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。     

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.     

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.     

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.     

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.     

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 model for contaminant mass flux in capped sediment under consolidation

The paper presents a model for contaminant transport and flux through a consolidating subaqueous sediment and overlying cap. The formulation is based on the effect of consolidation and excess pore pressure dissipation on transient, nonlinear advective component of transport through sediment and the cap. The consolidation is induced by the buoyant weight of the cap when it is placed on the contaminated sediments. One equation is presented for advective-diffusive transport through the sediment that is dependent upon soil/contaminant properties and transient advective velocity, which is calculated from a second equation based on the Terzaghi consolidation theory. A third equation is provided to describe the transport of contaminants in the cap. The parameters, including advective velocity, and boundary conditions used for contaminant transport through the cap are derived from the solution of the first two equations. The finite difference method is used to solve the system of equations for consolidation and contaminant transport. A hypothetical case is analyzed to demonstrate the formulation, and the results show that advection due to consolidation can accelerate breakthrough of contaminant through the cap by orders of magnitude. The derivation and results show that consolidation should be included for cap design, and that reactive caps are essential for delaying and reducing dissolved contaminant flux.     

处理高氮公厕污水改进A/O工艺试验研究

根据旅游区公厕污水水质水量特征,采用常规A/O工艺以武汉市动物园公厕化粪池污水为实例进行研究.试验证明A/O工艺虽能有效去除水中COD,但NH 4-N的去除率较低,难以超过60%.针对此问题,本研究提出了该工艺的改进措施,将好氧段按功能分为二级,即碳氧化段和硝化段.试验结果表明,A/O工艺经改进后,在有效去除COD的同时,NH 4-N去除率由60%上升为80%以上.     

A Simulation Model for Air Pollution over Connecticut

A different approach to mathematically modeling large-scale atmospheric processes is presented. Whereas past approaches have been to develop a model based on an accumulation of information from a specific geographical area, resulting in a model applicable to that area only, we have developed a general mathematical model applicable to any geographical area. The model’s applicability is controlled by specifying the input information describing the meteorological situation and pollution source configuration. A rectangular array of grid points is used to specify both the wind field, by using stream functions, and the average source strength of some pollutant for the area represented by the grid. The diffusion problem is divided into two areas: transport by the mean wind field, and dispersion based on travel time and distance as described by empirical equations. Trajectories of pollutants are traced backwards from the points of interest in the course of the calculations and the contributions of all sources that affect the points of interest are accumulated. The model requires an array of source strength information. An inventory of pollution sources in the State of Connecticut was compiled and maps of source strengths were prepared for five pollutants on a 5000-ft grid-square array. Maps of sulfur dioxide and carbon monoxide source strengths are presented with the resulting concentration distribution for “typical” meteorological conditions. The model permits the changing of meteorological or source values at predetermined intervals so that diurnal changes are incorporated in the calculations. The model has not been verified, but the values of pollution concentration are the right order of magnitude and the resulting patterns are as expected.     

Transport and degradation of pesticides in a biopurification system under variable flux Part II: A macrocosm study

Transport of bentazone, isoproturon, linuron, metamitron and metalaxyl were studied under three different flows in macrocosms. The aim was to verify the observations from Part I of the accompanying paper, with an increase in column volume and decrease in chemical and hydraulic load. Very limited breakthrough occurred in the macrocosms for all pesticides, except bentazone, at all flows.From batch degradation experiments, it was observed that the lag time of metamitron and linuron decreased drastically in time for all flows, indicating a growth in the pesticide degrading population. This in contrast to isoproturon and metalaxyl, where an increase in lag time could be observed in time for all flows. From the batch degradation experiments, it could be concluded that the influence of flow on the lag time was minimal and that the inoculation of the pesticide-primed soil had a little surplus value on degradation.     

Preliminary measurements of summer nitric acid and ammonia concentrations in the Lake Tahoe Basin air-shed: implications for dry deposition of atmospheric nitrogen

Over the past 50 years, Lake Tahoe, an alpine lake located in the Sierra Nevada mountains on the border between California and Nevada, has seen a decline in water clarity. With significant urbanization within its borders and major urban areas 130 km upwind of the prevailing synoptic airflow, it is believed the Lake Tahoe Basin is receiving substantial nitrogen (N) input via atmospheric deposition during summer and fall. We present preliminary inferential flux estimates to both lake surface and forest canopy based on empirical measurements of ambient nitric acid (HNO3), ammonia (NH3), and ammonium nitrate (NH4NO3) concentrations, in an effort to identify the major contributors to and ranges of atmospheric dry N deposition to the Lake Tahoe Basin. Total flux from dry deposition ranges from 1.2 to 8.6 kg N ha-1 for the summer and fall dry season and is significantly higher than wet deposition, which ranges from 1.7 to 2.9 kg N ha-1 year-1. These preliminary results suggest that dry deposition of HNO3 is the major source of atmospheric N deposition for the Lake Tahoe Basin, and that overall N deposition is similar in magnitude to deposition reported for sites exposed to moderate N pollution in the southern California mountains.     

A novel bioscrubber for the treatment of high loads of ammonia from polluted gas

Environmental Science and Pollution Research - This work presents a novel bioscrubber configuration for the treatment of high ammonia loads at short contact times. The biological reactor was...     

Transport and degradation of pesticides in a biopurification system under variable flux, part I: A microcosm study

The efficiency of a biopurification system, developed to treat pesticide contaminated water, is to a large extent determined by the chemical and hydraulic load. Insight into the behaviour of pesticides under different fluxes is necessary. The behaviour of metalaxyl, bentazone, linuron, isoproturon and metamitron was studied under three different fluxes with or without the presence of pesticide-primed soil in column experiments. Due to the time-dependent sorption process, retention of the pesticides with intermediate mobility was significantly influenced by the flux. The higher the flux, the slower pesticides will be sorbed, which resulted in a lower retention. Degradation of the intermediate mobile pesticides was also submissive to variations in flux. An increase in flux, led to a decrease in retention, which in turn decreased the opportunity time for biodegradation. Finally, the presence of pesticide-primed soil was only beneficial for the degradation of metalaxyl.