in the Azores from the west and northwest sectors.

Indoor and outdoor suspended particulate matter and associated carbonaceous species at residential homes in northwestern Portugal.

Particulate matter with an aerodynamic diameter equal to or less than 10 µm (PM10), organic carbon (OC) and elemental carbon (EC) concentrations were measured simultaneously in the indoor and outdoor air of 4 residences located in urban and sub-urban areas in northwestern Portugal. The residences were studied with occupants. One residence was also studied without any indoor activity, taking advantage of the fact that the occupants had moved into a new home. First, 48-h aerosol samples were collected on quartz fiber filters with low-volume samplers equipped with size selective inlets. The filters were weighed and then analyzed for OC and EC using a thermal-optical transmittance method. The average indoor and outdoor PM10 concentrations in the occupied residences were 71.9 ± 38.3 µg/m(3) and 54.0 ± 13.3 µg/m(3), respectively. Despite the higher concentration of PM10 indoors, outdoor sources were found to be a significant contributor to indoor concentrations. An estimate based on data from the residence studied under different occupancy conditions indicated that outdoor sources can account for 68% of the indoor PM10 mass concentration. Average indoor to outdoor (I/O) ratios for OC ranged from 1.7 to 5.6 in occupied residences, showing that indoor sources, such as cooking, smoking, biomass burning and movement of people, strongly influenced indoor OC concentrations. In contrast, I/O ratios for EC were close to 1, except for a smokers' residence, suggesting that indoor concentrations were mainly controlled by outdoor sources, most likely from vehicular emissions and biomass burning.

Convergence of potential net ecosystem production among contrasting C3 grasslands.

Metabolic theory and body size constraints on biomass production and decomposition suggest that differences in the intrinsic potential net ecosystem production (NEPPOT ) should be small among contrasting C3 grasslands and therefore unable to explain the wide range in the annual apparent net ecosystem production (NEPAPP ) reported by previous studies. We estimated NEPPOT for nine C3 grasslands under contrasting climate and management regimes using multiyear eddy covariance data. NEPPOT converged within a narrow range, suggesting little difference in the net carbon dioxide uptake capacity among C3 grasslands. Our results indicate a unique feature of C3 grasslands compared with other terrestrial ecosystems and suggest a state of stability in NEPPOT due to tightly coupled production and respiration processes. Consequently, the annual NEPAPP of C3 grasslands is primarily a function of seasonal and short-term environmental and management constraints, and therefore especially susceptible to changes in future climate patterns and associated adaptation of management practices.

Emission of trace gases and organic components in smoke particles from a wildfire in a mixed-evergreen forest in Portugal.

On May 2009, both the gas and particulate fractions of smoke from a wildfire in Sever do Vouga, central Portugal, were sampled. Total hydrocarbons and carbon oxides (CO(2) and CO) were measured using automatic analysers with flame ionisation and non-dispersive infrared detectors, respectively. Fine (PM(2.5)) and coarse (PM(2.5-10)) particles from the smoke plume were analysed by a thermal-optical transmission technique to determine the elemental and organic carbon (EC and OC) content. Subsequently, the particle samples were solvent extracted and fractionated by vacuum flash chromatography into different classes of organic compounds. The detailed organic speciation was performed by gas chromatography-mass spectrometry. The CO, CO(2) and total hydrocarbon emission factors (g kg(-1) dry fuel) were 170 ± 83, 1485 ± 147, and 9.8 ± 0.90, respectively. It was observed that the particulate matter and OC emissions are significantly enhanced under smouldering fire conditions. The aerosol emissions were dominated by fine particles whose mass was mainly composed of organic constituents, such as degradation products from biopolymers (e.g. levoglucosan from cellulose, methoxyphenols from lignin). The compound classes also included homologous series (n-alkanes, n-alkenes, n-alkanoic acids and n-alkanols), monosaccharide derivatives from cellulose, steroid and terpenoid biomarkers, and polycyclic aromatic hydrocarbons (PAHs). The most abundant PAH was retene. Even carbon number homologs of monoglycerides were identified for the first time as biomarkers in biomass burning aerosols.

Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal.

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49µm. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products.

Determination of saccharides in atmospheric aerosol using anion-exchange high-performance liquid chromatography and pulsed-amperometric detection.

An improved method is described for the quantification of primary sugars, sugar alcohols and anhydrosugars in atmospheric aerosols, making use of separation by high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD). Quartz fibre filters from high-volume samplers were extracted with water and the extract injected directly. Repeatability is typically 4% RSD, for e.g. levoglucosan at 50 ng m(-3) in air, better for winter levels around 700 ng m(-3). Limits of detection for individual sugars are in the range 0.02-0.05 microg mL(-1) in solution, corresponding to 2-5 ng m(-3) from a 20 m(3) air sample. The overlap of arabitol and levogluocosan is overcome by using a Dionex PA-1 column, with appropriate control of eluent composition, and peak deconvolution software, allowing quantification of both sugars in difficult summer samples containing low-levels of levoglucosan. Analysis of a set of ambient aerosol samples by both GC-flame ionization detection and HPAEC-PAD shows good agreement. The new method has the advantage of requiring no sample pretreatment or derivatization and is thus well suited to handling large numbers of samples.

Atmospheric carbonaceous aerosols over grasslands of central Europe and a Boreal forest.

A labour-intensive analytical technique was applied to atmospheric particulate matter samples collected in a German urban/industrial influenced grassland location (Melpitz) and in a Finnish forest area (Hyytiälä) in order to achieve a detailed chemical speciation of the organic content. The representative nature of the solvent and water-extractable fractions was determined. The organic compounds identified in the solvent extracts are represented by primary compounds with both anthropogenic and biogenic origin, which mainly derive from the vegetation waxes and from petrogenic sources. Secondary products resulting from the oxidation of volatile organic compounds were also detected. The German meadow presented the highest levels of sugars and acidic compounds in the water extracts, whilst polyols were the most abundant class in the Finnish forest. The major compounds of these classes were malic acid, mannitol, arabitol, glucose and sucrose. Levoglucosan was also found in the water extract.