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.     

Adaptation of a speciation sampling cartridge for measuring ammonia flux from cattle feedlots using relaxed eddy accumulation

Improved measurements of ammonia losses from cattle feedlots are needed to quantify the national NH₃ emissions inventory and evaluate management techniques for reducing emissions. Speciation cartridges composed of glass honeycomb denuders and filter packs were adapted to measure gaseous NH₃ and aerosol NH₄⁺ fluxes using relaxed eddy accumulation (REA). Laboratory testing showed that a cartridge equipped with four honeycomb denuders had a total capture capacity of 1800 μg of NH₃. In the field, a pair of cartridges was deployed adjacent to a sonic anemometer and an open-path gas analyzer on a mobile tower. High-speed valves were attached to the inlets of the cartridges and controlled by a datalogger so that up- and down-moving eddies were independently sampled based on direction of the vertical wind speed and a user-defined deadband. Air flowed continuously through the cartridges even when not sampling by means of a recirculating air handling system. Eddy covariance measurement of CO₂ and H₂O, as measured by the sonic and open-path gas analyzer, were used to determine the relaxation factor needed to compute REA-based fluxes. The REA system was field tested at the Beef Research Unit at Kansas State University in the summer and fall of 2007. Daytime NH₃ emissions ranged between 68 and 127 μg m^?2 s^?1; fluxes tended to follow a diurnal pattern correlated with latent heat flux. Daily fluxes of NH₃ were between 2.5 and 4.7 g m^?2 d^?1 and on average represented 38% of fed nitrogen. Aerosol NH₄⁺ fluxes were negligible compared with NH₃ emissions. An REA system designed around the high-capacity speciation cartridges can be used to measure NH₃ fluxes from cattle feedlots and other strong sources. The system could be adapted to measure fluxes of other gases and aerosols.     

A study of the total atmospheric sulfur dioxide load using ground-based measurements and the satellite derived Sulfur Dioxide Index

We present characteristics of the sulfur dioxide (SO₂) loading over Thessaloniki, Greece, and seven other selected sites around the world using SO₂ total column measurements from Brewer spectrophotometers together with satellite estimates of the Version 8 TOMS Sulfur Dioxide Index (SOI) over the same locations, retrieved from Nimbus 7 TOMS (1979–1993), Earth Probe TOMS (1996–2003) and OMI/Aura (2004–2006). Traditionally, the SOI has been used to quantify the SO₂ quantities emitted during great volcanic eruptions. Here, we investigate whether the SOI can give an indication of the total SO₂ load for areas and periods away from eruptive volcanic activity by studying its relative changes as a correlative measure to the SO₂ total column. We examined time series from Thessaloniki and another seven urban and non-urban stations, five in the European Union (Arosa, De Bilt, Hohenpeissenberg, Madrid, Rome) and two in India (Kodaikanal, New Delhi). Based on the Brewer data, Thessaloniki shows high SO₂ total columns for a European Union city but values are still low if compared to highly affected regions like those in India. For the time period 1983–2006 the SO₂ levels above Thessaloniki have generally decreased with a rate of 0.028 Dobson Units (DU) per annum, presumably due to the European Union's strict sulfur control policies. The seasonal variability of the SO₂ total column exhibits a double peak structure with two maxima, one during winter and the second during summer. The winter peak can be attributed to central heating while the summer peak is due to synoptic transport from sources west of the city and sources in the north of Greece. A moderate correlation was found between the seasonal levels of Brewer total SO₂ and SOI for Thessaloniki, Greece (R = 0.710–0.763) and Madrid, Spain (R = 0.691) which shows that under specific conditions the SOI might act as an indicator of the SO₂ total load.     

The variability of free tropospheric ozone over Beltsville,Maryland (39N, 77W) in the summers 2004–2007

Ozone profiles are often used to investigate day-to-day and year-to-year variability in origins of free tropospheric ozone. With this in mind, more than 50 ozonesonde launches were conducted in Beltsville, MD, during the summers of 2004 through 2007. Budgets of free tropospheric ozone were calculated for each ozone profile in the four summers using a laminar identification (LID) method and unusual episodes were analyzed with respect to meteorological variables. The laminar method showed that stratosphere-to-troposphere transport (ST) accounted for greater than 50% of the free tropospheric ozone column on 17% of days sampled, a more pronounced influence than regional convective and lightning (RCL) sources. The ST origins were confirmed with trajectories, and tracers (water vapor and potential vorticity). The amount of free tropospheric ozone from ST and RCL sources varied from year-to-year (up to 13%) and can be explained by differences in mean meteorological patterns. On average, almost 30% of the free tropospheric column was attributed to ST influence, about twice as much as RCL, although the LID method may not capture weeks-old lightning influences as in a chemical model. The prevalence of ST ozone in summertime Beltsville soundings was similar to six sounding sites in the IONS-04 campaign [Thompson, A.M., et al., 2007b. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 1. Summertime upper tropospheric/lower stratosphere ozone over northeastern North America. J. Geophys. Res. 112, D12S12; Thompson, A.M., et al., 2007c. Intercontinental Transport Experiment Ozonesonde Network Study (IONS, 2004): 2. Tropospheric ozone budgets and variability over northeastern North America. J. Geophys. Res. 112, D12S13.] and to statistics from a 30 year climatology of European soundings [Collette, A., Ancellet, G., 2005. Impact of vertical transport processes on the tropospheric ozone layering above Europe. Part II: Climatological analysis of the past 30 years. Atmos. Environ. 39, 5423–5435]. The Beltsville record also demonstrated the value of soundings for air quality forecasting in an urban area. The 22 nighttime soundings collected over Beltsville in 2004–2007 can be divided into distinct polluted and unpolluted subsets, the former 20 ppbv higher in residual layer ozone (1 km) than the latter. These distinctions propagated to daytime differences of 10 ppbv at the surface in the Washington, DC, area, with the high-ozone residual layers leading to non-attainment of the National Ambient Air Quality Standard for ozone. More frequent ozone observations aloft appear essential for better understanding ozone variability and for enabling air quality modelers to achieve more accurate ozone forecasts.     

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.     

Can we trust odor databases? Example of t- and n-butyl acetate

The US EPA has exempted t-butyl acetate from VOC regulations, which increases the likelihood that it may replace other solvents in some settings. This investigation probes its chemosensory properties. In Study 1, subjects (n = 29) sought to detect the odor of t-butyl acetate and of n-butyl acetate in forced-choice testing of stable concentrations, analytically confirmed. Subjects sniffed from cones with a high enough volumetric flow to insure against dilution by nonodorized air. A subject made hundreds of judgments, enough for a psychometric function for each material. The points of 50% detection above chance (“threshold”) occurred at 8 and 2 ppb for t-butyl acetate and n-butyl acetate, respectively. In study 2, subjects (n = 26) sought to detect vapor with the eye via chemesthesis (sensory irritation) in 10-s exposures. Detection at 50% occurred at 177 and 113 ppm for t-butyl acetate and n-butyl acetate, respectively, more than 10,000 times above that for odor detection. The protocols produced results of uncommon precision compared to those in often-misleading archival databases. The nose exhibits much higher sensitivity than the databases indicate. The collections rarely exhibit accuracy better than ±1000%. Collection of accurate data for a VOC can ironically bring on stricter regulation for just it, a situation that calls for a strategy to improve the database by collection of new data, importation of better data, and development of quantitative structure–activity modeling.     

Assessment of source apportionment by Positive Matrix Factorization analysis on fine and coarse urban aerosol size fractions

This study was conducted in order to investigate the differences observed in source profiles in the urban environment, when chemical composition parameters from different aerosol size fractions are subjected to factor analysis. Source apportionment was performed in an urban area where representative types of emission sources are present. PM₁₀ and PM₂ samples were collected within the Athens Metropolitan area and analysed for trace elements, inorganic ions and black carbon. Analysis by two-way and three-way Positive Matrix Factorization was performed, in order to resolve sources from data obtained for the fine and coarse aerosol fractions. A difference was observed: seven factors describe the best solution in PMF3 while six factors in PMF2. Six factors derived from PMF3 analysis correspond to those described by the PMF2 solution for the fine and coarse particles separately. These sources were attributed to road dust, marine aerosol, soil, motor vehicles, biomass burning, and oil combustion. The additional source resolved by PMF3 was attributed to a different type of road dust. Combustion sources (oil combustion and biomass burning) were correctly attributed by PMF3 solely to the fine fraction and the soil source to the coarse fraction. However, a motor vehicle's contribution to the coarse fraction was found only by three-way PMF. When PMF2 was employed in PM₁₀ concentrations the optimum solution included six factors. Four source profiles corresponded to the previously identified as vehicles, road dust, biomass burning and marine aerosol, while two could not be clearly identified. Source apportionment by PMF2 analysis based solely on PM₁₀ aerosol composition data, yielded unclear results, compared to results from PMF2 and PMF3 analyses on fine and coarse aerosol composition data.     

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.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.     

Evaluating the efficacy of wood shreds for mitigating erosion

An erosion control product made by shredding on-site woody materials was evaluated for mitigating erosion through a series of rainfall simulations. Tests were conducted on bare soil and soil with 30, 50, and 70% cover on a coarse and a fine-grained soil. Results indicated that the wood product known as wood shreds reduced runoff and soil loss from both soil types. Erosion mitigation ranged from 60 to nearly 100% depending on the soil type and amount of concentrated flow and wood shred cover. Wood shreds appear to be a viable alternative to agricultural straw. A wood shred cover of 50% appears optimal, but the appropriate coverage rate will depend on the amount of expected concentrated flow and soil type.