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.     

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.     

Effects of Fireplace Use on Forest Vegetation and Amount of Woody Debris in Suburban Forests in Northwestern Switzerland

Urban forests are popular recreation areas in Europe. Several of these temperate broad-leaved forests also have a high conservation value due to sustainable management over many centuries. Recreational activities, particularly the use of fireplaces, can cause extensive damage to soil, ground vegetation, shrubs, and trees. Firewood collection depletes woody debris, leading to a loss of habitat for specialized organisms. We examined the effects of fireplace use on forest vegetation and the amount of woody debris by comparing disturbed and control plots in suburban forests in northwestern Switzerland. At frequently used fireplaces, we found reduced species densities in the ground vegetation and shrub layer and changes in plant species composition due to human trampling within an area of 150–200 m². Picnicking and grilling also reduced the height and changed the age structure of shrubs and young trees. The amount of woody debris was lower in disturbed plots than in control plots. Pieces of wood with a diameter of 0.6–7.6 cm were preferentially collected by fireplace users. The reduction in woody debris volume extended up to a distance of 16 m from the fire ring, covering an area of 800 m² at each picnic site. In order to preserve the ecological integrity of urban forests and to maintain their attractiveness as important recreation areas, we suggest depositing logging residues to be used as firewood and to restrict visitor movements near picnic sites.     

Epiphytische Flechten im Wandel von Immissionen und Klima ? Ergebnisse einer Vergleichskartierung 1989/2007 in Nordwestdeutschland

Zusammenfassung   Hintergrund, Ziel und Zweck Borkenbewohnende (epiphytische) Flechten reagieren sehr empfindlich auf verschiedene Umwelteinflüsse wie Stoffgehalte in der Atmosph?re und Temperaturen. Sie haben als Bioindikatoren für Luftverunreinigungen einen hohen Stellenwert bei Umweltuntersuchungen. Basierend auf einer 1989 durchgeführten Kartierung borkenbewohnender (epiphytischer) Flechten in einem landwirtschaftlich intensiv genutzten Raum Nordwestdeutschlands erfolgte 2007 eine Wiederholungsuntersuchung. Dabei galt es, m?gliche Ver?nderungen der Immissionssituation und des Klimas zu erkennen. Material und Methoden Die Studie basiert auf einer vergleichenden Kartierung epiphytischer Flechten von 355 Tr?gerb?umen an 45 Monitoringpunkten. Die angewandte Methode orientiert sich an der 1989 angewandten halb-quantitativen Erfassung. Ergebnisse Es stellten sich gravierende Ver?nderungen in der Vegetation rindenbewohnender Flechten heraus. Insgesamt war eine Erh?hung der Artenzahl an nahezu allen Monitoringpunkten festzustellen. Es wurde eine sehr starke Abnahme s?uretoleranter Arten und eine deutliche Zunahme basen- und n?hrstofffordernder Flechtenarten festgestellt. Darüber hinaus zeigte sich eine deutliche Zunahme w?rmeliebender Flechtenarten mit einem Verbreitungsschwerpunkt in Südeuropa bei gleichzeitigem Rückgang von Arten mit einem boreal-montanem Verbreitungsschwerpunkt. Diskussion Die festgestellte Entwicklung steht im Einklang mit überregionalen Beobachtungen. Sie wird im Wesentlichen auf eine gro?r?umig ver?nderte Immissionssituation, d. h. einer Abnahme der atmosph?rischen SO₂-Belastung und Zunahme der Ammoniakbelastung zurückgeführt. Ebenso treten deutliche Auswirkungen der Klimaerw?rmung hervor. Schlussfolgerungen Mit relativ geringem Untersuchungsaufwand lie?en sich Ver?nderungen bei den epiphytischen Flechten in den letzten 18 Jahren aufzeigen. Diese sind relevant für die Beurteilung regional und kleinr?umig ver?nderter Umweltbedingungen, die auch für andere Organismen und ?kosysteme l?ngerfristig von gro?er Bedeutung sind. Empfehlungen und Ausblick Unter Verwendung standardisierter Methoden vermitteln epiphytische Flechten ein differenziertes Bild der Luftbelastungssituation in Ballungsr?umen und in landwirtschaftlich genutzten Regionen. Darüber hinaus sind sie offensichtlich gute Indikatoren für Temperatur?nderungen ihrer Umgebung. Weiterer Forschungsbedarf besteht für die Verwendung epiphytischer Flechten zum Biomonitoring von Klimaver?nderungen.      

Spatial distribution of uranium and thorium in the surface soil around proposed uranium mining site at Lambapur and its vertical profile in the Nagarjuna Sagar Dam

The understanding and evaluation of the possible interactions of various naturally occurring radionuclides in the world's third largest man-made dam, Nagarjuna Sagar located in Andhra Pradesh, India and built on river Krishna assumed significance with the finding of uranium deposits in locations near the dam. For the present work, surface soil samples from the mineralized area of Lambapur, Mallapuram, Peddagattu and sediment core samples from the Nagarjuna Sagar dam were analyzed for naturally occurring radionuclides namely uranium and thorium using gamma spectrometric technique. Also toxic elements lead and chromium were analysed by the Energy Dispersive X-ray Fluorescence Spectrometer (EDXRF) technique. Surface soil samples show a variation from 25 to 291 Bq/kg (2.02–23.5 mg/kg) for ²³⁸U and 32–311 Bq/kg (7.9–76.9 mg/kg) for ²³²Th. U/Th concentration ratio in surface soil samples ranged from 0.19 to 0.31 and was found comparable with the nation wise average of 0.26. The study of sediment core samples reflected higher U/Th concentration ratio of 0.30–0.33 in the bottom section of the core as compared to 0.22–0.25 in the upper section. The concentration ratio in the upper section of the core was similar to the ratio 0.23 found in the western Deccan Basalt region through which the river originates. A higher concentration of lead and chromium was observed in the upper section of the core compared to bottom section indicating the impact of river input on the geochemical character of dam sediment.     

High time-resolved measurements of organic air toxics in different source regimes

High time-resolved (HTR) measurements can provide significant insight into sources and exposures of air pollution. In this study, an automated instrument was developed and deployed to measure hourly concentrations of 18 gas-phase organic air toxics and 6 volatile organic compounds (VOCs) at three sites in and around Pittsburgh, Pennsylvania. The sites represent different source regimes: a site with substantial mobile-source emissions; a residential site adjacent to a heavily industrialized zone; and an urban background site. Despite the close proximity of the sites (less than 13 km apart), the temporal characteristic of outdoor concentrations varied widely. Most of the compounds measured were characterized by short periods of elevated concentrations or plume events, but the duration, magnitude and composition of these events varied from site to site. The HTR data underscored the strong role of emissions from local sources on exposure to most air toxics. Plume events contributed more than 50% of the study average concentrations for all pollutants except chloroform, 1,2-dichloroethane, and carbon tetrachloride. Wind directional dependence of air toxic concentrations revealed that emissions from large industrial facilities affected concentrations at all of the sites. Diurnal patterns and weekend/weekday variations indicated the effects of the mixing layer, point source emissions patterns, and mobile source air toxics (MSATs) on concentrations. Concentrations of many air toxics were temporally correlated, especially MSATs, indicating that they are likely co-emitted. It was also shown that correlations of the HTR data were greater than lower time resolution data (24-h measurements). This difference was most pronounced for the chlorinated pollutants. The stronger correlations in HTR measurements underscore their value for source apportionment studies.