Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Assessment of indoor levels of volatile organic compounds and carbon dioxide in schools in Kuwait

Indoor air quality (IAQ) in schools is a matter of concern because children are most vulnerable and sensitive to pollutant exposure. Conservation of energy at the expense of ventilation in heating, ventilation, and air conditioning (HVAC) systems adversely affects IAQ. Extensive use of new materials in building, fitting, and refurbishing emit various pollutants such that the indoor environment creates its own discomfort and health risks. Various schools in Kuwait were selected to assess their IAQ. Comprehensive measurements of volatile organic compounds (VOCs) consisting of 72 organic compounds consisting of aliphatic (C₃–C₆), aromatic (C₆–C₉), halogenated (C₁–C₇), and oxygenated (C₂–C₉) functional groups in indoor air were made for the first time in schools in Kuwait. The concentrations of indoor air pollutants revealed hot spots (science preparation rooms, science laboratories, arts and crafts classes/paint rooms, and woodworking shops/decoration rooms where local sources contributed to the buildup of pollutants in each school. The most abundant VOC pollutant was chlorodifluoromethane (R22; ClF₂CH), which leaked from air conditioning (AC) systems due to improper operation and maintenance. The other copious VOCs were alcohols and acetone at different locations due to improper handling of the chemicals and their excessive uses as solvents. Indoor carbon dioxide (CO₂) levels were measured, and these levels reflected the performance of HVAC systems; a specific rate or lack of ventilation affected the IAQ. Recommendations are proposed to mitigate the buildup of indoor air pollutants at school sites.

Implications: Indoor air quality in elementary schools has been a subject of extreme importance due to susceptibility and sensibility of children to air pollutants. The schools were selected based on their surrounding environment especially downwind direction from the highly industrialized zone in Kuwait. Extensive sampling from different sites in four schools for comprehensive VOCs and CO₂ were completed for an extended period of over a year. Different hot spots were identified where leaked refrigerant and inadequate handling of laboratory solvents contributed to the high VOCs in the respective locations. CO₂ levels reflected HVAC performance and poor ventilation. A list of recommendations has been proposed to eradicate these high levels of air pollution.     

Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers

A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver–Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.     

Spatial analysis of volatile organic compounds in South Philadelphia using passive samplers

Select volatile organic compounds (VOCs) were measured in the vicinity of a petroleum refinery and related operations in South Philadelphia, Pennsylvania, USA, using passive air sampling and laboratory analysis methods. Two-week, time-integrated samplers were deployed at 17 sites, which were aggregated into five site groups of varying distances from the refinery. Benzene, toluene, ethylbenzene, and xylene isomers (BTEX) and styrene concentrations were higher near the refinery’s fenceline than for groups at the refinery’s south edge, mid-distance, and farther removed locations. The near fenceline group was significantly higher than the refinery’s north edge group for benzene and toluene but not for ethylbenzene or xylene isomers; styrene was lower at the near fenceline group versus the north edge group. For BTEX and styrene, the magnitude of estimated differences generally increased when proceeding through groups ever farther away from the petroleum refining. Perchloroethylene results were not suggestive of an influence from refining. These results suggest that emissions from the refinery complex contribute to higher concentrations of BTEX species and styrene in the vicinity of the plant, with this influence declining as distance from the petroleum refining increases.

Implications: Passive sampling methodology for VOCs as discussed here is employed in recently enacted U.S. Environmental Protection Agency Methods 325A/B for determination of benzene concentrations at refinery fenceline locations. Spatial gradients of VOC concentration near the refinery fenceline were discerned in an area containing traffic and other VOC-related sources. Though limited, these findings can be useful in application of the method at such facilities to ascertain source influence.     

Decomposition of volatile organic compounds using corona discharge plasma technology

This paper explores the application of corona plasma technology as a tool in treatment of volatile organic compounds (VOCs). The review introduces the principle of corona discharge and describes the characteristics of plasma, especially of various corona plasma reactors. By summarizing the main features of such reactors, this paper provides a brief background to different power sources and reactor configurations and their application to VOC treatment design. Considering chlorinated compounds, benzene series and sulfur compounds, this paper reveals the probable mechanism of corona plasma in VOC degradation. Additionally, the effects of numerous technical parameters – such as reactor structure, shape and materials of electrodes, and humidity – are analyzed comprehensively. Product distribution, energy efficiency and economic benefits are invoked as factors to evaluate the performance of VOC degradation. Finally, the practical application of corona plasma and its advantages are briefly introduced. The review aims to illustrate the enormous potential of corona plasma technology in the treatment of VOCs, and identifies future directions.

Implications: This paper comprehensively describes the principle, characteristics, research progress and engineering application examples of the degradation of volatile organics by corona discharge plasma, to provide a theoretical basis for the industrial application of this process.     

Future-year ozone prediction for the United States using updated models and inputs

The relationship between emission reductions and changes in ozone can be studied using photochemical grid models. These models are updated with new information as it becomes available. The primary objective of this study was to update the previous Collet et al. studies by using the most up-to-date (at the time the study was done) modeling emission tools, inventories, and meteorology available to conduct ozone source attribution and sensitivity studies. Results show future-year, 2030, design values for 8-hr ozone concentrations were lower than base-year values, 2011. The ozone source attribution results for selected cities showed that boundary conditions were the dominant contributors to ozone concentrations at the western U.S. locations, and were important for many of the eastern U.S. locations. Point sources were generally more important in the eastern United States than in the western United States. The contributions of on-road mobile emissions were less than 5 ppb at a majority of the cities selected for analysis. The higher-order decoupled direct method (HDDM) results showed that in most of the locations selected for analysis, NOx emission reductions were more effective than VOC emission reductions in reducing ozone levels. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.

Implications: The relationship between emission reductions and changes in ozone can be studied using photochemical grid models, which are updated with new available information. This study was to update the previous Collet et al. studies by using the most current, at the time the study was done, models and inventory to conduct ozone source attribution and sensitivity studies. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.     

Application of an integrated Weather Research and Forecasting (WRF)/CALPUFF modeling tool for source apportionment of atmospheric pollutants for air quality management: A case study in the urban area of Benxi,China

In this study, the authors endeavored to develop an effective framework for improving local urban air quality on meso-micro scales in cities in China that are experiencing rapid urbanization. Within this framework, the integrated Weather Research and Forecasting (WRF)/CALPUFF modeling system was applied to simulate the concentration distributions of typical pollutants (particulate matter with an aerodynamic diameter <10 μm [PM₁₀], sulfur dioxide [SO₂], and nitrogen oxides [NO_x]) in the urban area of Benxi. Statistical analyses were performed to verify the credibility of this simulation, including the meteorological fields and concentration fields. The sources were then categorized using two different classification methods (the district-based and type-based methods), and the contributions to the pollutant concentrations from each source category were computed to provide a basis for appropriate control measures. The statistical indexes showed that CALMET had sufficient ability to predict the meteorological conditions, such as the wind fields and temperatures, which provided meteorological data for the subsequent CALPUFF run. The simulated concentrations from CALPUFF showed considerable agreement with the observed values but were generally underestimated. The spatial-temporal concentration pattern revealed that the maximum concentrations tended to appear in the urban centers and during the winter. In terms of their contributions to pollutant concentrations, the districts of Xihu, Pingshan, and Mingshan all affected the urban air quality to different degrees. According to the type-based classification, which categorized the pollution sources as belonging to the Bengang Group, large point sources, small point sources, and area sources, the source apportionment showed that the Bengang Group, the large point sources, and the area sources had considerable impacts on urban air quality. Finally, combined with the industrial characteristics, detailed control measures were proposed with which local policy makers could improve the urban air quality in Benxi. In summary, the results of this study showed that this framework has credibility for effectively improving urban air quality, based on the source apportionment of atmospheric pollutants.

Implications: The authors endeavored to build up an effective framework based on the integrated WRF/CALPUFF to improve the air quality in many cities on meso-micro scales in China. Via this framework, the integrated modeling tool is accurately used to study the characteristics of meteorological fields, concentration fields, and source apportionments of pollutants in target area. The impacts of classified sources on air quality together with the industrial characteristics can provide more effective control measures for improving air quality.

Through the case study, the technical framework developed in this study, particularly the source apportionment, could provide important data and technical support for policy makers to assess air pollution on the scale of a city in China or even the world.     

Components and dispersion characteristics of organic and inorganic odorous gases in a large-scale dairy farm

The rapid development of large-scale livestock husbandry has caused serious air pollution problems (e.g., The Tuzuoqi demonstration farm belonging to the Yili Group. The farm is located in the suburb of Hohhot City in northern China). In this study, the gases in typical areas of a large-scale dairy farm were sampled and measured for volatile organic compounds (VOCs), hydrogen sulfide, and ammonia concentrations. Fifty-two species of VOCs were identified. The VOCs emitted from the cowshed mainly consisted of halogenated hydrocarbons (16,960 µg/m³), ketones (15,700 µg/m³), esters (9889 µg/m³), and sulfur compounds (3677 µg/m³). The VOCs from the oxidation pond were mainly composed of halogenated hydrocarbons (21,940 µg/m³) and ketones (3589 µg/m³). The VOCs from the solid–liquid separation tank comprised halogenated hydrocarbons (32,010 µg/m³), ketones (7169 µg/m³), and sulfur compounds (1003 µg/m³). The highest concentrations of ammonia and hydrogen sulfide were obtained from the milking parlor and solid–liquid separation tank, respectively. The ammonia concentration declined gradually due to the superposition of ammonia emitted from the cowshed and milking parlor. Analysis results of the influences of distance and meteorological factors on the dispersion of ammonia and hydrogen sulfide suggested that the dilution factors decreased with increasing distance from the emission source. Within distance ranges of 0–10 and 10–25 m, the concentration dilution factors were positively correlated with wind speed and temperature but negatively correlated with humidity and atmospheric pressure. The results of our work can provide a theoretical basis for the prevention and control of odorous gases in large-scale livestock farms.

Implications: Gases in typical areas of a large-scale dairy farm were sampled, and a total of 52 species of VOCs were identified. The highest concentrations of ketones, sulfur compounds, and esters were obtained at the cowshed (15,700, 3677, and 9889 µg/m³, respectively). Within the distance ranges of 0–10 and 10–25 m, the concentration dilution factors were positively correlated with wind speed and temperature.     

Long-term dust aerosol production from natural sources in Iceland

Iceland is a volcanic island in the North Atlantic Ocean with maritime climate. In spite of moist climate, large areas are with limited vegetation cover where >40% of Iceland is classified with considerable to very severe erosion and 21% of Iceland is volcanic sandy deserts. Not only do natural emissions from these sources influenced by strong winds affect regional air quality in Iceland (“Reykjavik haze”), but dust particles are transported over the Atlantic ocean and Arctic Ocean >1000 km at times. The aim of this paper is to place Icelandic dust production area into international perspective, present long-term frequency of dust storm events in northeast Iceland, and estimate dust aerosol concentrations during reported dust events.

Meteorological observations with dust presence codes and related visibility were used to identify the frequency and the long-term changes in dust production in northeast Iceland. There were annually 16.4 days on average with reported dust observations on weather stations within the northeastern erosion area, indicating extreme dust plume activity and erosion within the northeastern deserts, even though the area is covered with snow during the major part of winter. During the 2000s the highest occurrence of dust events in six decades was reported. We have measured saltation and Aeolian transport during dust/volcanic ash storms in Iceland, which give some of the most intense wind erosion events ever measured.

Icelandic dust affects the ecosystems over much of Iceland and causes regional haze. It is likely to affect the ecosystems of the oceans around Iceland, and it brings dust that lowers the albedo of the Icelandic glaciers, increasing melt-off due to global warming. The study indicates that Icelandic dust may contribute to the Arctic air pollution.

Implications: Long-term records of meteorological dust observations from Northeast Iceland indicate the frequency of dust events from Icelandic deserts. The research involves a 60-year period and provides a unique perspective of the dust aerosol production from natural sources in the sub-Arctic Iceland. The amounts are staggering, and with this paper, it is clear that Icelandic dust sources need to be considered among major global dust sources. This paper presents the dust events directly affecting the air quality in the Arctic region.     

Mapping air quality zones for coastal urban centers

This study presents a new method that incorporates modern air dispersion models allowing local terrain and land–sea breeze effects to be considered along with political and natural boundaries for more accurate mapping of air quality zones (AQZs) for coastal urban centers. This method uses local coastal wind patterns and key urban air pollution sources in each zone to more accurately calculate air pollutant concentration statistics. The new approach distributes virtual air pollution sources within each small grid cell of an area of interest and analyzes a puff dispersion model for a full year’s worth of 1-hr prognostic weather data. The difference of wind patterns in coastal and inland areas creates significantly different skewness (S) and kurtosis (K) statistics for the annually averaged pollutant concentrations at ground level receptor points for each grid cell. Plotting the S-K data highlights grouping of sources predominantly impacted by coastal winds versus inland winds. The application of the new method is demonstrated through a case study for the nation of Kuwait by developing new AQZs to support local air management programs. The zone boundaries established by the S-K method were validated by comparing MM5 and WRF prognostic meteorological weather data used in the air dispersion modeling, a support vector machine classifier was trained to compare results with the graphical classification method, and final zones were compared with data collected from Earth observation satellites to confirm locations of high-exposure-risk areas. The resulting AQZs are more accurate and support efficient management strategies for air quality compliance targets effected by local coastal microclimates.

Implications: A novel method to determine air quality zones in coastal urban areas is introduced using skewness (S) and kurtosis (K) statistics calculated from grid concentrations results of air dispersion models. The method identifies land–sea breeze effects that can be used to manage local air quality in areas of similar microclimates.     

Control of ammonia and urea emissions from urea manufacturing facilities of Petrochemical Industries Company (PIC), Kuwait

Petrochemical Industries Company (PIC) in Kuwait has mitigated the pollution problem of ammonia and urea dust by replacing the melting and prilling units of finished-product urea prills with an environmentally friendly granulation process. PIC has financed a research project conducted by the Coastal and Air Pollution Program’s research staff at the Kuwait Institute for Scientific Research to assess the impact of pollution control strategies implemented to maintain a healthy productive environment in and around the manufacturing premises. The project was completed in three phases: the first phase included the pollution monitoring of the melting and prilling units in full operation, the second phase covered the complete shutdown period where production was halted completely and granulation units were installed, and the last phase encompassed the current modified status with granulation units in full operation. There was substantial decrease in ammonia emissions, about 72%, and a 52.7% decrease in urea emissions with the present upgrading of old melting and prilling units to a state-of-the-art technology “granulation process” for a final finished product. The other pollutants, sulfur dioxide (SO₂), nitrogen oxides (NO_x), and volatile organic compounds (VOCs), have not shown any significant change, as the present modification has not affected the sources of these pollutants.

Implications: Petrochemical Industries Company (PIC) in Kuwait has ammonia urea industries, and there were complaints about ammonia and urea dust pollution. PIC has resolved this problem by replacing “melting and prilling unit” of final product urea prills by more environmentally friendly “granulation unit.” Environmental Pollution and Climate Program has been assigned the duty of assessing the outcome of this change and how that influenced ammonia and urea dust emissions from the urea manufacturing plant.     

Probability analyses of combining background concentrations with model-predicted concentrations

In order to calculate total concentrations for comparison to ambient air quality standards, monitored background concentrations are often combined with model predicted concentrations. Models have low skill in predicting the locations or time series of observed concentrations. Further, adding fixed points on the probability distributions of monitored and predicted concentrations is very conservative and not mathematically correct. Simply adding the 99th percentile predicted to the 99th percentile background will not yield the 99th percentile of the combined distributions. Instead, an appropriate distribution can be created by calculating all possible pairwise combinations of the 1-hr daily maximum observed background and daily maximum predicted concentration, from which a 99th percentile total value can be obtained. This paper reviews some techniques commonly used for determining background concentrations and combining modeled and background concentrations. The paper proposes an approach to determine the joint probabilities of occurrence of modeled and background concentrations. The pairwise combinations approach yields a more realistic prediction of total concentrations than the U.S. Environmental Protection Agency's (EPA) guidance approach and agrees with the probabilistic form of the National Ambient Air Quality Standards.

Implications: EPA's current approaches to determining background concentrations for compliance modeling purposes often lead to “double counting” of background concentrations and actual plume impacts and thus lead to overpredictions of total impacts. Further, the current Tier 1 approach of simply adding the top ends of the background and model predicted concentrations (e.g., adding the 99th percentiles of these distributions together) results in design value concentrations at probabilities in excess of the form of the National Ambient Air Quality Standards.     

The study on biomass fraction estimate methodology of municipal solid waste incinerator in Korea

In Korea, the amount of greenhouse gases released due to waste materials was 14,800,000 t CO₂eq in 2012, which increased from 5,000,000 t CO₂eq in 2010. This included the amount released due to incineration, which has gradually increased since 2010. Incineration was found to be the biggest contributor to greenhouse gases, with 7,400,000 t CO₂eq released in 2012. Therefore, with regards to the trading of greenhouse gases emissions initiated in 2015 and the writing of the national inventory report, it is important to increase the reliability of the measurements related to the incineration of waste materials.

This research explored methods for estimating the biomass fraction at Korean MSW incinerator facilities and compared the biomass fractions obtained with the different biomass fraction estimation methods. The biomass fraction was estimated by the method using default values of fossil carbon fraction suggested by IPCC, the method using the solid waste composition, and the method using incinerator flue gas.

The highest biomass fractions in Korean municipal solid waste incinerator facilities were estimated by the IPCC Default method, followed by the MSW analysis method and the Flue gas analysis method. Therefore, the difference in the biomass fraction estimate was the greatest between the IPCC Default and the Flue gas analysis methods. The difference between the MSW analysis and the flue gas analysis methods was smaller than the difference with IPCC Default method. This suggested that the use of the IPCC default method cannot reflect the characteristics of Korean waste incinerator facilities and Korean MSW.

Implications: Incineration is one of most effective methods for disposal of municipal solid waste (MSW). This paper investigates the applicability of using biomass content to estimate the amount of CO₂ released, and compares the biomass contents determined by different methods in order to establish a method for estimating biomass in the MSW incinerator facilities of Korea. After analyzing the biomass contents of the collected solid waste samples and the flue gas samples, the results were compared with the Intergovernmental Panel on Climate Change (IPCC) method, and it seems that to calculate the biomass fraction it is better to use the flue gas analysis method than the IPCC method. It is valuable to design and operate a real new incineration power plant, especially for the estimation of greenhouse gas emissions.     

Public health and components of particulate matter: The changing assessment of black carbon

In 2012, the WHO classified diesel emissions as carcinogenic, and its European branch suggested creating a public health standard for airborne black carbon (BC). In 2011, EU researchers found that life expectancy could be extended four to nine times by reducing a unit of BC, vs reducing a unit of PM_2.5. Only recently could such determinations be made. Steady improvements in research methodologies now enable such judgments.

In this Critical Review, we survey epidemiological and toxicological literature regarding carbonaceous combustion emissions, as research methodologies improved over time. Initially, we focus on studies of BC, diesel, and traffic emissions in the Western countries (where daily urban BC emissions are mainly from diesels). We examine effects of other carbonaceous emissions, e.g., residential burning of biomass and coal without controls, mainly in developing countries.

Throughout the 1990s, air pollution epidemiology studies rarely included species not routinely monitored. As additional PM_2.5. chemical species, including carbonaceous species, became more widely available after 1999, they were gradually included in epidemiological studies. Pollutant species concentrations which more accurately reflected subject exposure also improved models.

Natural “interventions” - reductions in emissions concurrent with fuel changes or increased combustion efficiency; introduction of ventilation in highway tunnels; implementation of electronic toll payment systems – demonstrated health benefits of reducing specific carbon emissions. Toxicology studies provided plausible biological mechanisms by which different PM species, e.g., carbonaceous species, may cause harm, aiding interpretation of epidemiological studies.

Our review finds that BC from various sources appears to be causally involved in all-cause, lung cancer, and cardiovascular mortality, morbidity, and perhaps adverse birth and nervous system effects. We recommend that the U.S. EPA rubric for judging possible causality of PM_2.5. mass concentrations, be used to assess which PM_2.5. species are most harmful to public health.

Implications: Black carbon (BC) and correlated co-emissions appear causally related with all-cause, cardiovascular, and lung cancer mortality, and perhaps with adverse birth outcomes and central nervous system effects. Such findings are recent, since widespread monitoring for BC is also recent. Helpful epidemiological advances (using many health relevant PM_2.5 species in models; using better measurements of subject exposure) have also occurred. “Natural intervention” studies also demonstrate harm from partly combusted carbonaceous emissions. Toxicology studies consistently find biological mechanisms explaining how such emissions can cause these adverse outcomes. A consistent mechanism for judging causality for different PM_2.5 species is suggested.

A list of acronyms will be found at the end of the article.     

An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppm_v). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression.

Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.     

Analysis of air quality in Dire Dawa,Ethiopia

Ambient air quality was monitored and analyzed to develop air quality index and its implications for livability and climate change in Dire Dawa, Ethiopia. Using survey research design, 16 georeferenced locations, representing different land uses, were randomly selected and assessed for sulfur dioxide (SO₂), nitrogen dioxide (NO₂), carbon dioxide (CO₂), carbon monoxide (CO),volatile organic compounds (VOCs), and meteorological parameters (temperature and relative humidity). The study found mean concentrations across all land uses for SO₂ of 0.37 ± 0.08 ppm, NO₂ of 0.13 ± 0.17 ppm, CO₂ of 465.65 ± 28.63 ppm, CO of 3.35 ± 2.04 ppm, and VOCs of 1850.67 ± 402 ppm. An air quality index indicated that ambient air quality for SO₂ was very poor, NO₂ ranged from moderate to very poor, whereas CO rating was moderate. Significant positive correlations existed between temperature and NO₂, CO₂, and CO and between humidity and VOCs. Significant relationships were also recorded between CO₂ and NO₂ and between CO and CO₂. Poor urban planning, inadequate pollution control measure, and weak capacity to monitor air quality have implications for energy usage, air quality, and local meteorological parameters, with subsequent feedback into global climate change. Implementation of programs to monitor and control emissions in order to reduce air pollution will provide health, economic, and environmental benefits to the city.

Implications: The need to develop and implement emission control programs to reduce air pollution in Dire Dawa City is urgent. This will provide enormous economic, health, and environmental benefits. It is expected that economic effects of air quality improvement will offset the expenditures for pollution control. Also, strategies that focus on air quality and climate change present a unique opportunity to engage different stakeholders in providing inclusive and sustainable development agenda for Dire Dawa.     

Statistical analysis of winter ozone exceedances in the Uintah Basin,Utah, USA

Because of the confluence of several factors (persistent multiday inversions, petroleum production, and snow cover), the Uintah Basin of eastern Utah, USA, exhibits high concentrations of winter ozone. A regression analysis is presented that successfully predicts daily ozone concentration with a standard error of about 11 ppb. It also predicts with 90% accuracy whether any given day will exceed the National Ambient Air Quality Standard for ozone, 70 ppb. An analysis is introduced for calculating a “pseudo-lapse rate,” a determination of inversion intensity in the absence of sounding data. By combining the model with historical meteorological data, it is possible to make long-range predictions about ozone formation. The odds of observing no exceedance days in any given season are 38%. The odds of only three or fewer exceedance days in any given season are 46%.

Implications: This paper provides an improved understanding of the scientific underpinnings of the winter ozone phenomenon and an ability to make long-range predictions.     

Intercomparison of chemical mechanisms for air quality policy formulation and assessment under North American conditions

The intercomparison of seven chemical mechanisms for their suitability for air quality policy formulation and assessment is described. Box modeling techniques were employed using 44 sets of background environmental conditions covering North America to constrain the chemical development of the longer lived species. The selected mechanisms were modified to enable an unbiased assessment of the adequacy of the parameterizations of photochemical ozone production from volatile organic compound (VOC) oxidation in the presence of NO_x. Photochemical ozone production rates responded differently to 30% NO_x and VOC reductions with the different mechanisms, despite the striking similarities between the base-case ozone production rates. The 30% reductions in NO_x and VOCs also produced changes in OH. The responses in OH to 30% reductions in NO_x and VOCs appeared to be more sensitive to mechanism choice, compared with the responses in the photochemical ozone production rates. Although 30% NO_x reductions generally led to decreases in OH, 30% reductions in VOCs led to increases in OH, irrespective of mechanism choice and background environmental conditions. The different mechanisms therefore gave different OH responses to NO_x and VOC reductions and so would give different responses in terms of changes in the fate and behavior of air toxics, acidification and eutrophication, and fine particle formation compared with others, in response to ozone control strategies. Policymakers need to understand that there are likely to be inherent differences in the responses to ozone control strategies between different mechanisms, depending on background environmental conditions and the extents of NO_x and VOC reductions under consideration.

Implications: The purpose of this paper is to compare predicted ozone responses to NO_x and VOC reductions with seven chemical mechanisms under North American conditions. The good agreement found between the tested mechanisms should provide some support for their application in the air quality models used for policymaking.     

Comparison of stack measurement data from R&D facilities to regulatory criteria: A case study from PNNL

Chemical emissions from research and development (R&D) activities are difficult to estimate because of the large number of chemicals used and the potential for continual changes in processes. In this case study, stack measurements taken from R&D facilities at Pacific Northwest National Laboratory (PNNL) were examined, including extreme worst-case emissions estimates and alternate analyses using a Monte Carlo method that takes into account the full distribution of sampling results. The objective of this study was to develop techniques to estimate emissions from stack measurement data that take into account a high degree of variability in the actual emissions. The results from these analyses were then compared to emissions estimated from chemical inventories. Results showed that downwind ambient air concentrations calculated from the stack measurement data were below acceptable source impact levels (ASILs) for almost all compounds, even under extreme worst-case analyses. However, for compounds with averaging periods of a year, the unrealistic but simplifying extreme worst-case analysis often resulted in calculated emissions that were above the lower level regulatory criteria used to determine modeling requirements or to define trivial releases. Compounds with 24-hr averaging periods were nearly all several orders of magnitude below all, including the trivial release, criteria. The alternate analysis supplied a more realistic basis of comparison and an ability to explore effects under different operational modes.

Implications:

Air emissions from research operations are difficult to estimate because of the changing nature of research processes and the small quantity and wide variety of chemicals used. Stack measurements can be used to verify compliance with applicable regulatory criteria. This study shows that while extreme worst-case assumptions can be used for a relatively simple initial comparison, methods that take into account the full range of measurement data are needed to provide a more realistic estimate of emissions for comparison to regulatory criteria, particularly those criteria that define trivial levels of environmental concern.     

Separation of brown carbon from black carbon for IMPROVE and Chemical Speciation Network PM2.5 samples

The replacement of the Desert Research Institute (DRI) model 2001 with model 2015 thermal/optical analyzers (TOAs) results in continuity of the long-term organic carbon (OC) and elemental carbon (EC) database, and it adds optical information with no additional carbon analysis effort. The value of multiwavelength light attenuation is that light absorption due to black carbon (BC) can be separated from that of brown carbon (BrC), with subsequent attribution to known sources such as biomass burning and secondary organic aerosols. There is evidence of filter loading effects for the 25% of all samples with the highest EC concentrations based on the ratio of light attenuation to EC. Loading corrections similar to those used for the seven-wavelength aethalometer need to be investigated. On average, nonurban Interagency Monitoring of PROtected Visual Environments (IMPROVE) samples show higher BrC fractions of short-wavelength absorption than urban Chemical Speciation Network (CSN) samples, owing to greater influence from biomass burning and aged aerosols, as well as to higher primary BC contributions from engine exhaust at urban sites. Sequential samples taken during an Everglades National Park wildfire demonstrate the evolution from flaming to smoldering combustion, with the BrC fraction increasing as smoldering begins to dominate the fire event.

Implications: The inclusion of seven wavelengths in thermal/optical carbon analysis of speciated PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) samples allows contributions from biomass burning and secondary organic aerosols to be estimated. This separation is useful for evaluating control strategy effectiveness, identifying exceptional events, and determining natural visibility conditions.