Relationship between leaf antioxidants and ozone injury in Nicotiana tabacum ‘Bel-W3’ under environmental conditions in São Paulo,SE – Brazil

Previous studies have reported that the extent of leaf injury in Nicotiana tabacum “Bel-W3” exposed to environmental conditions in the city of São Paulo is influenced by weather conditions. This influence may occur by means of antioxidant responses. Thus, this study aimed to evaluate whether daily antioxidant responses to environmental variations interfere on the progression of leaf injury on plants of this cultivar during their exposure in a state park of São Paulo and to determine a linear combination of variables, among antioxidants and environmental factors, which mostly explain this visible response. Plants were exposed at the mentioned site for 14 days in four different experiments. During each experiment, three plants were daily sampled to determine the accumulated percentage of leaf area affected by necrosis and antioxidant responses (concentrations of total ascorbic acid (AA) and activity of superoxide dismutase (SOD) and peroxidases (POD)). Ozone concentrations and weather conditions were also daily measured. Pearson correlations and multivariate analyses assessed the relationship between biological and environmental variables. Leaf injury appeared between the 3rd and 6th days of exposure and increased over the exposure periods. The daily concentrations of AA tended to decrease with time of exposure in all experiments, but the activity of SOD and POD oscillated during plant exposure. Positive correlations were observed between AA or SOD and O₃ concentrations, as well as negative correlations between AA and air temperature. The increasing percentage of leaf necrosis across the whole period was explained by decreasing levels of AA 2 days before injury estimation and by higher O₃ concentrations 5 days before (R² = 0.36; p < 0.001). The use of N. tabacum Bel-W3 as a bioindicator can be restricted by leaf antioxidant responses to both atmospheric contamination and weather conditions.     

Ultrafine particle fluxes above four major European cities

Little information is known about the behaviour of ultrafine particles (UFP) on a citywide scale. Total particle number flux, dominated by UFP, and other meteorological parameters were collected from tower sites in Manchester, London, Edinburgh and Gothenburg between 1999 and 2006 using the eddy covariance technique. Averaged diurnal cycles were produced for particle number flux, concentration, sensible heat flux, emission velocity, friction velocity, wind speed and temperature. UFP flux cycles showed clear diurnal trends which were linked to traffic activity and local sources. Wind sector analysis showed contributions to flux from local heavily urbanised areas. A simple parameterised model linking UFP flux to traffic activity, sensible heat and friction velocity above the city was produced.     

Ultrafine particles near a major roadway in Raleigh,North Carolina: Downwind attenuation and correlation with traffic-related pollutants

Ultrafine particles (UFPs, diameter < 100 nm) and co-emitted pollutants from traffic are a potential health threat to nearby populations. During summertime in Raleigh, North Carolina, UFPs were simultaneously measured upwind and downwind of a major roadway using a spatial matrix of five portable industrial hygiene samplers (measuring total counts of 20–1000 nm particles). While the upper sampling range of the portable samplers extends past the defined “ultrafine” upper limit (100 nm), the 20–1000 nm number counts had high correlation (Pearson R = 0.7–0.9) with UFPs (10–70 nm) measured by a co-located research-grade analyzer and thus appear to be driven by the ultrafine range. Highest UFP concentrations were observed during weekday morning work commutes, with levels at 20 m downwind from the road nearly fivefold higher than at an upwind station. A strong downwind spatial gradient was observed, linearly approximated over the first 100 m as an 8% drop in UFP counts per 10 m distance. This result agreed well with UFP spatial gradients estimated from past studies (ranging 5–12% drop per 10 m). Linear regression of other vehicle-related air pollutants measured in near real-time (10-min averages) against UFPs yielded moderate to high correlation with benzene (R² = 0.76), toluene (R² = 0.49), carbon monoxide (R² = 0.74), nitric oxide (R² = 0.80), and black carbon (R² = 0.65). Overall, these results support the notion that near-road levels of UFPs are heavily influenced by traffic emissions and correlate with other vehicle-produced pollutants, including certain air toxics.     

Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

Evaluation and application of biomagnetic monitoring of traffic-derived particulate pollution

Inhalation of particulate pollutants below 10 μm in size (PM₁₀) is associated with adverse health effects. Here we use magnetic remanence measurements of roadside tree leaves to examine levels of vehicle-derived PM around Lancaster, UK. Leaf saturation remanence (SIRM) values exhibit strong correlation with both the SIRM and particulate mass of co-located, pumped-air samples, indicating that these leaf magnetic values are an effective proxy for ambient PM₁₀ concentrations. Biomagnetic monitoring using tree leaves can thus provide high spatial resolution data sets for assessment of particulate pollution levels at pedestrian-relevant heights. Leaf SIRM values not only increase with proximity to roads with higher traffic volumes, but are also ～100% higher at 0.3 m than at ～1.5–2 m height. Magnetic and SEM data indicate that the particle populations are dominated by spherical, iron-rich particles ～0.1–1 μm in diameter, with fewer larger, more angular, silica-rich particles. Comparison of the roadside leaf-calculated PM₁₀ concentrations with PM₁₀ concentrations predicted by a widely-used atmospheric dispersion model indicates some agreement between them. However, the model under-predicts PM₁₀ concentrations at ‘urban hotspots’ such as major–minor road junctions and traffic lights. Conversely, the model over-predicts PM₁₀ concentrations with distance from the road wherever one tree is screened by another, indicating the filtering/protective effect of roadside trees in leaf.     

Influence of air mass source region on nanoparticle events and hygroscopicity in central Virginia,U.S.

During autumn, 2006, variation in the frequency of aerosol nucleation events, as inferred from nanoparticle growth events, and associated hygroscopicity were investigated as a function of air mass transport history at a mixed deciduous forest in central Virginia, U.S. Above-canopy size distributions of aerosols between 0.012 and 0.700 μm diameter, size-resolved particle hygroscopicity at eight dry diameters between 0.012 and 0.400 μm, and cloud condensation nuclei (CCN) activity were characterized. Air mass back trajectories were clustered to identify source regions. Growth events were most frequent in fast-moving air masses (mean = 9 m s^?1) that originated over the north central U.S. Under these flow regimes, mean values for preexisting sub-μm aerosol number concentrations (4700 cm^?3), corresponding surface area (142 μm² cm^?3), air temperature (6.2 °C), and relative humidity (RH, 49.4%) were relatively low compared to other regimes. Under stagnant flow conditions (mean = 3 m s^?1), mean number concentrations were higher (>6000 cm^?3) and size fractions <0.1 μm diameter exhibited enhanced hygroscopicity compared to other source regions. These results indicate that precursors emitted into relatively clean, cold, and dry air transported over the southeastern U.S. reacted to form condensable intermediates that subsequently produced new aerosols via nucleation and growth. This pathway was an important source for CCN. During events in October, nanoparticles were produced in greater numbers and grew more rapidly compared to November and December.     

Near roadway concentrations of organic source markers

Concentrations of elemental carbon (EC), organic carbon (OC), and 33 organic source markers (12 alkanes, 18 polycyclic aromatic hydrocarbons and ketones, and 3 hopanes) are reported near a highway in Raleigh, NC with an annual average daily traffic count of approximately 125,000 vehicles. Daily samples (24-h) were collected at two locations, one approximately 10 m and the other 275 m perpendicular from the road. Concentrations of OC were similar between near (mean = 7.6 μg m^?3) and far (8.0 μg m^?3) locations, but concentrations of most organic species at the near site were between 1.5 and 2 times higher than those at the far site.     

Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

Temperature dependence of secondary organic aerosol

Temperature was found to have a dramatic effect on secondary organic aerosol formation from two ozonolysis systems, cyclohexene and α-pinene. Isothermal experiments were conducted for both systems where the lowest temperature, 278 K, formed approximately 2.5–3 times and 5–6 times the SOA formed at 300 K and 318 K, respectively. Changing the cyclohexene system temperature to a different isothermal experimental set point after completion of SOA formation did not lead to sufficient condensation/evaporation to reproduce the SOA formation at other temperature set points. When the system temperature was cycled between two set points at the end of an experiment, the α-pinene system showed reversibility between the initial temperature 318 K and 300 K. For temperature cycles between the initial temperature of 300 K–318 K, an irreversible loss of mass is observed after the first heating cycle with reversibility observed between subsequent temperature cycles. The SOA formed at 278 K was reversible over a 22 K range but was unable to evaporate sufficiently to match the SOA mass formed at 300 K. Hygroscopicity measurements, taken after the completion of SOA formation, indicate that hygroscopicity of the aerosol is also a function of temperature and that the aerosol does not continue to be oxidized after initial growth is complete. The differing hygroscopicity of the semi-volatile component of the aerosol is evident during system temperature changes after completion of the experiment.