Modeling the surface–atmosphere exchange of ammonia

New parameterizations for surface–atmosphere exchange of ammonia are presented for application in atmospheric transport models and compared with parameterizations of the literature. The new parameterizations are based on a combination of the results of three years of ammonia flux measurements over a grassland canopy (dominated by Lolium perenne and Poa trivialis) near Wageningen, the Netherlands and existing parameterizations from literature. First, a model for the surface–atmosphere exchange of ammonia that includes the concentration at the external leaf surface is derived and validated. Second, a parameterization for the stomatal compensation point (expressed as Γ_s, the ratio of [NH₄⁺]/[H⁺] in the leaf apoplast) that accounts for the observed seasonal variation is derived from the measurements. The new, temperature-dependent Γ_s describes the observed seasonal behavior very well. It is noted, however, that senescence of plants and field management practices will also influence the seasonal variation of Γ_s on a shorter timescale. Finally, a relation that links Γ_s to the atmospheric pollution level of the location through the ‘long-term’ NH₃ concentration in the air is proposed.     

Ambient TSP concentration and dustfall in major cities of China: Spatial distribution and temporal variability

Based on environmental monitoring data in 93 major cities and meteorological records at 398 weather stations in China from 1981 to 2007, total suspended particle (TSP) concentration, the intensity of dustfall, and sand and dust storm frequency (F_d) were analysed. During the past 27 years, the annual average TSP concentration (C_TSP) in 93 cities was 402 μg m^?3. Annual average C_TSP decreased from the north to the south and from inland to the coast areas with a peak value of 628.8 μg m^?3 in Lanzhou. In the 1980s, 1990s and 2000s, annual average C_TSP was 628.7, 319.2, and 250.1 μg m^?3, respectively. Annual average intensity of dustfall (I_d) was 240.5 t km^?2 a^?1, decreased from northern to southern China and from inland to the coast areas with the maximum value of 717.2 t km^?2 a^?1 in Baotou. In the 1980s, 1990s and 2000s, annual average I_d was 334.8, 220.9, 146 t km^?2 a^?1 respectively. Annual average I_d in the Loess Plateau region was commonly higher than 200 t km^?2 a^?1. The annual average F_d decreased from arid regions in northwestern China to humid areas in southeastern China with two sand and sand storm centers existing in Xinjiang Taklamakan Desert and western Inner Mongolia. The annual average F_d in the 1980s, 1990s, 2000s was 16, 8, 6 days respectively, decreased steadily from 18 days in 1981–5 days in 2007. Annual average I_d had a positive linear relation to annual average C_TSP (R² = 0.96). Annual average F_d had a positive relation with annual average C_TSP (R² = 0.97) as well as annual average I_d (R² = 0.94). TSP was the chief pollutant influencing Air Pollution Index (API) in northern China in spring and winter seasons. Sand and dust storm might be a major factor affecting the temporal variability and spatial distribution of TSP and dustfall in China.     

Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston,Texas

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from emission sources in the urban surface layer. We describe a new relaxed eddy accumulation (REA) system combined with a dual-channel GC-FID used for VOC flux measurements, focusing on benzene, toluene, ethylbenzene and xylenes (BTEX) results. Ambient air sampled from 60 m above the ground next to a sonic anemometer was subsampled by a membrane pump and pushed into an REA valve system with two Teflon bag reservoirs, then transferred to two preconcentration units for thermal desorption. We discuss the performance of our system and the selected BTEX measurement results using approximately 8 weeks of data (May 22–July 22, 2008), presenting diurnal variations of concentrations and fluxes of these traffic tracers. The measured values exhibited diurnal cycles with dominant morning and midday peaks during weekdays related to rush hour traffic and additional weekday daytime toluene and xylenes emissions. Local evaporative emissions, likely from solvent usage, significantly contributed to the measured fluxes. We upscaled measured emissions to the county level using a high resolution land cover data set and compared the results with EPA’s National Emission Inventory (NEI).     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

Chemical mass balance source apportionment for combined PM2.5 measurements from U.S. non-urban and urban long-term networks

The Minnesota Particulate Matter 2.5 (PM_2.5) Source Apportionment Study was undertaken to explore the utility of PM_2.5 mass, element, ion, and carbon measurements from long-term speciation networks for pollution source attribution. Ambient monitoring data at eight sites across the state were retrieved from the archives of the Interagency Monitoring of Protected Visual Environments (IMPROVE) and the Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and analyzed by an Effective Variance – Chemical Mass Balance (EV-CMB) receptor model with region-specific geological source profiles developed in this study. PM_2.5 was apportioned into contributions of fugitive soil dust, calcium-rich dust, taconite (low grade iron ore) dust, road salt, motor vehicle exhaust, biomass burning, coal-fired utility, and secondary aerosol. Secondary sulfate and nitrate contributed strongly (49–71% of PM_2.5) across all sites and was dominant (≥60%) at IMPROVE sites. Vehicle exhausts accounted for 20–70% of the primary PM_2.5 contribution, largely exceeding the proportion in the primary PM_2.5 emission inventory. The diesel exhaust contribution was separable from the gasoline engine exhaust contribution at the STN sites. Higher detection limits for several marker elements in the STN resulted in non-detectable coal-fired boiler contributions which were detected in the IMPROVE data. Despite the different measured variables, analytical methods, and detection limits, EV-CMB results from a nearby IMPROVE-STN non-urban/urban sites showed similar contributions from regional sources – including fugitive dust and secondary aerosol. Seasonal variations of source contributions were examined and extreme PM_2.5 episodes were explained by both local and regional pollution events.     

Evaluation of limits for effective flame acceleration in hydrogen mixtures

Results of experiments and data analysis on turbulent flame propagation in obstructed channels are presented. The data cover a wide range of mixtures: H₂/air, H₂/air/steam (from lean to rich) at normal and elevated initial temperatures (from 298 to 650 K) and pressures (from 1 to 3 bar); and stoichiometric H₂/O₂ mixtures diluted with N₂, Ar, He and CO₂ at normal initial conditions. The dataset chosen also covers a wide range of scales exceeding two orders of magnitude. It is shown that basic flame parameters, such as mixture expansion ratio σ, Zeldovich number β and Lewis number Le, can be used to estimate a priori a potential for effective flame acceleration for a given mixture. Critical conditions for effective flame acceleration are suggested in the form of correlations of critical expansion ratio σ^* versus dimensionless effective activation energy. On this basis, limits for effective flame acceleration for hydrogen combustibles can be estimated. Uncertainties in determination of critical σ^* values are discussed.     

Simulating Land-Cover Change in Montane Mainland Southeast Asia

We used the conversion of land use and its effects (CLUE-s) model to simulate scenarios of land-cover change in Montane mainland southeast Asia (MMSEA), a region in the midst of transformation due to rapid intensification of agriculture and expansion of regional trade markets. Simulated changes affected approximately 10 % of the MMSEA landscape between 2001 and 2025 and 16 % between 2001 and 2050. Roughly 9 % of the current vegetation, which consists of native species of trees, shrubs, and grasses, is projected to be replaced by tree plantations, tea, and other evergreen shrubs during the 50 years period. Importantly, 4 % of this transition is expected to be due to the expansion of rubber (Hevea brasiliensis), a tree plantation crop that may have important implications for local-to-regional scale hydrology because of its potentially high water consumption in the dry season.     

Capacity of biochar application to maintain energy crop productivity: soil chemistry, sorghum growth, and runoff water quality effects

Pyrolysis of crop biomass generates a by-product, biochar, which can be recycled to sustain nutrient and organic C concentrations in biomass production fields. We evaluated effects of biochar rate and application method on soil properties, nutrient balance, biomass production, and water quality. Three replications of eight sorghum [ (L.) Moench] treatments were installed in box lysimeters under greenhouse conditions. Treatments comprised increasing rates (0, 1.5, and 3.0 Mg ha) of topdressed or incorporated biochar supplemented with N fertilizer or N, P, and K fertilizer. Simulated rain was applied at 21 and 34 d after planting, and mass runoff loss of N, P, and K was measured. A mass balance of total N, P, and K was performed after 45 d. Returning 3.0 Mg ha of biochar did not affect sorghum biomass, soil total, or Mehlich-3-extractable nutrients compared to control soil. Yet, biochar contributed to increased concentration of dissolved reactive phosphorus (DRP) and mass loss of total phosphorus (TP) in simulated runoff, especially if topdressed. It was estimated that up to 20% of TP in topdressed biochar was lost in surface runoff after two rain events. Poor recovery of nutrients during pyrolysis and excessive runoff loss of nutrients for topdressed biochar, especially K, resulted in negative nutrient balances. Efforts to conserve nutrients during pyrolysis and incorporation of biochar at rates derived from annual biomass yields will be necessary for biochar use in sustainable energy crop production.     

Influence of biochar on nitrogen fractions in a coastal plain soil

Interest in the use of biochar from pyrolysis of biomass to sequester C and improve soil productivity has increased; however, variability in physical and chemical characteristics raises concerns about effects on soil processes. Of particular concern is the effect of biochar on soil N dynamics. The effect of biochar on N dynamics was evaluated in a Norfolk loamy sand with and without NHNO. High-temperature (HT) (≥500°C) and low-temperature (LT) (≤400°C) biochars from peanut hull ( L.), pecan shell ( Wangenh. K. Koch), poultry litter (), and switchgrass ( L.) and a fast pyrolysis hardwood biochar (450-600°C) were evaluated. Changes in inorganic, mineralizable, resistant, and recalcitrant N fractions were determined after a 127-d incubation that included four leaching events. After 127 d, little evidence of increased inorganic N retention was found for any biochar treatments. The mineralizable N fraction did not increase, indicating that biochar addition did not stimulate microbial biomass. Decreases in the resistant N fraction were associated with the high pH and high ash biochars. Unidentified losses of N were observed with HT pecan shell, HT peanut hull, and HT and LT poultry litter biochars that had high pH and ash contents. Volatilization of N as NH in the presence of these biochars was confirmed in a separate short-term laboratory experiment. The observed responses to different biochars illustrate the need to characterize biochar quality and match it to soil type and land use.     

Switchgrass biochar affects two aridisols

The use of biochar has received growing attention because of its ability to improve the physicochemical properties of highly weathered Ultisols and Oxisols, yet very little research has focused on its effects in Aridisols. We investigated the effect of low or high temperature (250 or 500°C) pyrolyzed switchgrass () biochar on two Aridisols. In a pot study, biochar was added at 2% w/w to a Declo loam (Xeric Haplocalcids) or to a Warden very fine sandy loam (Xeric Haplocambids) and incubated at 15% moisture content (by weight) for 127 d; a control (no biochar) was also included. Soils were leached with 1.2 to 1.3 pore volumes of deionized HO on Days 34, 62, 92, and 127, and cumulative leachate Ca, K, Mg, Na, P, Cu, Fe, Mn, Ni, Zn, NO-N, NO-N, and NH-N concentrations were quantified. On termination of the incubation, soils were destructively sampled for extractable Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Zn, NO-N, and NH-N, total C, inorganic C, organic C, and pH. Compared with 250°C, the 500°C pyrolysis temperature resulted in greater biochar surface area, elevated pH, higher ash content, and minimal total surface charge. For both soils, leachate Ca and Mg decreased with the 250°C switchgrass biochar, likely due to binding by biochar's functional group sites. Both biochars caused an increase in leachate K, whereas the 500°C biochar increased leachate P. Both biochars reduced leachate NO-N concentrations compared with the control; however, the 250°C biochar reduced NO-N concentrations to the greatest extent. Easily degradable C, associated with the 250°C biochar's structural make-up, likely stimulated microbial growth, which caused NO-N immobilization. Soil-extractable K, P, and NO-N followed a pattern similar to the leachate observations. Total soil C content increases were linked to an increase in organic C from the biochars. Cumulative results suggest that the use of switchgrass biochar prepared at 250°C could improve environmental quality in calcareous soil systems by reducing nutrient leaching potential.