Intercalibration of a passive wind-vane flux sampler against a continuous-flow denuder for the measurements of atmospheric ammonia concentrations and surface exchange fluxes

A passive wind-vane flux sampler is a simple low-cost device used to estimate long-term vertical fluxes of ammonia in the atmospheric surface boundary layer. The passive flux sampler measures the horizontal flux of ammonia. A vertical gradient of the horizontal flux, combined with micro-meteorological measurements of wind speed and temperature, is used to estimated the vertical flux of ammonia using a modified aerodynamic gradient technique. The passive wind-vane flux sampler gradient was calibrated against a gradient measured with fast response (6 min) continuous-flow denuders. The measurements were carried out at a heathland located in an intensive farming area in the centre of the Netherlands. A field campaign took place over 70 day period in the summer of 1996, during which the sampling periods of the passive wind-vane flux sampler varied between 3 and 9 days. The comparison clearly showed that the long-term measurements with the passive wind-vane flux samplers gave accurate average ammonia deposition values for the field campaign as a whole which deviated by only 18% from the reference flux. However, there was no significant correlation between the fluxes from the passive samplers and the reference method for the individual 10 periods which were compared. Possible explanations found for the lacking correlation were (I) a high percentage number of half-hour emission events within each period resulted in a significant large relative deviation between the fluxes, and (II) uncertainties in the reference method might also explain the lacking correlation. The passive wind-vane flux samplers proved to be a stable method for long-term measurements (months to years) due to a close to 100% optimal functioning during the field campaign.     

Estimation of the net air-sea flux of ammonia over the southern bight of the North Sea

Measurements of airborne gaseous ammonia and total dissolved ammonium in sea water determined on cruises on the North Sea have been used to calculate net fluxes of ammonia between air and sea. The system is finely balanced with the majority of net fluxes from air to sea, but some periods occur when the sea becomes a net source of ammonia in air. Examination of the field data suggests that the main factor determining the direction of flux is the airborne ammonia concentration, which when elevated causes ammonia deposition to the sea. It is calculated that ammonia deposition to the southern bight of the North Sea (below 56°N) amounts to 7.6 x 103 tonnes N per year, about one-half of an earlier upper limit estimate. Comparison with studies from the Pacific Ocean, in which the sea acts as a source of atmospheric ammonia, reveals that the major differences arise from much higher concentrations of airborne ammonia in the North Sea atmosphere caused by advection from adjacent land.     

Evaluation of a diode laser based photoacoustic instrument combined with preconcentration sampling for measuring surface–atmosphere exchange of ammonia with the aerodynamic gradient method

We present here a novel instrument for measuring surface–atmosphere exchange fluxes of ammonia. The instrument is the upgraded version of a recently developed near-infrared diode laser based photoacoustic ammonia concentration monitoring instrument, i.e. the original instrument is supplemented with two additional sampling lines, an appropriate gas handling system and an advanced software controlling gradient measurements. As a result of these developments, ammonia concentration can be measured simultaneously at three different heights above the ground and ammonia fluxes can be calculated from these data using the aerodynamic gradient method. The instrument operates fully automatically, requires minimal maintenance and has a temperature controlled, waterproof housing which makes it suitable for measurements even under harsh field conditions. Preliminary tests on stability and accuracy were carried out during two two-week field measurement campaigns, with the three sampling inlets being placed at the same height together with the inlet of a reference instrument. The readings of the three channels agreed well (with correlation coefficients above 0.96). Comparison to reference instruments showed good stability of the photoacoustic instrument, there was no measurable zero-drift or change in sensitivity during the tests. Flux measurements were carried out during a three-week field campaign in southern Scotland over fertilized grassland with reference to a wet-chemical AMANDA instrument in gradient configuration. Ammonia fluxes calculated from the data of the two instruments agreed well. Fluxes up to 2500 ng m^?2 s^?1 were observed after fertilization. The minimum detectable ammonia flux was calculated on the basis of “virtual ammonia fluxes”, from measurements carried out with all inlets at the same height and was found to be ±60 ng m^?2 s^?1 which ensures reliable measurements above intensively managed grasslands or agricultural fields.     

Estimation of NH3 bi-directional flux from managed agricultural soils

The Community Multi-Scale Air Quality model (CMAQ) is used to assess regional air quality conditions for a wide range of chemical species throughout the United States (U.S.). CMAQ representation of the regional nitrogen budget is limited by its treatment of ammonia (NH₃) soil emission from, and deposition to underlying surfaces as independent rather than tightly coupled processes, and by its reliance on soil emission estimates that do not respond to variable meteorology and ambient chemical conditions. The present study identifies an approach that addresses these limitations, lends itself to regional application, and will better position CMAQ to meet future assessment challenges. These goals were met through the integration of the resistance-based flux model of Nemitz et al. (2001) with elements of the United States Department of Agriculture EPIC (Environmental Policy Integrated Climate) model. Model integration centers on the estimation of ammonium and hydrogen ion concentrations in the soil required to estimate soil NH₃ flux. The EPIC model was calibrated using data collected during an intensive 2007 field study in Lillington, North Carolina. A simplified process model based on the nitrification portion of EPIC was developed and evaluated. It was then combined with the Nemitz et al. (2001) model and measurements of near-surface NH₃ concentrations to simulate soil NH₃ flux at the field site. Finally, the integrated flux (emission) results were scaled upward and compared to recent national ammonia emission inventory estimates. The integrated model results are shown to be more temporally resolved (daily), while maintaining good agreement with established soil emission estimates at longer time-scales (monthly). Although results are presented for a single field study, the process-based nature of this approach and NEI comparison suggest that inclusion of this flux model in a regional application should produce useful assessment results if nationally consistent sources of driving soil and agricultural management information are identified.     

Measuring ammonia emissions from land applied manure: an intercomparison of commonly used samplers and techniques

A number of techniques have been developed to quantify ammonia (NH(3)) emissions following land application of manure or fertiliser. In this study, coefficients of variation were determined for three commonly used field techniques (mass balance integrated horizontal flux, wind tunnels and the equilibrium concentration technique) for measuring emissions from a range of manure types. Coefficients of variation (CV) for absorption flasks, passive flux samplers and passive diffusion samplers were 21, 10 and 14%, respectively. In comparative measurements, concentrations measured using passive flux samplers and absorption flasks did not differ significantly, but those measured using passive diffusion samplers were on average 1.8 times greater. The mass balance technique and wind tunnels gave broadly similar results in two out of four field tests. Overexposure of passive diffusion samplers for some sampling periods meant that estimation of cumulative NH(3) emission using the equilibrium concentration technique in the field tests could not be made. For cumulative NH(3) emissions, CVs were in the range of 23-52, 46-74 and 21-39% for the mass balance, wind tunnel and equilibrium concentration techniques, respectively. Lower CVs were associated with measurements following slurry compared with solid manure applications. Our conclusions from this study are that for the measurement of absolute emissions the mass balance technique is to be preferred, and for small-plot comparative measurements the wind tunnel system is preferred to the equilibrium concentration technique.     

New particle formation of ternary droplets in the atmosphere — a steady-state nucleation kinetics approach

A self-consistent expression for the kinetics of ternary nucleation is developed based on the nucleation flux theory derived by Langer, 1969, Annals of Physics 54, 258–275. The method for obtaining the ternary nucleation flux is based on the solution of a Fokker–Planck equation for the concentration of clusters where both number and cluster energy fluctuations are included. The theory is applied to a nonideal solution of water–sulphuric acid that is nonideally mixed with ammonia. The nucleation rates predicted for this ternary system studied show a considerable increase on the nucleation rate compared to the binary water–sulphuric acid system for gaseous concentrations of ammonia which are likely to occur in the atmosphere. The results of the present study are in qualitative agreement with current laboratory and theoretical studies where a considerable enhancement in the nucleation rate is observed with the addition of tens of parts per trillion by volume of NH₃ in the binary H₂SO₄–H₂O system.     

氨水土壤混合物脱除CO2温室气体的实验研究

为了脱除CO2温室气体,提出了利用氨水土壤混合物去除CO2的新方法。分别考察了土壤颗粒粒径、CO2初始流量、氨水浓度（质量比）和温度对CO2脱除量和脱除率的影响。实验结果表明,该方法去除CO2的量较土壤物理吸附量和氨水化学吸收量的总和提高了大约15%;随着氨水浓度的增大,CO2的脱除率和脱除量都增大;随着土壤颗粒粒径和CO2初始流量的增大,CO2的脱除率和脱除量都减小;当温度由22℃升高到31℃,CO2的脱除率随着温度的升高而增大,但是继续升高温度到40℃,CO2的脱除率反而下降。     

Measuring chemical emissions using open-path Fourier transform infrared (OP-FTIR) spectroscopy and computer-assisted tomography

This paper reports on a field study that was part of a large-scale, multi-seasonal research study with the North Carolina Department of Environment, Health, and Natural Resources, to measure nitrogen emissions from an intensive swine confinement facility. The study measured emission rates using tracer gases and a horizontal network of open-path Fourier transform infrared (FTIR) optical rays placed less than a meter above the surface of an approximately 6 acre intensive swine waste lagoon in Eastern North Carolina. This network of rays simultaneously monitored the ammonia and the tracer gases every 2 min. The open-path measurements were combined with the mathematical mapping techniques of computer-assisted tomography (CAT) to create two-dimensional concentration maps of the gases for the entire lagoon surface. For this study, a ratioing technique was applied to the tomographic concentration maps to estimate the nitrogen emission rates (from ammonia) using known tracer emission rates. The average concentrations of ammonia measured in August, November, and May were 0.81, 0.25, and 0.74 ppm, respectively. In general, ammonia concentrations were lowest at the center of the lagoon and could vary across a lagoon from 2 to 4 times depending upon the time of the day and the meteorological conditions. Emission rates were only calculated for November and May, up until midnight. In November 1997, the average flux was 1910 μg N m⁻²-min⁻¹ (range 542–4695 μg N m⁻²-min⁻¹) and in May the average flux was 4775 μg N m⁻²-min⁻¹ (range 2572–8499 μg N m⁻²-min⁻¹). This study was important because it not only provided nitrogen emission rate measurements using a new technology which can measure concentrations over large areas in real time, it was the first large-scale outdoor field study using this application.     

Measuring ammonia concentrations and emissions from agricultural land and liquid surfaces: a review

Aerial ammonia concentrations (Cg) are measured using acid scrubbers, filter packs, denuders, or optical methods. Using Cg and wind speed or airflow rate, ammonia emission rate or flux can be directly estimated using enclosures or micrometeorological methods. Using nitrogen (N) recovery is not recommended, mainly because the different gaseous N components cannot be separated. Although low cost and replicable, chambers modify environmental conditions and are suitable only for comparing treatments. Wind tunnels do not modify environmental conditions as much as chambers, but they may not be appropriate for determining ammonia fluxes; however, they can be used to compare emissions and test models. Larger wind tunnels that also simulate natural wind profiles may be more useful for comparing treatments than micrometeorological methods because the latter require larger plots and are, thus, difficult to replicate. For determining absolute ammonia flux, the micrometeorological methods are the most suitable because they are nonintrusive. For use with micrometeorological methods, both the passive denuders and optical methods give comparable accuracies, although the latter give real-time Cg but at a higher cost. The passive denuder is wind weighted and also costs less than forced-air Cg measurement methods, but it requires calibration. When ammonia contamination during sample preparation and handling is a concern and separating the gas-phase ammonia and aerosol ammonium is not required, the scrubber is preferred over the passive denuder. The photothermal interferometer, because of its low detection limit and robustness, may hold potential for use in agriculture, but it requires evaluation. With its simpler theoretical basis and fewer restrictions, the integrated horizontal flux (IHF) method is preferable over other micrometeorological methods, particularly for lagoons, where berms and land-lagoon boundaries modify wind flow and flux gradients. With uniform wind flow, the ZINST method requiring measurement at one predetermined height may perform comparably to the IHF method but at a lower cost.     

氨水土壤混合物脱除CO2温室气体的实验研究

为了脱除CO2温室气体,提出了利用氨水土壤混合物去除CO2的新方法.分别考察了土壤颗粒粒径、CO2初始流量、氨水浓度(质量比)和温度对CO2脱除量和脱除率的影响.实验结果表明,该方法去除CO2的量较土壤物理吸附量和氨水化学吸收量的总和提高了大约15%;随着氨水浓度的增大,CO2的脱除率和脱除量都增大;随着土壤颗粒粒径和CO2初始流量的增大,CO2的脱除率和脱除量都减小;当温度由22℃升高到31℃,CO2的脱除率随着温度的升高而增大,但是继续升高温度到40 ℃,CO2的脱除率反而下降.     

Open-path tunable diode laser absorption spectroscopy for acquisition of fugitive emission flux data

Air pollutant emission from unconfined sources is an increasingly important environmental issue. The U.S. Environmental Protection Agency (EPA) has developed a ground-based optical remote-sensing method that enables direct measurement of fugitive emission flux from large area sources. Open-path Fourier transform infrared spectroscopy (OP-FTIR) has been the primary technique for acquisition of pollutant concentration data used in this emission measurement method. For a number of environmentally important compounds, such as ammonia and methane, open-path tunable diode laser absorption spectroscopy (OP-TDLAS) is shown to be a viable alternative to Fourier transform spectroscopy for pollutant concentration measurements. Near-IR diode laser spectroscopy systems offer significant operational and cost advantages over Fourier transform instruments enabling more efficient implementation of the measurement strategy. This article reviews the EPA's fugitive emission measurement method and describes its multipath tunable diode laser instrument. Validation testing of the system is discussed. OP-TDLAS versus OP-FTIR correlation testing results for ammonia (R2 = 0.980) and methane (R2 = 0.991) are reported. Two example applications of tunable diode laser-based fugitive emission measurements are presented.     

Conditioning of Fly Ash with Ammonia

This paper presents the results of an investigation of the conditioning of fly ash with ammonia in electrostatic pre-cipitators of power plants operated by the Tennessee Valley Authority. It focuses attention primarily on the mechanisms of conditioning encountered under the particular circumstances available for study. No effect of ammonia on the electrical resistivity of fly ash was evident. Instead, the effect of ammonia appeared to be an enhancement pf the space-charge component of the electric field used for charging and precipitating particles of fly ash. In addition, a second effect appeared to be an increase in the cohesiveness of precipitated ash and a reduction in the quantity of ash reentrained during electrode rapping. Data demonstrating the value of ammonia conditioning for lowering the emission pf fly ash during three precipitator studies are presented. Reasons for the ineffectiveness of ammonia conditioning during a fourth precipitator study are discussed. In conclusion, comments are made about the effects to be expected from ammonia conditioning under circumr stances different from those investigated experimentally, particularly with ammonia as a conditioning agent for fly ash from low sulfur western coal.     

Measuring Ammonia Concentrations and Emissions from Agricultural Land and Liquid Surfaces: A Review

Abstract

Aerial ammonia concentrations (C _g) are measured using acid scrubbers, filter packs, denuders, or optical methods. Using C _g and wind speed or airflow rate, ammonia emission rate or flux can be directly estimated using enclosures or micrometeorological methods. Using nitrogen (N) recovery is not recommended, mainly because the different gaseous N components cannot be separated. Although low cost and replicable, chambers modify environmental conditions and are suitable only for comparing treatments. Wind tunnels do not modify environmental conditions as much as chambers, but they may not be appropriate for determining ammonia fluxes; however, they can be used to compare emissions and test models. Larger wind tunnels that also simulate natural wind profiles may be more useful for comparing treatments than micrometeorological methods because the latter require larger plots and are, thus, difficult to replicate. For determining absolute ammonia flux, the micrometeorological methods are the most suitable because they are nonintrusive. For use with micrometeorological methods, both the passive denuders and optical methods give comparable accuracies, although the latter give real-time C _g but at a higher cost. The passive denuder is wind weighted and also costs less than forced-air C _g measurement methods, but it requires calibration. When ammonia contamination during sample preparation and handling is a concern and separating the gas-phase ammonia and aerosol ammonium is not required, the scrubber is preferred over the passive denuder. The photothermal interferometer, because of its low detection limit and robustness, may hold potential for use in agriculture, but it requires evaluation. With its simpler theoretical basis and fewer restrictions, the integrated horizontal flux (IHF) method is preferable over other micrometeorological methods, particularly for lagoons, where berms and land-lagoon boundaries modify wind flow and flux gradients. With uniform wind flow, the ZINST method requiring measurement at one predetermined height may perform comparably to the IHF method but at a lower cost.     

Calibration and testing of a dynamic flow-through chamber for field determination of methyl bromide volatilization flux

Accurate emission measurement of highly volatile chemicals such as methyl bromide (MeBr) is a crucial step in assessing their potential for environmental contamination. Use of flux chambers is a simple method for measuring emission rate under field conditions. To validate the applicability of a dynamic flow-through chamber for measuring MeBr emission, we provide a complete presentation of calibration and testing of the chamber. The calibration was made under a controlled system subject to ambient temperature changes. Two field experiments were conducted to test the chamber for measuring MeBr flux under conditions similar to commercial soil fumigation practices. In both the calibration and the two field experiments, the chamber provided accurate emission estimates. The maximum mass balance error was < 10% which is comparable to the micrometerological method. Because of its simplicity, we believe this dynamic flux chamber can be used reliably in quantifying the emission dynamics of highly volatile chemicals such as MeBr.     

A passive flux denuder for evaluating emissions of ammonia at a dairy farm

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH3), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling has required active sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH3 from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH3 flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH3 flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH3 emissions.     

Decrease of time for pathogen inactivation in alkaline disinfection systems using pressure.

From field studies conducted by Tulane University (New Orleans, Louisiana), efficiency of advanced alkaline disinfection in closed systems was found to depend on ammonia concentration, pH, exposure time, temperature, total solids content, pretreatment storage time, and mixing effectiveness. In this study of a closed alkaline system, an additional pathogen stressor pressure was tested. The effect of the alkaline dosing has been assessed for dewatered raw and aerobically and anaerobically digested municipal sludge cake that produce un-ionized ammonia at concentrations of 0.05 to 2% on a dry-weight basis. Inactivation of Ascaris suum eggs increased from 50 to 99% as the temperature was increased from 40 to 55 degrees C, thus achieving Class A levels. The systems studied were compared with an alkaline process operated under open conditions, which limited the concentrations of ammonia available because of Henry's Law. Under a closed pressurized system, the effect of un-ionized ammonia was greatly increased, and the resulting time required for inactivation was reduced from hours or days to minutes. In the next few years, it is expected that alkaline disinfection of biosolids will be optimized in relation to the factors stated above, at much lower doses of the alkaline agents. The closed-system alkaline processes that will be developed will be more energy-efficient, cost-effective, and have full control of potential odorous emissions.     

A laboratory study of microalgae-based ammonia gas mitigation with potential application for improving air quality in animal production operations

Ammonia gas emission is a major concern in concentrated animal production operations. It not only reduces the manure value as fertilizer due to nitrogen loss, but also has considerable environmental consequences for both animals and ecosystem. In this work, a microalgae culture system was developed as an ammonia gas bioscrubber to reduce ammonia gas emission. The green algae Scenedesmus dimorphus was grown in a flat-panel photobioreactor aerated with ammonia-laden air. A continuous culture was performed at different operational conditions including dilution rate (D = 0.05, 0.1, 0.2, and 0.3 day^?1), ammonia gas loading rate (9.4, 19.3, 28.9, 39.9, 55.6 mg/L-day), and medium pH (5, 6, 7, and 8). The alga culture at 0.1 day^?1 dilution rate, 39.9 mg/L-day ammonia gas loading rate, and pH 7 resulted in the highest cell density and biomass productivity. In order to provide a wide spectrum evaluation of the algae-based ammonia mitigation system, four parameters were determined, including ammonia removal rate, overall ammonia gas removal efficiency, cellular ammonia consumption rate, and cell yield based on ammonia input. Depending on the operational conditions used, the maximum values of those four evaluative parameters were 50.92 ± 2.91 mg/L-day of ammonia removal rate, 94.90 ± 1.87% of ammonia removal efficiency, 0.0597 ± 0.0024 g NH₃/g cell-day of cellular ammonia consumption rate, and 19.40 ± 2.52 g cell/g NH₃ of cell yield based on ammonia. It was also found that the majority of nitrogen in the ammonia gas was assimilated by the algal cells. At D = 0.1 day^?1, 39.9 mg/L-day of ammonia gas loading rate and pH 7, algal biomass assimilated 98.6% of nitrogen contained in the ammonia gas input, with less than 5% of inlet ammonia gas was exhausted after the algal treatment.

Implications: This study demonstrated the effectiveness of using microalgae for mitigating ammonia gas emission from animal production operations. The results enabled us to better understand the mechanisms of ammonia assimilation by microalgae, the engineering design parameters for the process scale up, and the economic viability of the system. Eventually, it will lead to a novel, alternative method for mitigating ammonia gas emission from concentrated animal operations while producing biomass as high-quality feed ingredient.     

Measurements of air–surface exchange rates of volatile organic compounds

Vertical gradients of volatile organic compounds (VOCs) were measured over a maize field and a soybean field in 1995 and 1996, respectively, in the Lower Coastal Plains of North Carolina. The measurements over the maize field were conducted in its early growth period, during May 1995, and the measurements over the soybean field were conducted in its middle and later growth periods during July through August 1996 at the same location. These measurements were combined with micrometeorological flux measurements to determine emission flux measurements for various VOCs. This measurement programme was part of project NOVA (Natural emissions of Oxidant precursors: Validation of techniques and Assessment) to estimate the flux of VOCs. Methanol was identified as the major biogenic compound for both years with the average flux of 3450 ± 1456 µg/m²/hr over maize and 3079 ± 2766 µg/m²/hr over soybean. Acetone is another compound that was identified as a biogenic compound for both years with the average flux of 425 ± 223 µg/m²/hr over maize and 2701 ± 1710 µg/m²/hr over soybean. In addition to biogenic compounds, a large number of aromatic compounds, including styrene and 1,2,4-trimethylbenzene, were also identified as emissions from the ground over the soybean field.     

Response of a grassland ecosystem to air pollutants: III--The chemical climate: Vertical flux densities of gaseous species in the atmosphere near the ground

The establishment of element balances for ecosystems presupposes a knowledge of the amounts of the respective element exchanged between the ecosystem and the atmosphere near the ground by determining their vertical flux densities. Any adequate approach to calculate flux densities of gaseous species in the atmosphere has to use micrometeorological techniques. The authors applied the ratiometric method, which is described in detail. Results of flux density calculations for sulfur dioxide, nitrogen dioxide, nitric oxide and ammonia obtained during two years of measurement are discussed with regard to their role in element balances. Flux densities and deposition velocities of ozone are interpreted as functions of meteorological parameters as well as of the biological activity of the canopy. The latter is characterized by the flux density and flux-to-concentration ratio of carbon dioxide.