Use of Project MOHAVE perfluorocarbon tracer data to evaluate source and receptor models

Project MOHAVE was a major monitoring, modeling, and data analysis study whose objectives included the estimation of the contributions of the Mohave Power Project (MPP) and other sources to visibility impairment in the southwestern United States, in particular at Grand Canyon National Park. A major element of Project MOHAVE was the release of perfluorocarbon tracers at MPP and other locations during 50-day summer and 30-day winter intensive study periods. Tracer data (from about 30 locations) were sequestered until several source and receptor models were used to predict tracer concentrations. None of the models was successful in predicting the tracer concentrations; squared correlation coefficients between predicted and measured tracer were all less than 0.2, and most were less than 0.1.     

The project MOHAVE tracer study: study design,data quality,and overview of results

In the winter and summer of 1992, atmospheric tracer studies were conducted in support of project MOHAVE, a visibility study in the southwestern United States. The primary goal of project MOHAVE is to determine the effects of the Mohave power plant and other sources upon visibility at Grand Canyon National Park. Perfluorocarbon tracers (PFTs) were released from the Mohave power plant and other locations and monitored at about 30 sites. The tracer data are being used for source attribution analysis and for evaluation of transport and dispersion models and receptor models. Collocated measurements showed the tracer data to be of high quality and suitable for source attribution analysis and model evaluation. The results showed strong influences of channeling by the Colorado River canyon during both winter and summer. Flow from the Mohave power plant was usually to the south, away from the Grand Canyon in winter and to the northeast, toward the Grand Canyon in summer. Tracer released at Lake Powell in winter was found to often travel downstream through the entire length of the Grand Canyon. Data from summer tracer releases in southern California demonstrated the existence of a convergence zone in the western Mohave Desert.     

Relating summer ambient particulate sulfur, sulfur dioxide, and light scattering to gaseous tracer emissions from the MOHAVE Power Project

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-north-east of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO2, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data. Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO2 to particulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO2 and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO2 and tracer emission "signals" to particulate sulfur or light scattering.     

Exploring spatial patterns of particulate sulfur and OMH from the Project MOHAVE summer intensive regional network using analyses of variance techniques and meteorological parameters as sort determinants

Project MOHAVE (Measurements of Haze and Visual Effects) encompassed a 1-yr field study in the southwestern United States from September 1991 through August 1992. The congressionally mandated study was a joint partnership between the U.S. Environmental Protection Agency, Southern California Edison, and the National Park Service. A major objective of this study was to quantify the potential haze impacts on the nearby Grand Canyon National Park from the 1580 MW coal-fired MOHAVE Power Project (MPP). Any regional impacts from MPP were from secondary fine sulfate. In this paper, we explore the temporal and spatial patterns of particulate sulfur (Sp) and "organic mass by hydrogen" (OMH) during the summer intensive, conducted from mid-July through the end of August 1992. Using an innovative hierarchical pattern recognition classification scheme, we developed 6 groups of Sp and 8 groups of OMH temporally similar behaving patterns in the sampling region. From a regional understanding of synoptic meteorology, these Sp patterns were explainable. We observed two regional gradients. One gradient was a west-to-east decreasing gradient, most likely the result of major sources from urban southern California, including the San Joaquin Valley. The other decreasing gradient was from south-to-north, perhaps the result of emissions emanating from the large urban centers in northern Mexico. The patterns for OMH were not as regionally homogeneous as the patterns for Sp. A west-to-east decreasing gradient was observed for OMH, along with reduced values in the lower Colorado River Valley and some higher values in central and eastern Arizona. The west-to-east decreasing gradient suggests the presence of the Los Angeles urban plume, while the higher values in central and eastern Arizona may be due to biogenic emissions and increased seasonal fires.     

Validation of the lagrangian particle dispersion model FLEXPART against large-scale tracer experiment data

A comprehensive validation of FLEXPART, a recently developed Lagrangian particle dispersion model based on meteorological data from the European Centre for Medium-Range Weather Forecasts, is described in this paper. Measurement data from three large-scale tracer experiments, the Cross-Appalachian Tracer Experiment (CAPTEX), the Across North America Tracer Experiment (ANATEX) and the European Tracer Experiment (ETEX) are used for this purpose. The evaluation is based entirely on comparisons of model results and measurements paired in space and time. It is found that some of the statistical parameters often used for model validation are extremely sensitive to small measurement errors and should not be used in future studies. 40 cases of tracer dispersion are studied, allowing a validation of the model performance under a variety of different meteorological conditions. The model usually performs very well under undisturbed meteorological conditions, but it is less skilful in the presence of fronts. The two ETEX cases reveal the full range of the model’s skill, with the first one being among the best cases studied, and the second one being, by far, the worst. The model performance in terms of the statistical parameters used stays rather constant with time over the periods (up to 117 h) studied here. It is shown that the method used to estimate the concentrations at the receptor locations has a significant effect on the evaluation results. The vertical wind component sometimes has a large influence on the model results, but on the average only a slight improvement over simulations which neglect the vertical wind can be demonstrated. Subgrid variability of mixing heights is important and must be accounted for.     

Use of Project MOHAVE Perfluorocarbon Tracer Data to Evaluate Source and Receptor Models

ABSTRACT

Project MOHAVE was a major monitoring, modeling, and data analysis study whose objectives included the estimation of the contributions of the Mohave Power Project (MPP) and other sources to visibility impairment in the southwestern United States, in particular at Grand Canyon National Park. A major element of Project MOHAVE was the release of perfluorocarbon tracers at MPP and other locations during 50-day summer and 30-day winter intensive study periods. Tracer data (from about 30 locations) were sequestered until several source and receptor models were used to predict tracer concentrations. None of the models was successful in predicting the tracer concentrations; squared correlation coefficients between predicted and measured tracer were all less than 0.2, and most were less than 0.1.     

A simple urban dispersion model tested with tracer data from Oklahoma City and Manhattan

A simple urban dispersion model is tested that is based on the Gaussian plume model and modifications to the Briggs urban dispersion curves. An initial dispersion coefficient (σ_o) of 40 m is assumed to apply in built-up downtown areas, and the stability is assumed to be slightly unstable during the day and slightly stable during the night. Observations from tracer experiments during the Joint Urban 2003 (JU2003) field study in Oklahoma City and the Madison Square Garden 2005 (MSG05) field study in Manhattan are used for model testing. The tracer SF₆ was released during JU2003 near ground level in the downtown area and concentrations were observed at over 100 locations within 4 km from the source. Six perfluorocarbon tracer (PFT) gases were released near ground level during MSG05 and sampled by about 20 samplers at the surface and on building roofs. The evaluations compare concentrations normalized by source release rate, C/Q, for each sampler location and each tracer release, where data were used only if both the observed and predicted concentrations exceeded threshold levels. At JU2003, for all samplers and release times, the fractional mean bias (FB) is about 0.2 during the day (20% mean underprediction) and 0.0 during the night. About 45 –50% of the predictions are within a factor of two (FAC2) of the observations day and night at JU2003. The maximum observed C/Q is about two times the maximum predicted C/Q both day and night. At MSG05, for all PFTs, surface samplers, and release times, FB is 0.14 and FAC2 is about 45%. The overall 60 min-averaged maximum C/Q is underpredicted by about 40% for the surface samplers and is overpredicted by about 25% for the building-roof samplers.     

Study of expiratory droplet dispersion and transport using a new Eulerian modeling approach

Understanding of droplet nuclei dispersion and transport characteristics can provide more engineering strategies to control transmission of airborne diseases. Droplet dispersion in a room under the conventional well-mixed and displacement ventilation is simulated. Two droplet nuclei sizes, 0.01 and 10 μm, are selected as they represent very fine and coarse droplets. The flow field is modeled using k–ε RNG model. A new Eulerian drift-flux methodology is employed to model droplet phase. Under the conventional ventilation scheme, both fine and coarse droplets are homogeneously dispersed within approximately 50 s. Droplet nuclei exhibit distinctive dispersion behavior, particularly for low airflow microenvironment. After 270 s of droplet emission, gravitational settling influences the dispersion for 10 μm droplets, and concentration gradient can still be observed for displacement ventilation.     

Prediction of some in situ tracer tests with sorbing tracers using independent data

Some recent converging tracer tests with sorbing tracers at the Asp? Hard Rock Laboratory in Sweden, the TRUE tests, have been predicted using only laboratory data and hydraulic data from borehole measurements. No model parameters were adjusted to obtain a better fit with the experiments. The independent data were fracture frequency and transmissivity data obtained in the field and laboratory data on sorption and matrix diffusion. Transmissivity measurements in five boreholes in the rock volume containing the region surrounding the injection and collection points show that there is a high frequency of water conducting fractures. Of 162 packed off sections with 0.5 m packer distances, 112 were found to have a transmissivity above the detection limit. The specific flow-wetted surface (FWS) of the rock mass could be estimated from these data. The transmissivities were found to be reasonably well described by a lognormal distribution. Laboratory data on diffusion and sorption properties together with the hydraulic data were used to "predict" the residence time distribution (RTD) of the sorbing tracers. The results were compared with the experimental breakthrough curves. In these experiments, the water residence time is very small compared to the residence time of the sorbing tracers due to their diffusion and sorption within the rock matrix. We thus could neglect the influence of the water residence time in our predictions. Therefore, no information on water residence times or on "dispersion" was needed. The dispersion of the sorbing tracers is caused by the different sorbing tracer residence times in different pathways. The sorbing tracer residence time is determined by the ratio of flowrate to the flow-wetted surface in the different pathways and not by the water residence time. Assuming a three-dimensional flow pattern and using the observed fracture frequency and flowrate distribution, breakthrough curves for three strongly sorbing tracers were predicted. Only the laboratory data, the transmissivity measurements and the pumping flowrate were used in the predictions. No information on the water residence time as obtained by the nonsorbing tracers was used. The predictions were surprisingly accurate.     

Analysis of air quality data near roadways using a dispersion model

We used a dispersion model to analyze measurements made during a field study conducted by the U.S. EPA in July–August 2006, to estimate the impact of traffic emissions on air quality at distances of tens of meters from an eight-lane highway located in Raleigh, NC. The air quality measurements consisted of long path optical measurements of NO at distances of 7 and 17 m from the edge of the highway. Sonic anemometers were used to measure wind speed and turbulent velocities at 6 and 20 m from the highway. Traffic flow rates were monitored using traffic surveillance cameras. The dispersion model [Venkatram, A., 2004. On estimating emissions through horizontal fluxes. Atmospheric Environment 38, 2439–2446] explained over 60% of the variance of the observed path averaged NO concentrations, and over 90% of the observed concentrations were within a factor of two of the model estimates.Sensitivity tests conducted with the model indicated that the traffic flow rate made the largest contribution to the variance of the observed NO concentrations. The meteorological variable that had the largest impact on the near road NO concentrations was the standard deviation of the vertical velocity fluctuations, σ_w. Wind speed had a relatively minor effect on concentrations. Furthermore, as long as the wind direction was within ±45° from the normal to the road, wind direction had little impact on near road concentrations. The measurements did not allow us to draw conclusions on the impact of traffic-induced turbulence on dispersion. The analysis of air quality and meteorological observations resulted in plausible estimates of on-road emission factors for NO.     

Relating Summer Ambient Particulate Sulfur,Sulfur Dioxide,and Light Scattering to Gaseous Tracer Emissions from the MOHAVE Power Project

ABSTRACT

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-northeast of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO₂, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data.

Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO₂ to par-ticulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO₂ and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO₂ and tracer emission “signals” to particulate sulfur or light scattering.     

Full-scale experiments on dispersion around an isolated building using an ionized air tracer technique with very short averaging time

Experiments are reported in which negatively ionized air is used as a tracer on the flow and dispersion in the vicinity of an isolated building. The technique permits very rapid response concentration measurements to be made, so that the characteristics of concentration fluctuations can be determined. Experiments have been carried out using both continuous and pulsed ion sources, and with several detectors deployed to reveal aspects of their sequential activation as a puff of ions is carried on a trajectory in the wake region. Statistical aspects of the multi-detector experiments are presented, and suggestions based on these results are put forward concerning further use of the method in examining this type of flow and dispersion behaviour.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Second Generation Chemical Mass Balance Source Apportionment of Sulfur Oxides and Sulfate at the Grand Canyon during the Project MOHAVE Summer Intensive

ABSTRACT

Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SO_x, SO₂ plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO₂ can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SO_x present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SO_x at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SO_x and sulfate.     

Analysis of field observations of tracer transport in a fractured till

We analyze a set of observations from a recently published, field-scale tracer test in a fractured till. These observations demonstrate a dominant, underlying non-Fickian behavior, which cannot be quantified using traditional modeling approaches. We use a continuous time random walk (CTRW) approach which thoroughly accounts for the measurements, and which is based on a physical picture of contaminant motion that is consistent with the geometric and hydraulic characterization of the fractured formation. We also incorporate convolution techniques in the CTRW theory, to consider transport between different regions containing distinct heterogeneity patterns. These results enhance the possibility that limitations in predicting non-Fickian modes of contaminant migration can be overcome.     

Verification of a three-dimensional transport model using tetroon data from project state

During August 1978, The Environmental Protection Agency (EPA) conducted a major field study at the Cumberland Steam Plant of the Tennessee Valley Authority. This study, known as the Tennessee Plume Study, was conducted as part of the EPA Sulfur Transport and Transformation in the Environment (STATE) Project. The field experiments included the release and tracking of tetroons from Cumberland during numerous intervals within the period of the study. On 15 August, 10 tetroons were released, traveling distances ranging from less than 25 km to in excess of 200 km. The tetroon position data were compared with three-dimensional (3-D) kinematic trajectory predictions from a 3-D regional-scale dynamic model. The average directional error was 7° where the maximum error was 14° and an error of less than 2° prevailed for 2 trajectories. The average displacement error was 9 % of the observed path of the tetroon, with the maximum being 30% and an error of 3% or less prevailing for 4 trajectories.     

Comparison of constant volume balloons, model trajectories and tracer transport during ETEX

In the field phases of the European Tracer EXperiment (ETEX), an inert tracer was released for 12 h into the atmosphere and samples taken at several locations downwind. During the same time, several Constant Volume Balloons (CVB) (10 and 6 for ETEX first and second release, respectively) were launched into different altitudes and followed as far as 21–188 km, to indicate the initial dispersion directions of the tracer puff. A model simulating the CVB behaviour in hydrostatic meso-scale model forecasts is applied to ETEX data to demonstrate its capability to predict the tracer puff mean axis over long distances (−2000 km). CVB model results are first compared to air parcels trajectories and 2D (i.e. isentropic, isobaric and isodensity) trajectories. Then they are compared to the measured CVB trajectories and finally to the tracer puff trajectories. As expected, the CVB model and isodensity model trajectories are found to be identical. The 16 CVBs calculated trajectories nearly overlap the real ones over 21–188 km with mean absolute horizontal transport deviations less than 20 km (average value of 8.2 km). The corresponding relative transport deviations are less than 45% with an average value of 20.6%. Better predictions are obtained for the ETEX second release. During the 60 h following ETEX’s first release start, the simulated CVBs are mainly found in the area of the maximum surface concentrations of the released tracer, up to 2000 km. Up to 36 h after ETEX second tracer release start, the simulated CVB trajectories predict well the mean axis of the tracer puff, but failed later.     

Second generation chemical mass balance source apportionment of sulfur oxides and sulfate at the Grand Canyon during the Project MOHAVE summer intensive

Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SOx, SO2 plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO2 can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SOx present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SOx at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SOx and sulfate.