Ambient Air Measurements of Petroleum Refinery Emissions

An ambient air monitoring program to characterize airborne emissions from the Exxon petroleum refinery at Benicia, California was conducted during September 8–22, 1975. Ground level sampling facilities and an instrumented aircraft provided an integrated, three-dimensional monitoring network. Measurements made during the study included ozone, oxides of nitrogen, methane, carbon monoxide, individual C₂-C₆ hydrocarbons, halocarbons, condensation nuclei, visual distance and various meteorological parameters. The study focused on three major areas: (1) the characterization of gaseous components within the refinery effluent, especially non-methane hydrocarbons and ozone, (2) natural sunlight bag irradiation experiments to determine the ozone forming potential of refinery emissions, and (3) an investigation of changes in plume chemistry as refinery emissions were transported downwind.     

Simultaneous Total Oxidant and Chemiluminescent Ozone Measurements in Ambient Air

The purpose of this project was to investigate the relationship of ambient air quality measurements between two analytical methods, referred to as the total oxidant method and the chemiluminescent method. These two well documented analytical methods were run simultaneously, side by side, at a site on the Houston ship channel. They were calibrated daily. The hourly averages were analyzed by regression techniques and the confidence intervals were calculated for the regression lines. Confidence intervals for point estimates were also calculated. These methods were used with all data sets with values greater than 10 parts per billion and again with values greater than 30 parts per billion. A regression line was also calculated for a second set of data for the preceding year. These data were generated before a chromium triox-ide scrubber was installed to eliminate possible chemical interferences with the Kl method.

The results show that in general the chemiluminescent ozone method tends to produce values as much as two times higher than the simultaneous total oxidant values. In one set of data collected an 80 ppb chemiluminescent ozone value predicted a value of 43.9 ppb total oxidant with a 95% confidence interval of 7.7 to 80.4 ppb. In the second set of data an 80 ppb chemiluminescent ozone value predicted a value of 78 ppb total oxidant with a 95% confidence interval of 0.4 to 156 ppb. Other statistical analyses confirmed that either measurement was a very poor predictor of the other.     

A Method for Using Air Pollution Measurements and Public Opinion to Establish Ambient Air Quality Standards

Air quality was comprehensively evaluated by means of sampling at 21 locations over metropolitan Birmingham during a period of one year. Thousands of integrated samples of three common atmospheric gaseous pollutants and two common particulate pollutants were collected and analyzed. Following the year of sampling in 1964, a random household survey was completed by conducting personal interviews at more than 7200 households over metropolitan Birmingham. Statistical reduction of household survey results by census tract and by neighborhood area provided domestic fuel and waste burning emission data as well as public (resident) opinion on specific air pollution effects. The relationship between ambient air quality and neighborhood opinion of air pollution effects on health and property are evaluated statistically. Ambient standards are suggested which are based upon those air pollution levels shown to have adverse effects on approximately one-third of the people.     

Measurement of Ozone Concentrations in Ambient Air Using a Badge-Type Passive Monitor

Abstract

A badge-type passive monitor was used to evaluate the effectiveness of four ozone trapping reagents for measuring O₃ concentrations in the air. These were sodium nitrite (NaNO₂), 3-methyl-2-benzothiazolinone acetone azine (MBTH), p-acetamidophenol (p-ATP), and indigo carmine. Experiments in an exposure chamber showed that only NaNO₂ and MBTH monitors gave sensitive and linear responses over realistic ranges of O₃ concentrations. When tested in ambient air, NaNO₂ and MBTH monitors with a single-layer diffusion barrier overestimated O₃ concentrations by a significant amount. This was largely canceled out in the NaNO₂ monitor by using a multi-layered diffusion barrier to combat wind turbulence effects. However it had almost no effect on the MBTH monitor, and it was found that NO₂ was a source of serious interference. We concluded that using the NaNO₂ monitor with an effective diffusion barrier can measure O₃ in ambient air with an accuracy of ±16%.     

Exposure of Chronic Obstructive Pulmonary Disease Patients to Particulate Matter: Relationships between Personal and Ambient Air Concentrations

ABSTRACT

Most time-series studies of particulate air pollution and acute health outcomes assess exposure of the study population using fixed-site outdoor measurements. To address the issue of exposure misclassification, we evaluate the relationship between ambient particle concentrations and personal exposures of a population expected to be at risk of particle health effects.

Sampling was conducted within the Vancouver metropolitan area during April-September 1998. Sixteen subjects (non-smoking, ages 54-86) with physician-diagnosed chronic obstructive pulmonary disease (COPD) wore personal PM_{2 5} monitors for seven 24-hr periods, randomly spaced approximately 1.5 weeks apart. Time-activity logs and dwelling characteristics data were also obtained for each subject. Daily 24-hr ambient PM₁₀ and PM_2.5 concentrations were measured at five fixed sites spaced throughout the study region. SO₄ ^2-, which is found almost exclusively in the fine particle fraction and which does not have major indoor sources, was measured in all PM_{2 5} samples as an indicator of accumulation mode particu-late matter of ambient origin.     

A Method of Predicting Point and Path- Averaged Ambient Air VOC Concentrations,Using Meteorological Data

A method of predicting point and path-averaged ambient air VOC concentrations is described. This method was developed for the case of a plume generated from a single point source, and is based on the relationship between wind directional frequency and concentration. One-minute means of wind direction and wind speed were used as inputs to a Gaussian dispersion model to develop this relationship.

Both FTIR spectrometry and a whole-air sampling method were used to monitor VOC plumes during simulated field tests. One test set was also conducted using only whole-air samplers deployed in a closely-spaced network, thus providing an evaluation of the prediction technique free of any bias that might exist between the two analytical methods.

Correlations between observed point concentrations and wind directional frequencies were significant at the 0.05 level in most cases. Predicted path-integrated concentrations, based on observed point concentrations and meteorological data, were strongly correlated with observed values. Predicted point concentrations, based on observed path-integrated concentrations and meteorological data, accurately reflected the location and magnitude of the highest concentrations from each test, as well as the shape of the concentration-versus-crosswind distance curve.     

Receptor Model Evaluation of the Southeast Michigan Ozone Study Ambient NMOC Measurements

Abstract

Large-scale studies like the Southeast Michigan Ozone Study (SEMOS) have focused attention on quantifying and spedating inventories for volatile organic compounds (VOCs). One approach for evaluating the accuracy of a VOC emission inventory is the development of a chemical mass balance (CMB) receptor model for ambient non-methane organic compound (NMOC) measurements. CMB evaluations of ambient hydrocarbon data provide a sample-specific allocation of emissions to individual source categories. This study summarizes the results of an application of the CMB model to the NMOC data from the SEMOS study. Comparison of CMB results with emission inventory values for the Detroit area show that vehicle emissions are well represented by the inventory, as are architectural coatings and coke ovens. Estimated emissions from petroleum refineries and graphic arts industries are much lower in the inventory than determined from the receptor allocation. Under-reporting of fugitive VOC emissions from petroleum refineries is an ongoing problem. Emissions from graphic arts industries are underestimated in the inventory partly because of the broad characterization of the emission factor (i.e., mass emitted/capita), which may be less useful when specific locations and days are under consideration. This study also demonstrates the effectiveness of the CMB approach when used prospectively to track the implementation of emission control strategies. While vehicle emission concentrations were unchanged from 1988 to 1993, measurement-based CMB results suggest a decrease in evaporative emissions during this time period resulting from Reid vapor pressure (RVP) reductions (from 11.0 psi in 1988 to 8.6 psi in 1993) and fleet turnover. Changes in emissions from coke plants and petroleum refineries were also seen in the CMB allocations for these sources.     

A Study of the Association between Daily Mortality and Ambient Air Pollutant Concentrations in Pittsburgh,Pennsylvania

ABSTRACT

We have studied the possible association of daily mortality with ambient pollutant concentrations (PM₁₀, CO, O₃, SO₂, NO₂, and fine [PM_{2 5}] and coarse PM) and weather variables (temperature and dew point) in the Pittsburgh, PA, area for two age groups—less than 75, and 75 and over—for the 3-year period of 1989-1991. Correlation functions among pollutant concentrations show important seasonal dependence, and this fact necessitates the use of seasonal models to better identify the link between ambient pollutant concentrations and daily mortality. An analysis of the seasonal model results for the younger-age group reveals significant multicollinearity problems among the highly correlated concentrations of PM₁₀, CO, and NO₂ (and O₃ in spring and summer), and calls into question the rather consistent results of the single- and multi-pollutant non-seasonal models that show a significant positive association between PM₁₀ and daily mortality. For the older-age group, dew point consistently shows a significant association with daily mortality in all models. Collinearity problems appear in the multi-pollutant seasonal and non-seasonal models such that a significant, positive PM₁₀ coefficient is accompanied by a significant, negative coefficient of another ambient pollutant, and the identity of this other pollutant changes with season. The PM₂₅ data set is half that of PM₁₀. Identical-model runs for both data sets reveal instability in the pollutant coefficients, especially for the younger age group. The concern for the instability of the pollutant coefficients due to a small signal-to-noise ratio makes it impossible to ascertain credibly the relative associations of the fine- and coarse-particle modes with daily mortality. In this connection, we call for caution in the interpretation of model results for causal inference when the models use fully or partially estimated PM values to fill large data gaps.     

Demonstrating Attainment of the Air Quality Standards: Integration of Observations and Model Predictions into the Probabilistic Framework

ABSTRACT

This paper introduces an integrated observational-modeling approach to transform the deterministic nature of attainment demonstrations of the National Ambient Air Quality Standard (NAAQS) into the probabilistic framework. While the methods presented here can be used to address any air quality standard that is based on extreme values, this paper focuses on the application to the 1-hr and 8-hr NAAQS for ozone. Extreme value statistics and resampling techniques are applied to estimate the probability of exceeding the NAAQS for both 1-hr and 8-hr ozone concentrations. Within the integrated observation-modeling analysis approach, we show that the model-to-model differences in the predicted responses to emission reductions are smaller than the model-to-model differences in predicted absolute ozone concentrations. We illustrate that the emission reductions stemming from a real-world emission control strategy would substantially reduce the probability of exceeding the NAAQS over a large portion of the eastern United States, especially for the 8-hr average ozone concentrations.     

Ambient Air Quality and Automotive Emission Control

This paper is concerned with uncertainties involved in projecting ambient air quality. Ambient air quality was projected by assuming a linear dependence on estimated future emissions. Future automotive emissions were estimated by a method recommended by EPA. Projections were made for the locations reported to have the highest ambient air concentrations of each pollutant; Chicago for carbon monoxide and the California South Coast Air Basin for hydrocarbon and oxidant. The sensitivity of the projections to several input parameters was determined.

The uncertainty in projection of air quality due to the use of a maximum, once-per-year concentration is large. For example, the reduction in total CO emissions in Chicago in 1975, necessary to meet the air quality standard, was as high as 68% or as low as 26%, depending on whether the historic high, 8 hr average concentration of 44 ppm or the 1970 maximum of 21 ppm was used. The effects of uncertainties in growth rates and fraction of emissions attributed to the automobile were also sizeable. Differences in automotive growth rate had a large near-term effect on projected concentrations, while differences in nonautomotive growth rate or fraction of emissions attributed to the automobile had a large long-term effect. The effect of 1975 interim automotive emission standards on projected air quality was negligible when compared with projected air quality based on the previous Federal automotive emission standards for 1975.     

Ambient Air Benzene Concentrations in Canada (1989-1993): Seasonal and Day of Week Variations,Trends, and Source Influences

Abstract

Since 1987, the Pollution Measurement Division of the Environmental Protection Service, Environment Canada, has operated a field program for measuring benzene in ambient air. With the cooperation of provincial and municipal environmental agencies, samples have been collected at over 30 urban and rural monitoring sites across the country. Samples are collected in evacuated canisters and analyzed by gas chromatography with a mass-selective detector. Using data from all sites, the composite average benzene concentration for Canada over the years 1989 to 1993 was 3.6 μg/m³ and the composite median was found to be 2.6 μ/m³. Benzene concentrations are highest at urban sites near major streets and at sites influenced by industrial sources. For eighteen urban and suburban trend sites (those with no nearby industrial sources), composite annual median benzene concentrations decreased by 20% between 1989 and 1993. For the same period, median benzene concentrations decreased by 33% at four trend sites with nearby industries. At most monitoring sites the parameters for benzene and CO are highly correlated; supporting the inventory estimate that most emissions of benzene are due to vehicle exhaust. For sites with nearby industrial sources of benzene, the industries are estimated to account for 35 to 70% of the benzene dose experienced at the sites. These site specific contributions are much more significant than the estimated national emissions assigned to industrial sources.     

Quality Assured Measurements of Animal Building Emissions: Gas Concentrations

Abstract

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH₃), hydrogen sulfide (H₂S), carbon dioxide (CO₂), methane (CH₄), nonmethane hydrocarbons (NMHC), particulate matter <10 µm in diameter, and total suspended particulate from swine and poultry production buildings in the United States.

This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with ≥10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH₃, H₂S, CO₂, CH₄, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

High Volume Sampling:Evaluation of an Inverted Sampler for Ambient TSP Measurements

Recent advances in the development of receptor-oriented source apportionment techniques (models) have provided a new approach to evaluating the performance of particulate dispersion models. Rather than limiting performance evaluations to comparisons of particulate mass, receptor model estimates of source impacts can be used to open new opportunities for in-depth analysis of dispersion model performance. Recent experiences in the joint application of receptor and dispersion models have proven valuable in developing increased confidence in source impact projections used for control strategy development. Airshed studies that have followed this approach have identified major errors in emission inventory data bases and provided technical support for modeling assumptions.

This paper focuses on the joint application of dispersion and receptor models to particulate source impact analysis and dispersion model performance and evaluation. The limitations and advantages of each form of modeling are reviewed and case studies are examined. The paper is offered to provide several new perspectives into the model evaluation process in the hope that they may prove useful to those that manage our nation’s air resources.     

Measurement of Particulate Bound Mercury,Gaseous Elemental Mercury,and Reactive Gaseous Mercury Concentrations by Using an Ambient Air Mercury Collection System

In this investigation, the concentrations of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate bound mercury (PBM) in ambient air were measured at the Hung Kuang (traffic) sampling site during September 27 to October 6, 2014. An ambient air mercury collection system (AAMCS) was utilized to measure simultaneously PBM, GEM, and RGM concentrations in ambient air. The results thus obtained demonstrate that the mean concentrations of PBM, GEM, and RGM were 38.57 ± 11.4 (pg/m³), 17.67 ± 5.56 (ng/m³) and 10.78 ± 2.8 (pg/m³), respectively, at this traffic-sampling site. The mean GEM/PBM and GEM/RGM concentration ratios were 458 and 1639, respectively. The results obtained herein demonstrate that AAMCS can be utilized to collect three phases of mercury simultaneously. The mean PBM, GEM, and RGM concentrations herein were compared with others found in Asia, America, Europe and Antarctica. The mean PBM, GEM, and RGM concentrations were found to be lowest in Asia and Antarctica. The mean PBM concentration in Europe was approximately eight times that in this investigation. The mean GEM and RGM concentrations in this study were 1.21 and 170 times those found in the United States.     

Characteristic Study of Ambient Air Total Gaseous Mercury (TGM) Concentrations During Rainy and Non-Rainy Periods at a Traffic Site in Taiwan

This investigation studied the concentrations of ambient air total gaseous mercury (TGM) during the rainy periods at the Hung-Kuang traffic sampling site in central Taiwan from May 26 to June 16, 2014. The results were compared with those of a previous study for ambient air TGM during non-rainy daytime and nighttime periods at the Hung-Kuang traffic sampling site, which was conducted during March 21 to July 20, 2012. The observed mean concentration of ambient air TGM was 1.16 ng/m³ during the rainy periods at the Hung-Kuang traffic sampling site. The mean ambient air TGM concentrations were higher in the non-rainy sampling period in daytime than in the rainy sampling period from this study. The mean ratio of non-rainy sampling period in daytime to that of rainy sampling period for ambient air TGM were 3.15. Furthermore, the mean ambient air TGM concentrations were higher in the non-rainy sampling period in nighttime in than in the rainy sampling period for this study. The mean rations for non-rainy sampling period in nighttime to that of the rainy sampling period for ambient air TGM were 2.70. The results obtained in this study also revealed that the ambient air TGM concentrations during the rainy period had the lowest concentrations when compared with the other sampling sites in other world regions.     

Weekday vs. Weekend Ambient Ozone Concentrations: Discussion and Hypotheses with Focus on Northern California

Abstract

Since the early 1970s, researchers and data analysts have reported differences between weekday and weekend ozone concentrations, with higher ozone concentrations occurring on Sundays in some locations. At that time, the phenomenon was referred to as the “Sunday effect.” In the late 1980s, additional papers focused on weekday/weekend differences in air quality in the South Coast (Los Angeles) Air Basin.

Analyses of ozone concentrations measured at a number of locations in northern California reveal that average ozone concentrations are frequently higher on weekends than on weekdays. Violations of the California 0.09 ppm 1-hour air quality standard for ozone also occur in disproportionately greater frequency on weekends. We hypothesize that this phenomenon is based largely on the differences between weekday and weekend emission patterns. We believe that the observed differences may provide information regarding which pollutant reduction strategy, NO_x or ROG control, may be more effective in reducing ambient ozone concentrations. For the northern California region, the presence of higher weekend ozone concentrations suggests the need for ROG control is greater than for NO_x control. If both NO_x and ROG are to be controlled, it is important to understand the interdependence of the two pollutants in forming ozone. With the current uncertainty and debate regarding official vehicular emission inventories, this phenomenon emphasizes the importance of using observation-based data to examine ambient pollution and emission relationships. This natural experiment of varying emissions provides an interesting test case for sophisticated air pollution model performance and evaluation.

Using a Bay Area emission inventory and an estimate of its change from weekday to weekend, combined with a generic Empirical Kinetic Modeling Approach (EKMA) diagram, we demonstrate the weekend effect. In addition, changes in the Bay Area emission inventory from 1980 to 1990, when combined with the EKMA diagram, also show why the weekend effect is more evident in the 1990s.

It is our hypothesis that the presence of the weekend effect, positive or negative, combined with changes in emission changes, provides a simple clue to whether an area is NO_xor ROG limited with respect to ozone formation.     

Polychlorinated Biphenyl Recovery Efficiency from Stack Gas and Ambient Air

Polychlorinated biphenyls (PCBs) are now recognized as presenting a severe environmental hazard because of their toxicity and persistence in the environment. High temperature combustion has been shown to be an effective method for destroying these compounds.¹ Unfortunately, few facilities are available for their destruction. As part of a feasibility study to convert a liquid-waste incinerator designed for waste fuel to a PCB waste, the sampling efficiency of toluene filled fritted impingers and Chromosorb 102 filled tubes was evaluated.     

Estimation of Ambient PM2.5 Concentrations in Maryland and Verification by Measured Values

Abstract

In 1997, Maryland had no available ambient Federal Reference Method data on particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5), but did have annual ambient data for PM smaller than 10 μm (PM₁₀) at 24 sites. The PM₁₀ data were analyzed in conjunction with local annual and seasonal zip-code-level emission inventories and with speciated PM_2.5 data from four nearby monitors in the IMPROVE network (located in the national parks, wildlife refuges, and wilderness areas) in an effort to estimate annual average and seasonal high PM_2.5 concentrations at the 24 PM₁₀ monitor sites operating from 1992 to 1996. All seasonal high concentrations were estimated to be below the 24-hr PM_2.5 National Ambient Air Quality Standards (NAAQS) at the sites operating in Maryland between 1992 and 1996. The estimates also indicated that 12 monitor sites might exceed the 3-year annual average PM_2.5 NAAQS of 15 ug/m³, but Maryland’s air quality shows signs that it has been improving since 1992. The estimates also were compared with actual measurements after the PM_2.5 monitor network was installed. The estimates were adequate for describing the chemical composition of the PM_2.5, forecasting compliance status with the 24-hr and annual standards, and determining the spatial variations in PM_2.5 across central Maryland.     

Application of Artificial Neural Networks to Modeling and Prediction of Ambient Ozone Concentrations

ABSTRACT

The deterministic modeling of ambient O₃ concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O₃ concentrations based on a limited number of measured hydrocarbon species, NO_x compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O₃, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O₃ concentrations from measured VOC and NO concentrations. To predict the future concentrations of O₃, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species.

The steady-state model produced an approximation of O₃ data and demonstrated the functional relationship between O₃ and VOC-NO_x concentrations. The dynamic models were able to the adequately predict the O₃ concentration and behavior of VOC-NO_x-O₃ system a number of hourly intervals into the future. For 3 hr into the future, O₃ concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.