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.     

Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O₃). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O₃, total reactive nitrogen (NO_y) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O₃ and PAN concentration maxima showed a strong correlation (r² = 0.91) in LZ, with a regression slope (PAN/O₃) of 0.091 ppbv ppbv^?1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.     

Impact of large scale circulation on European summer surface ozone and consequences for modelling forecast

In this study, we investigate the benefit for European ozone simulation of using day-to-day varying chemical boundary conditions produced by a global chemical weather forecast platform instead of climatological monthly means at the frontiers of a regional model. We performed two simulations over Europe using the regional (0.5 × 0.5°) CHIMERE CTM forced by global scale simulations based on the LMDz-INCA CTM. For summer 2005, ozone differences exceeding 20 ppb can be punctually found between these two simulations in the borders of the domain. The mean of the differences ranges between 0 and 3 ppb beyond 15° of the frontiers of the regional model.Correlations with ground-based ozone measurements at more than 400 stations are slightly increased by the use of daily boundary conditions. The simulation of the temporal variability is significantly enhanced in particular for the daily means and daily maxima. As expected, the gain is higher at the borders of the regional domain.The change of percentile distribution shows that the net impact of high temporal resolution boundary conditions is not of major concern for surface ozone peaks which are mainly due to local photochemistry. The use of daily boundary conditions is however necessary to correctly simulate concentrations in the 20–35 ppb range which are of crucial interest for human and vegetation exposure effects.     

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.     

Measurement of gas-phase total peroxides at the summit of Mount Tai in China

Measurement of ambient gas-phase total peroxides was performed at the summit of Mount Tai (Mt. Tai, 1534 m above sea level) in central-eastern China during March 22–April 24 and June 16–July 20, 2007. The hourly averaged concentration of peroxides was 0.17 ppbv (± 0.16 ppbv, maximum: 1.28 ppbv) and 0.55 ppbv (± 0.67 ppbv, maximum: 3.55 ppbv) in the spring and summer campaigns, respectively. The average concentration of peroxides at Mt. Tai, which is in a heavily polluted region, was much lower than hydrogen peroxide measurements made at some rural mountain sites, suggesting that significant removal processes took place in this region. An examination of diurnal variation and a correlation analysis suggest that these removal processes could include chemical suppression of peroxide production due to the scavenging of peroxy and hydroxy radicals by high NO_x, wet removal by clouds/fogs rich in dissolved sulfur dioxide which reacts quickly with peroxides, and photolysis. These sinks competed with photochemical sources of peroxides, resulting in different mean concentrations and diurnal pattern of peroxides in the spring and summer. A principal component analysis was conducted to quantify the major processes that influenced the variation of peroxide concentrations. This analysis shows that in the spring photochemical production was an important source of peroxides, and the major sink was scavenging during upslope transport of polluted and humid air from the lower part of the planetary boundary layer (PBL) and wet removal by synoptic scale clouds. During the summer, highly polluted PBL air (with high NO_x) was often associated with very low peroxides due to the chemical suppression of HO₂ by high NO_x and wet-removal by clouds/fogs in this sulfur-rich atmosphere, especially during the daytime. Higher concentrations of peroxides, which often appeared at mid-nighttime, were mainly associated with subsidence of air masses containing relatively lower concentrations of NO_y.     

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.     

A validated 2-D diffusion–advection model for prediction of drift from ground boom sprayers

Correct field drift prediction is a key element in environmental risk assessment of spraying applications. A reduced order drift prediction model based on the diffusion–advection equation is presented. It allows fast assessment of the drift potential of specific ground boom applications under specific environmental wind conditions that obey the logarithmic wind profile. The model was calibrated based on simulations with a validated Computational Fluid Dynamics (CFD) model. Validation of both models against 38 carefully conducted field experiments is successfully performed for distances up to 20 m from the field edge, for spraying on flat pasture land. The reduced order model succeeded in correct drift predictions for different nozzle types, wind velocities, boom heights and spray pressures. It used 4 parameters representing the physical aspects of the drift cloud; the height of the cloud at the field edge, the mass flux crossing the field edge, the settling velocity of the droplets and the turbulence. For the parameter set and range considered, it is demonstrated for the first time that the effect of the droplet diameter distribution of the different nozzle types on the amount of deposition spray drift can be evaluated by a single parameter, i.e., the volume fraction of droplets with a diameter smaller than 191 μm. The reduced order model can be solved more than 4 orders of magnitude faster than the comprehensive CFD model.     

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.     

Analysis of cloud and precipitation chemistry at Whiteface Mountain,NY

Federal and state programs over the past two decades have resulted in the reduction of emissions of precursors of acid rain. Concomitant with these changes, measured concentrations of acidity in precipitation and in watersheds have shown a downward trend or improvement. However, another pathway for these precursors is through cloud and fog events that often tend to occur at high-elevation regions affecting the fauna and flora as well. In this study we report on long-term measurements of cloud water and precipitation chemistry made from 1994 onwards at a high-elevation location, Whiteface Mountain NY, in the northeastern United States. Trends and inter-relationship between the ions were examined along with ambient SO₂ measurements and Adirondack lakes chemistry data.     

Night-time radical chemistry during the TORCH campaign

We present one of the most comprehensive studies of night-time radical chemistry to date, from the Tropospheric ORganic CHemistry experiment (TORCH) in the summer of 2003. TORCH provided a wealth of measurements with which to study the oxidizing capacity of the atmosphere. The measurements provided input to a zero-dimensional box model which has been used to study night-time radical chemistry during the campaign. Average night-time predicted concentrations of OH (2.6 × 10⁵ molecule cm^?3), HO₂ (2.9 × 10⁷ molecule cm^?3) and [HO₂+ΣRO₂] radicals (2.2 × 10⁸ molecule cm^?3) were an order of magnitude smaller than those predicted during the daytime. The model under-predicted the night-time measurements of OH, HO₂ and [HO₂+ΣRO₂] radicals, on average by 41%, 16% and 8% respectively. Whilst the model captured the broad features of night-time radical behaviour, some of the specific features that were observed are hard to explain. A rate of radical production assessment was carried out for the whole campaign between the hours of 00:00 and 04:00. Whilst radical production was limited owing to the absence of photolytic reactions, production routes via the reactions of alkenes with O₃ provided an effective night-time radical source. Nitrate radical concentrations were predicted to be 0.6 ppt on average with a peak of 18 ppt on August 9th during a polluted heat wave period. Overall, the nitrate radical contributes about a third of the total initiation via RO₂, mostly through reaction with alkenes.