Causes of haze in the Columbia River Gorge

Visibility impairment in the Columbia River Gorge National Scenic Area is an area of concern. A field study conducted from July 2003 to February 2005 was followed by data analysis and receptor modeling to better understand the temporal and spatial patterns of haze and the sources contributing to the haze in the Columbia River Gorge in the states of Washington and Oregon. The nephelometer light scattering and surface meteorological data at eight sites along the gorge showed five distinct wind patterns, each with its characteristic diurnal and spatial patterns in light scattering by particles (bsp). In summer, winds were nearly always from west to east (upgorge) and showed decreasing bsp with distance into the gorge and a pronounced effect of the Portland, OR, metropolitan area on haze, especially in the western portions of the gorge. Winter often had winds from the east with very high levels of bsp, especially at the eastern gorge sites, with sources east of the gorge responsible for much of the haze. The major chemical components responsible for haze were organic carbon, sulfate, and nitrate. Positive matrix factorization (PMF) using chemically speciated Interagency Monitoring of Protected Visual Environments data indicated seven source factors in the western gorge and five factors in the eastern gorge. Organic mass is a large contributor to haze in the gorge in all seasons, with a peak in fall. The PMF analysis suggests that approximately half of the organic mass is biomass smoke, with mobile sources as the second largest contributor. PMF analysis showed nitrates (important in fall and winter) mainly attributed to a generic secondary nitrate factor, with the next largest contributor being oil combustion at Mt. Zion, WA and mobile sources at Wishram, WA. Sulfate is a significant contributor in all seasons, with peak sulfate concentrations in summer.     

Sequencing diurnal air flow patterns for ozone exposure assessment around Houston,Texas

Understanding the human health impacts of ground level ozone requires detailed knowledge of its spatial–temporal distribution beyond that provided by surface monitoring networks. Here, a novel methodology based on unsupervised multivariate statistical techniques has been developed and used to identify the transport and dispersion patterns of tropospheric ozone. The hierarchical clustering method is used to visualize air flow patterns at two time scales relevant for ozone buildup. Sequentially executed statistical methods consider hourly 1-h surface wind field measurements. First, clustering is performed at the hourly time scale to identify 1-h surface flow patterns. Then, sequencing is performed at the daily time scale to identify groups of days sharing similar diurnal cycles for the surface flow. Selection of appropriate numbers of air flow patterns allows inference of regional transport and dispersion patterns for understanding population exposure to ozone. The methods are applied to the Houston, Galveston, and Beaumont-Port Arthur, TX study domain. Representative hourly wind field patterns are determined for the entire 2004 ozone season. Then, sequencing is performed for the 32 days in exceedance of the NAAQS for 8-h ozone. Four diurnal flow patterns capturing different ozone exceedance scenarios are isolated; each scenario is associated with a distinct spatial distribution for atmospheric pollutants.     

A modeling assessment of association between East Asian summer monsoon and fate/outflow of α-HCH in Northeast Asia

Using a dynamic numerical atmospheric transport model for organochlorine pesticides (OCPs), the relationship between the East Asian summer monsoon and the fate of α-hexachlorocyclohexane (α-HCH), a banned OCP, in the atmosphere over Northeast Asia was investigated and assessed. The modeled temporal and spatial patterns and variability of α-HCH air concentrations during the summer months of 2005 revealed a strong link between this chemical in the atmosphere over Northeast Asia and the East Asian summer monsoon. At lower atmospheric levels, easterly and southeasterly winds blowing from relatively cold ocean surface convey α-HCH air concentration from southeast China to northeast China. A monsoon front extending from southeast China to Japan, characterized by a strong wind convergence, carried the air concentration to a high elevation of the atmosphere where it was delivered by southerly monsoon flow to northern China and North Pacific Ocean. This summer monsoon associated northward atmospheric transport caused a reversal of the soil/air exchange from outgassing to net deposition during spring–summer period. The modeled wet deposition fluxes of α-HCH agreed well with the changes in the typical summer monsoon rain bands, designated as Meiyu in China, Changma in Korea, and Baiu in Japan. The major wet deposition flux paralleled with the monsoon front as well as the monsoon rain bands. The temporal change in the fluxes exhibits abrupt northward advances, which is associated with a stepwise northward and northeastward advance of the East Asian summer monsoon. The modeled α-HCH outflow in the atmosphere from China occurs mostly in the summer months and through northeast China, featured strongly by the evolution of the summer month. This study suggests that the East Asian summer monsoon provides a major atmospheric pathway and summer outflows to α-HCH over East Asia.     

Evaluation of watering to control dust in high winds

A field study was conducted to determine the effectiveness of watering in controlling PM10 emissions under high wind conditions. The focus of the study was the pickup of soil by a belly scraper at a landfill. Four low-volume PM10 samplers were positioned downwind of the storage pile (at two distances, 80 and 110 m, and two elevations, 1 and 3 m) and one was located upwind at 3 m elevation. Integrating nephelometers, which measure the particulate light scattering coefficient, bsp, were also set up at locations 80 and 110 m downwind of the storage pile. Wind speed and direction were measured on-site. Samples were collected for two periods, one with and one without water being applied. Watering was effective at reducing PM10 emissions at wind speeds up to the maximum 18 m sec-1 observed at the landfill soil pickup operation. Measurement of bsp provided an indication of PM10 concentrations with better time resolution than samplers, but not with sufficient resolution, under the instrumental conditions used, to correlate with wind gusts.     

Long-range transport potential of semivolatile organic chemicals in coupled air-water systems

Ongoing deliberations on the regulation of semivolatile organic chemicals require the assessment of chemical transport in atmospheric and marine systems. The characteristic travel distance was proposed as a measure for the transport potential in air and water. However, the existing definition treats the transport processes separately. It is shown that combined transport in coupled air-ocean systems can accelerate the overall transport into remote regions. Concentration ratios in air and water change with distance from sources depending on the initial concentration ratio and on the difference between the transport velocities. A measure is suggested facilitating the chemical screening with respect to transport potentials in such air-ocean systems. A case study for alpha and gamma-hexachlorocyclohexane shows that the suggested measure qualitatively reveals the transport potentials of these chemicals and exemplifies possible concentration patterns.     

PCB in soils and estimated soil-air exchange fluxes of selected PCB congeners in the south of Sweden

PCB concentrations were studied in different soils to determine the spatial variation over a region of approximately 11 000 km(2). PCB congener pattern was used to illustrate the spatial differences, as shown by principal component analysis (PCA). The relationship to different soil parameters was studied. PCB concentrations in soil showed a large variation between sampling-areas with median concentrations ranging between 2.3 and 332 ng g(-1) (dw). Highest concentrations were found at two sites with sandy soils, one with extremely high organic carbon content. Both sites were located on the west coast of southern Sweden. Soils with similar soil textures (i.e. sandy silt moraine) did not show any significant differences in PCB concentrations. PCB congener composition was shown to differ between sites, with congener patterns almost site-specific. PCB in air and precipitation was measured and the transfer of chemicals between the soil and air compartments was estimated. Soil-air fugacity quotient calculations showed that the PCBs in the soil consistently had a higher fugacity than the PCBs in the air, with a median quotient value of 2.7. The gaseous fluxes between soil and air were estimated using standard modelling equations and a net soil-air flux estimated by subtracting bulk deposition from gaseous soil-air fluxes. It was shown that inclusion of vertical sorbed phase transport of PCBs in the soil had a large effect on the direction of the net soil-air exchange fluxes.     

A numerical model for transient-hysteretic flow and solute transport in unsaturated porous media

A two-dimensional flow and transport model was developed for simulating transient water flow and nonreactive solute transport in heterogeneous, unsaturated porous media containing air and water. The model is composed of a unique combination of robust and accurate numerical algorithms for solving the Richards', Darcy flux, and advection-dispersion equations. The mixed form of Richards' equation is solved using a finite-element formulation and a modified Picard iteration scheme. Mass lumping is employed to improve solution convergence and stability behavior. The flow algorithm accounts for hysteresis in the pressure head-water content relationship. Darcy fluxes are approximated with a Galerkin and Petrov-Galerkin finite-element method developed for random heterogeneous porous media. The transport equation is solved using an Eulerian-Lagrangian method. A multi-step, fourth-order Runge-Kutta, reverse particle tracking technique and a quadratic-linear interpolation scheme are shown to be superior for determining the advective concentration. A Galerkin finite-element method is used for approximating the dispersive flux. The unsaturated flow and transport model was applied to a variety of rigorous problems and was found to produce accurate, mass-conserving solutions when compared to analytical solutions and published numerical results.     

The effects of roadside structures on the transport and dispersion of ultrafine particles from highways

Understanding local-scale transport and dispersion of pollutants emitted from traffic sources is important for urban planning and air quality assessments. Predicting pollutant concentration patterns in complex environments depends on accurate representations of local features (e.g., noise barriers, trees, buildings) affecting near-field air flows. This study examined the effects of roadside barriers on the flow patterns and dispersion of pollutants from a high-traffic highway in Raleigh, North Carolina, USA. The effects of the structures were analyzed using the Quick Urban & Industrial Complex (QUIC) model, an empirically based diagnostic tool which simulates fine-scale wind field and dispersion patterns around obstacles. Model simulations were compared with the spatial distributions of ultrafine particles (UFP) from vehicular emissions measured using a passenger van equipped with a Differential Mobility Analyzer/Condensation Particle Counter. The field site allowed for an evaluation of pollutant concentrations in open terrain, with a noise barrier present near the road, and with a noise barrier and vegetation present near the road.Results indicated that air pollutant concentrations near the road were generally higher in open terrain situations with no barriers present; however, concentrations for this case decreased faster with distance than when roadside barriers were present. The presence of a noise barrier and vegetation resulted in the lowest downwind pollutant concentrations, indicating that the plume under this condition was relatively uniform and vertically well-mixed. Comparison of the QUIC model with the mobile UFP measurements indicated that QUIC reasonably represented pollutant transport and dispersion for each of the study configurations.     

Thermal venting to recover less-volatile hydrocarbons from the unsaturated zone, 1. Theory

Thermal venting is a remediation technique suitable to the liquid unsaturated zone to enhance recovery of less-volatile residual hydrocarbon contaminants. Thermal venting is different to traditional soil venting because heated air instead of air at ambient conditions is applied to the contaminated zone. The vapor pressure of a less-volatile contaminants is typically increased by temperature causing the gas-phase concentrations to increase by three- to five-fold over a temperature increase of 20–30°C. The work described in this first paper provides the theoretical framework of analysis related to thermal venting. The analysis included nonisothermal gas flow, thermal energy transport and multicomponent mass transport in a multiphase porous medium. The transient gas flow analysis included the effect of temperature on fluid properties and gas compressibility. The heat energy transport analysis was performed under the thermodynamic equilibrium condition with phase-summed effective thermal properties. Multi-component mass transport was performed under local equilibrium for partitioning between phases. Model verification was performed to the extend possible using analytical and available experimental data for different physical processes. The second paper of this two-part series will demonstrate the applicability of thermal venting technique through numerical simulations of hypothetical laboratory and field-scale scenarios.     

Improved light extinction reconstruction in interagency monitoring of protected visual environments

The U.S. Environmental Protection Agency (EPA) published the Regional Haze Rule (RHR) in 1999. The RHR default goal is to reduce haze linearly from the baseline period of 2000 through 2004 to natural background in 2064. EPA-recommended method for estimating baseline and natural haze uses the Interagency Monitoring of Protected Visual Environments (IMPROVE) light extinction formula. The IMPROVE formula predicts light extinction from measured aerosol chemical concentrations and estimates of the relative humidity multiplier. On average, the IMPROVE formula overpredicts 6156 nephelometer days (24-hr average measured particle light scattering, bsp) of data by 25%. A new IMPROVED method that reconstructs light extinction using a concentration power law model overpredicts these nephelometer days of data by just 2%. Ignoring the 20% lowest light scattering days, this new IMPROVED formula has a 3% underprediction bias over the 4925 highest nephelometer days with light scattering > or =8 inverse megameters. For comparison, the IMPROVE formula has a 12% overprediction bias for the same days. The IMPROVE formula overprediction averages 77%, 27%, 17%, 9%, and -5% broken down by quintile from lowest to highest nephelometer measured light scattering days. The new IMPROVED formula average overprediction is 21%, -5%, -5%, -2%, and 0%. So, agreement between measured and predicted light scattering improves by modifying the current IMPROVE light extinction formula.     

Analysis of rainfall and fine aerosol data using clustered trajectory analysis for National Park sites in the Western US

We calculated daily back-trajectories using the NOAA-HYSPLIT model to analyze 7 years of precipitation and PM2.5 data from three National Park sites in the Western US. Using a k-means clustering algorithm, the trajectories were segregated into six main transport patterns. At each site, we calculated trajectory clusters for 1, 5, and 10 days to represent short, medium and long-range flow patterns. Most clusters show marked seasonality. Faster flow patterns are more prevalent in winter, and slower/stagnant patterns are more prevalent in summer. The analyses between the 1, 5, and 10-day clusters revealed that the clusters of different duration show very different predictive power for rainfall and PM2.5. We found that the 1-day clusters are a better predictor for precipitation and PM2.5 concentrations, followed by the 5-day clusters. The 10-day clusters did a poorer job of differentiating precipitation and PM2.5. This is because the 10-day clusters show the greatest variability during the first day or two of transport.     

Coupling air quality and land use modeling within an optimization framework

Land use regulations and air quality standards can be effective tools to control air pollution. Atmospheric transport/chemistry simulation models could be used to develop suitable regulations and standards; however, these models are not as efficient as air quality management models developed from embedding governing equations for atmospheric transport/chemistry into an optimization framework. Formulations of two steady-state air quality management models are presented to facilitate the development or evaluation of land use strategies to protect regional air quality from pollution generated from distributed point or nonpoint sources. Both models are linear programs constructed with equations that describe steady-state atmospheric pollutant fate and transport. The first model determines feasible pollutant loading patterns for multiple land use activities to accommodate the greatest regional population. The second model ascertains patterns of expanded land use which have a minimum impact on air quality. The primary goal of this paper is to explain how air pollution and land use modeling may be coupled to create an effective management tool to aid scientists and engineers with decisions affecting air quality and land use. The secondary goal is to show the types of air quality and regulatory information which could be obtained from these models. This latter goal is attained with general conclusions as consequence of applying ‘duality theory.’     

Characterization of polycyclic aromatic hydrocarbons in urban stormwater runoff flowing into the tidal Anacostia River, Washington, DC, USA

To investigate the sources, fate, and transport dynamics of PAHs (polycyclic aromatic hydrocarbons) in stormwater runoff that is a leading source of pollution in urban watersheds, storm and base flow samples were collected in six branches along the lower Anacostia River. PAHs in storm flow (1510-12,500 ng/L) were significantly enriched in the particle phase, which accounted for 68-97% of the total PAHs. It suggests that reducing particles in stormwater using post-treatment system would decrease PAHs considerably. The solid-water distribution coefficients (KD) of PAHs in the storm flow samples were up to 340 times higher than predicted values. A greater portion of high molecular weight PAHs and their distribution patterns indicate higher contribution of automobile originated pyrogenic PAHs. Total suspended solids in storm flow had a positive relationship with flow rates and exceeded benchmark level for the protection of aquatic biota in some samples.     

An anticyclonic point of view on low-level tropospheric long-range transport

Research on Arctic haze has provided an example when anticyclones may play a dominant role in carrying out low-level tropospheric long-range transport. This dominant role of anticyclones in transporting Arctic haze may be the result of the unique geographic and climatological situation existing during winter/spring in which both the huge Eurasian continent and the adjacent ice-covered Arctic Ocean tend to be regions where anticyclones form and exist over long periods of the winter and spring seasons. It is assumed that the seasonal variation of transport mechanisms provided by anticyclones is the primary cause for the seasonal variation of Arctic haze. Centers of anticyclones are the regions where air masses form and obtain their characteristics, both meteorological and chemical, due to the aerosols and gases released into the air. Transport within an air flow along the edges of quasi-stationary anticyclones will remain under stable atmospheric conditions, hence, dilution, lifting and removal of aerosols and gases will be less compared to a transport within the influence of a cyclonic pressure system. According to the concept of isentropic flow, anticyclones may dominate only low-level transport, whereas cyclones may be more important in controlling transport at upper tropospheric levels.     

Investigation into the use of satellite data in aiding characterization of particulate air quality in the Atlanta, Georgia metropolitan area

Poor air quality episodes occur often in metropolitan Atlanta, GA. The primary focus of this research is to assess the capability of satellites as a tool in characterizing air quality in Atlanta. Results indicate that intracity PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) concentrations show similar patterns as other U.S. urban areas, with the highest concentrations occurring within the city. PM2.5 and MODIS (Moderate Resolution Imaging Spectroradiometer) aerosol optical depth (AOD) have higher values in the summer than spring, yet MODIS AOD doubles in the summer unlike PM2.5. Most (80%) of the Ozone Monitoring Instrument aerosol index (AI) is below 0.5 with little differences between spring and summer. Using this value as a constraint of the carbonaceous aerosol signal in the urban area, aerosol transport events such as wildfire smoke associated with higher positive AI values can be identified. The results indicate that MODIS AOD is well correlated with PM2.5 on a yearly and seasonal basis with correlation coefficients as high as 0.8 for Terra and 0.7 for Aqua. A possible alternative view of the PM2.5 and AOD relationship is seen through the use of AOD thresholds. These probabilistic thresholds provide a means to describe the air quality index (AQI) through the use of multiyear AOD records for a specific area. The National Ambient Air Quality Standards (NAAQS) are used to classify the AOD into different AQI codes and probabilistically determine thresholds of AOD that represent most of a specific AQI category. For example, 80% of cases of moderate AQI days have AOD values between 0.5 and 0.6. The development of AOD thresholds provides a useful tool for evaluating air quality from the use of satellites in regions where there are sparse ground-based measurements of PM2.5.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

Monitoring of reduced sulfur compounds in the atmosphere of Gosan, Jeju Island during the Spring of 2001

The atmospheric concentrations of dimethylsulfide (DMS) and carbon disulfide (CS2) were measured concurrently with relevant environmental parameters at Gosan, Jeju Island, Korea during 5-26 April 2001. The mean concentrations for these two compounds were 18.7+/-17.9 and 6.4+/-9.9 pptv, respectively. Results of our analysis indicated that relative temporal variations between DMS and CS2 can be best described by dividing the whole data set into three different periods which reflect the variable transport patterns of air masses into the study area. (Periods I, II, and III denote: 5-10, 10-18, and 19-26 April.) The environmental conditions during those three periods varied greatly. The effects of continental and/or oceanic processes were evident for certain periods, yielding diverse relationships between DMS and CS2 in both absolute and relative terms. Most observed variations were best explained in terms of an interplay between source/sink processes and air mass transport patterns. The sea-to-air flux of DMS, when estimated using our measurement data during this study period, was approximately 4 micromole m(-2)d(-1).     

An online coupled meteorological and air quality modeling study of the effect of complex terrain on the regional transport and transformation of air pollutants over the Western United States

One of the most prominent of characteristics of the western United States that affects its meteorology is the complexity of its mountainous terrain. The meteorological Mesoscale Model, version 5 with Chemistry (MM5-Chem), an online-coupled atmospheric chemistry model, was used to investigate the effect of this terrain on a high air pollution event in the free troposphere. The simulations were evaluated by comparisons with data from the North American Regional Reanalysis (NARR). Complex terrain was shown to have an important influence on the vertical transport of air pollutants on the regional scale; emissions from ground level were vertically mixed as high as 5 km above sea surface level for the wintertime conditions simulated. The simulations showed that the vertical transport of emissions from the Earth's surface could have a more significant effect on mid and upper level chemical concentrations than chemical production. The vertical transport was caused predominately by terrain forced flow over the mountains’ ridge-line and the terrain forced flow was affected by the mountain peak height and the complexity of the terrain downwind.     

Two-phase simulations of an off-nominally operating dissolved-air flotation tank

The flow patterns of the contaminated water and the air bubbles inside a large-scale Dissolved Air Flotation (DAF) tank were examined using CFD modelling. The DAF tank was operating off-nominally in the sense that it was supplied with bubbles larger than originally designed for. Attention was drawn to the location for air injection and the effect of having more than one-size bubbles in the tank, regarding the good contact between phases and the subsequent bubble recovery at the tank free surface. The role of the inclination of the internal baffle of the tank and liquid flow rate was also examined.     

Atmospheric concentrations of PCDDs/PCDFs in southern California.

A comprehensive air toxics measurements program designed to establish baseline concentrations of atmospheric polychlorinated dioxins and dibenzofurans (PCDDs/PCDFs) in the South Coast Air Basin has been completed. The program utilized state-of-the-art air sampling and laboratory analysis techniques (HRGC/HRMS) to quantify the fifteen 2,3,7,8-substituted PCDDs/PCDFs congeners of primary toxicological significance. This study, which included nine discrete sampling sessions between December 1987 and March 1989, provides the first systematic assessment of ambient PCDDs/PCDFs concentrations in the state of California. The highest PCDDs/PCDFs concentrations noted during this study occurred in December 1987. This period was dominated by off-shore air flows, suggesting a regional air mass and transport phenomena. Concentrations of the PCDDs/PCDFs were diminished markedly in subsequent sampling sessions where air flow patterns were primarily of on-shore or of coastal origin. Ambient PCDDs/PCDFs concentrations, expressed as toxic equivalents, were highest during the December 1987 sampling period. The El Toro monitoring site, located approximately 40 miles southeast of Los Angeles, consistently showed the lowest measured ambient PCDDs/PCDFs concentrations and toxic equivalents values. In the majority of the sessions and samples examined the PCDDs/PCDFs congener profiles strongly suggest combustion source influences. Typical of combustion source profiles, 1,2,3,4,6,7,8-HpCDD was the predominant 2,3,7,8-substituted species and most prevalent PCDD after OCDD. The congener of highest toxicological significance, 2,3,7,8-TCDD, was reported below the 10-20 fg/m3 detection limit for most of the ambient air samples selected for analysis.