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.     

基于可调二极管激光技术的汽车尾气遥感监测系统

汽车尾气排放已成为最主要的城市污染源之一。汽车尾气的遥感监测系统作为一种高效实时监测汽车正常运行状况下的尾气排放方法已越来越受到人们的广泛关注。本文主要介绍基于可调二极管激光（TDL）技术的汽车尾气遥感监测系统。首先介绍遥感监测系统的产生与发展以及TDL技术的基本原理，其次阐述遥感监测系统的组成、关键技术以及系统的优点，并分析遥感监测系统在国内外的应用现状，最后提出目前应用中尚待解决的若干关键技术问题。     

基于可调二极管激光技术的汽车尾气遥感监测系统

汽车尾气排放已成为最主要的城市污染源之一。汽车尾气的遥感监测系统作为一种高效实时监测汽车正常运行状况下的尾气排放方法已越来越受到人们的广泛关注。本文主要介绍基于可调二极管激光(TDL)技术的汽车尾气遥感监测系统。首先介绍遥感监测系统的产生与发展以及TDL技术的基本原理,其次阐述遥感监测系统的组成、关键技术以及系统的优点,并分析遥感监测系统在国内外的应用现状,最后提出目前应用中尚待解决的若干关键技术问题。     

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.     

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.     

A fast response atmospheric CO2 sensor for eddy correlation flux measurements

The direct measurement of carbon dioxide fluxes in the atmospheric boundary layer is of considerable importance in studies of ocean-atmosphere exchange and in productivity of crops and forests. A promising technique for measuring CO₂ fluxes, the eddy correlation method, requires a sensitive fast response sensor. We describe the sensor requirements and present a design which has proved successful in a preliminary CO₂ flux measurement. The sensor responds to gas concentration fluctuations up to a frequency of 10 Hz with an rms noise corresponding to CO₂ concentration fluctuations of about 0.3 ppm.     

Diffusion scrubber technique used for measurements of atmospheric ammonia

A diffusion scrubber (DS) was developed to measure trace levels of gaseous ammonia in ambient air. The sampling resolution time for this method is 10 min and the detection limit is estimated to be 0.01 ppbv. The response to the NI-I₃ concentrations is found to be dependent on the relative humidity in the ambient air and the temperature. The method is calibrated by using a diluted NH₃ cylinder gas, and the concentrations of the calibration gas were in the range 0.02–2 ppbv during the test. Sampling performed with the DS-method is compared to sampling performed by a filter pack and a continuous flow denuder (AMANDA). The DS-method shows good agreement with the continuous flow denuder and the filter pack.     

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.     

Growing season total gaseous mercury (TGM) flux measurements over an Acer rubrum L. stand

Relaxed eddy accumulation (REA) measurements of the total gaseous mercury (TGM) flux measurements were taken over a deciduous forest predominantly composed of Red Maple (Acer rubrum L.) during the growing season of 2004 and the second half of the growing season of 2005. The magnitudes of the flux estimates were in the range of published results from other micrometeorological mercury fluxes taken above a tall canopy and larger than estimates from flux chambers. The magnitude and direction of the flux were not static during the growing season. There was a significant trend (p < 0.001), from net deposition of TGM in early summer to net evasion in the late summer and early fall before complete senescence. A growing season atmosphere-canopy total mercury (TGM) compensation point during unstable daytime conditions was estimated at background ambient concentrations (1.41 ng m^?3). The trend in the seasonal net TGM flux indicates that long term dry deposition monitoring is needed to accurately estimate mercury loading over a forest ecosystem.     

Real-time measurements of landfill atmospheric ammonia using mobile white cell differential optical absorption spectroscopy system and engineering applications

ABSTRACT

The real-time measurement of atmospheric ammonia at municipal solid waste (MSW) landfills and adjacent areas is necessary for landfill management and the health of nearby residence. Continuous, fast, and real-time monitoring of landfill odor gases is a challenge, especially for ammonia. To our knowledge, this was the first study for the characteristics and seasonal variabilities of atmospheric ammonia at a whole landfill using a Mobile White cell Differential Optical Absorption Spectroscopy (MW-DOAS) system, which also simultaneously offers high sensitivity and fast response. Results show that atmospheric ammonia levels at various landfill areas were significantly dependent on the characteristics of areas, such as municipal solid waste-related areas, leachate-related areas, sludge-related areas, and fly ash-related area, the atmospheric ammonia peak or average level at the active leachate pool of the active MSW site was the highest among all areas of the whole landfill, and the ammonia concentrations at the closed MSW landfill sites were low and dependent on the ages. Moreover, it was found that the seasonal variabilities of ammonia concentrations at most of those areas were significantly dependent on the ambient temperature, and ambient temperature variation caused the atmospheric ammonia level at the active leachate pool and active MSW landfill site in the summer survey to raise 3.5 times and 5.58 times than in the winter survey, respectively.

Implications: Continuous, fast, and real-time monitoring ambient ammonia at or nearby a landfill is critical for landfill operators and local EPAs. This study demonstrates that the mobile White cell Differential Optical Absorption Spectroscopy (MW-DOAS) system is an effective tool for real-time monitoring ambient ammonia of a whole landfill. The results in this article provided a guideline to the characteristics and seasonal changes of ambient ammonia at various types of areas of a whole landfill as well as the impact of age to ambient ammonia at the closed landfill areas.     

Field comparison of disjunct and conventional eddy covariance techniques for trace gas flux measurements

A field intercomparison experiment of the disjunct eddy covariance (DEC) and the conventional eddy covariance (EC) techniques was conducted over a grass field. The half-hourly water vapor fluxes measured by the DEC were within the estimated uncertainty from the fluxes measured by the EC. On the average there was a slight overestimation (<10%) of the fluxes measured by the DEC during the day and underestimation during the night as compared to the fluxes measured by the EC. As this bias does not appear in the simulated DEC measurements it is likely to be due to instrumental problems. The insensitivity of the quality of the fluxes measured by the DEC method to the deficiencies in the gas analysis shows the robustness of this new approach for measuring the surface-atmosphere exchange of trace gases.     

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 detailed ammonia emission inventory for Denmark

This paper describes the method used to create an ammonia inventory for Denmark and presents the emission factors used and their justification. The total Danish emission for 1996 was 92,700 t NH₄⁺–N, with agriculture accounting for nearly 99%. Emissions from animal manure accounted for 76% of agricultural emissions. We conclude that there will be a continued demand for inventories based on emission factors, despite their lack of physical and chemical realism, but that they will become more complex. This will place increased demands on the statistical information available and on the knowledge of the underlying science.     

An empirical method for the conversion of spectral UV irradiance measurements to actinic flux data

Routinely monitored radiation parameters, including those at UV wavelengths, most commonly refer to irradiance, that is the radiation incident on a flat horizontal plate. However, in the study of atmospheric chemistry, where UV radiation is a prime photochemical driver, the target molecules are approximately spherical and the actinic flux (radiation on the surface of a sphere) is a better measure of the effective radiation. Unfortunately actinic flux measurements (also known as scalar irradiance) are uncommon research measurements. The ability to convert irradiance data to actinic flux data within a reasonable degree of uncertainty would provide an actinic flux database mapped from existing irradiance databases, thus vastly increasing knowledge of actinic flux variability and climatology. Synchronised spectral UV irradiance and actinic flux measurements have been made during the ADMIRA project, and used to develop an empirical method for converting irradiance to actinic flux. With some prior knowledge of the sky conditions during the irradiance measurements the actinic flux can be estimated to within a few percent. If no knowledge of the sky conditions is available then the empirical method still returns actinic fluxes within 10% of those measured at the site for which the conversion was developed.     

Evaluation of sequentially-coupled POP fluxes estimated from simultaneous measurements in multiple compartments of an air-water-sediment system

Bulk atmospheric deposition fluxes, air-water exchange fluxes, particle settling fluxes out of the upper water column, sediment trap fluxes in deep waters, and sediment burial fluxes of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in the Koster Fjord, eastern Skagerak, on the Swedish west coast. The aim of the study was to compare the magnitude and direction of the compound fluxes in the system in order to diagnose key fate processes. The PCB and PAH fluxes via net atmospheric deposition, settling particles out of the surface and through deep waters, as well as into the accreting underlying sediments were shown to be remarkably similar, agreeing within a factor of a few for any given target compound. Fluxes of all PCB and PAH target compounds remained fairly constant with water column depth. Thus there was no evidence for net desorption from sinking particles. The net unidirectional and near balancing of vertical fluxes suggests a net transport of PCBs and PAHs from the atmosphere to the continental shelf sediments in the Koster Fjord, which is consistent with the hypothesis that the shelf sediments are important sinks for these compounds.     

A constant-volume rapid exhaust dilution system for motor vehicle particulate matter number and mass measurements

An improved version of the constant volume sampling (CVS) methodology that overcomes a number of obstacles that exist with the current CVS dilution tunnel system used in most diesel and gasoline vehicle emissions test facilities is presented. The key feature of the new sampling system is the introduction of dilution air immediately at the vehicle tailpipe. In the present implementation, this is done concentrically through a cylindrical air filter. Elimination of the transfer hose conventionally used to connect the tailpipe to the dilution tunnel significantly reduces the hydrocarbon and particulate matter (PM) storage release artifacts that can lead to wildly incorrect particle number counts and to erroneous filter-collected PM mass. It provides accurate representations of particle size distributions for diesel vehicles by avoiding the particle coagulation that occurs in the transfer hose. Furthermore, it removes the variable delay time that otherwise exists between the time that emissions exit the tailpipe and when they are detected in the dilution tunnel. The performance of the improved CVS system is examined with respect to diesel, gasoline, and compressed natural gas vehicles.     

A full year evaluation of the CALIOPE-EU air quality modeling system over Europe for 2004

The CALIOPE-EU high-resolution air quality modeling system, namely WRF-ARW/HERMES-EMEP/CMAQ/BSC-DREAM8b, is developed and applied to Europe (12 km × 12 km, 1 h). The model performances are tested in terms of air quality levels and dynamics reproducibility on a yearly basis. The present work describes a quantitative evaluation of gas phase species (O₃, NO₂ and SO₂) and particulate matter (PM2.5 and PM10) against ground-based measurements from the EMEP (European Monitoring and Evaluation Programme) network for the year 2004. The evaluation is based on statistics. Simulated O₃ achieves satisfactory performances for both daily mean and daily maximum concentrations, especially in summer, with annual mean correlations of 0.66 and 0.69, respectively. Mean normalized errors are comprised within the recommendations proposed by the United States Environmental Protection Agency (US-EPA). The general trends and daily variations of primary pollutants (NO₂ and SO₂) are satisfactory. Daily mean concentrations of NO₂ correlate well with observations (annual correlation r = 0.67) but tend to be underestimated. For SO₂, mean concentrations are well simulated (mean bias = 0.5 μg m^?3) with relatively high annual mean correlation (r = 0.60), although peaks are generally overestimated. The dynamics of PM2.5 and PM10 is well reproduced (0.49 < r < 0.62), but mean concentrations remain systematically underestimated. Deficiencies in particulate matter source characterization are discussed. Also, the spatially distributed statistics and the general patterns for each pollutant over Europe are examined. The model performances are compared with other European studies. While O₃ statistics generally remain lower than those obtained by the other considered studies, statistics for NO₂, SO₂, PM2.5 and PM10 present higher scores than most models.     

A hybrid method for inverse characterization of subsurface contaminant flux

The methods presented in this work provide a potential tool for characterizing contaminant source zones in terms of mass flux. The problem was conceptualized by considering contaminant transport through a vertical “flux plane” located between a source zone and a downgradient region where contaminant concentrations were measured. The goal was to develop a robust method capable of providing a statement of the magnitude and uncertainty associated with estimated contaminant mass flux values.In order to estimate the magnitude and transverse spatial distribution of mass flux through a plane, the problem was considered in an optimization framework. Two numerical optimization techniques were applied, simulated annealing (SA) and minimum relative entropy (MRE). The capabilities of the flux plane model and the numerical solution techniques were evaluated using data from a numerically generated test problem and a nonreactive tracer experiment performed in a three-dimensional aquifer model. Results demonstrate that SA is more robust and converges more quickly than MRE. However, SA is not capable of providing an estimate of the uncertainty associated with the simulated flux values. In contrast, MRE is not as robust as SA, but once in the neighborhood of the optimal solution, it is quite effective as a tool for inferring mass flux probability density functions, expected flux values, and confidence limits.A hybrid (SA-MRE) solution technique was developed in order to take advantage of the robust solution capabilities of SA and the uncertainty estimation capabilities of MRE. The coupled technique provided probability density functions and confidence intervals that would not have been available from an independent SA algorithm and they were obtained more efficiently than if provided by an independent MRE algorithm.     

A hybrid method for inverse characterization of subsurface contaminant flux

The methods presented in this work provide a potential tool for characterizing contaminant source zones in terms of mass flux. The problem was conceptualized by considering contaminant transport through a vertical "flux plane" located between a source zone and a downgradient region where contaminant concentrations were measured. The goal was to develop a robust method capable of providing a statement of the magnitude and uncertainty associated with estimated contaminant mass flux values. In order to estimate the magnitude and transverse spatial distribution of mass flux through a plane, the problem was considered in an optimization framework. Two numerical optimization techniques were applied, simulated annealing (SA) and minimum relative entropy (MRE). The capabilities of the flux plane model and the numerical solution techniques were evaluated using data from a numerically generated test problem and a nonreactive tracer experiment performed in a three-dimensional aquifer model. Results demonstrate that SA is more robust and converges more quickly than MRE. However, SA is not capable of providing an estimate of the uncertainty associated with the simulated flux values. In contrast, MRE is not as robust as SA, but once in the neighborhood of the optimal solution, it is quite effective as a tool for inferring mass flux probability density functions, expected flux values, and confidence limits. A hybrid (SA-MRE) solution technique was developed in order to take advantage of the robust solution capabilities of SA and the uncertainty estimation capabilities of MRE. The coupled technique provided probability density functions and confidence intervals that would not have been available from an independent SA algorithm and they were obtained more efficiently than if provided by an independent MRE algorithm.     

除氨循环喷淋填料塔系统建模及运行优化控制

喷淋填料塔是一种常见除氨设备。将喷淋除氨系统作为研究对象,以次氯酸溶液为喷淋液体,并对系统的优化运行进行研究。基于除氨逆流喷淋填料塔效率模型和系统溶液循环动态模型,建立了除氨循环喷淋填料塔系统仿真器,提出了一种以次氯酸溶液消耗量最小为目标的优化控制策略,通过仿真进行了验证,并与其他2个固定喷淋量控制策略进行了对比。与文献数据相比,喷淋填料塔效率模型的偏差在±3%以内,表明建立的仿真器精度较高。仿真验证结果表明：优化控制策略可使排放气体中氨浓度达到国标GB14554的排放限值要求,而且处理后的废液中氨含量低于其他2个控制策略;在相同的运行时长内,优化控制策略与2个固定喷淋量策略对比,次氯酸的消耗量分别节约34%和18%,说明提出的运行优化控制策略可有效节约次氯酸消耗。本研究提出的优化策略可有效提升除氨喷淋填料塔的运行效率。