A Device for Measuring Volatile Organic-Carbon Emissions from Cooling-Tower Water

A manual method for measuring reduced sulfur compounds in kraft pulp mill and sulfur recovery plant emissions was evaluated. The method involves removing SO₂ from the gas stream (if present) with a citric acid-potassium citrate buffer that passes reduced sulfur compounds; thermal oxidation of all reduced sulfur compounds to SO₂; collection of the SO₂ in H₂O₂; and a titrimetric analysis of the H₂O₂ for SO₄ ^2?. A heated filter removes alkaline particulate matter that would produce a negative interference if absorbed by the buffer. When used at kraft pulp mills, the method agrees closely with Reference Method 16, provided that nonregulated reduced sulfur compounds, such as carbonyl sulfide, are not present in the emissions. At sulfur recovery plants, nonregulated reduced sulfur compounds, such as thiophene, are likely to be present in the emissions and will produce a positive bias in the results obtained with this method. The precision of the method ranges from 1 to 7 percent relative standard deviation.     

Urban CO Concentrations and Vehicle Emissions

The effect of the general growth of CO vehicular emissions in urban areas on the CAMP station measurements in downtown areas, where vehicular traffic is saturated is considered. With the assumption that the street-level CO concentration is derived from the sum of an urban background term and a local street-effect term, the urban background CO concentration is computed with a diffusion model by introducing a simple area source distribution. The local street-effect term is taken to be constant at a saturation emission level corresponding to a saturation traffic density when the emission per vehicle-mile and meteorological conditions are fixed. The present analysis indicates that the local street-effect term, AC, has a major role in determining street-level concentrations for pollutants, such as CO, whose air quality standard is based on maximum concentrations with averaging times of 1 hour and 8 hours. The relevance of this analysis to the abatement requirements of the Clean Air Amendments and to the driving cycle adopted is discussed.     

Measuring Inorganic and Alkyl Lead Emissions from Stationary Sources

Described are the results from studies done to provide test methods for state and local air pollution control agencies to measure accurately the lead emissions from stationary source stacks as required in the National Ambient Air Quality Standard for Lead. Separate test methods were developed for measuring inorganic lead and alkyl lead compounds. Inorganic lead is collected in a standard particulate sampling train, digested with 50% (V/V) nitric acid and 3% hydrogen peroxide and analyzed by atomic absorption spectrometry. Alkyl lead compounds are collected in iodine monochloride and analyzed by atomic absorption spectrometry without prior solvent extraction. Standard solutions of inorganic lead in dilute nitric acid are used to calibrate the spectrophotometer in both methods. The inorganic lead test method was evaluated using baghouse dust samples from a primary copper and a primary lead smelter and stack samples from a lead recovery furnace, a primary battery manufacturing plant, a gray iron foundry and a secondary lead smelter. The alkyl lead method was evaluated using alkyl lead motor mix fluids and samples from an alkyl lead manufacturing plant vent stack.     

Seasonal and Spatial Variations of Ammonia Emissions from an Open-Lot Dairy Operation

Abstract

There is a need for a robust and accurate technique to measure ammonia (NH₃) emissions from animal feeding operations (AFOs) to obtain emission inventories and to develop abatement strategies. Two consecutive seasonal studies were conducted to measure NH₃ emissions from an open-lot dairy in central Texas in July and December of 2005. Data including NH₃ concentrations were collected and NH₃ emission fluxes (EFls), emission rates (ERs), and emission factors (EFs) were calculated for the open-lot dairy. A protocol using flux chambers (FCs) was used to determine these NH₃ emissions from the open-lot dairy. NH₃ concentration measurements were made using chemiluminescence-based analyzers. The ground-level area sources (GLAS) including open lots (cows on earthen corrals), separated solids, primary and secondary lagoons, and milking parlors were sampled to estimate NH₃ emissions. The seasonal NH₃ EFs were 11.6 ± 7.1 kg-NH₃ yr^-1head^-1 for the summer and 6.2 ± 3.7 kg-NH₃ yr^-1head^-1 for the winter season. The estimated annual NH₃ EF was 9.4 ± 5.7 kg-NH₃ yr^-1head^-1 for this open-lot dairy. The estimated NH₃ EF for winter was nearly 47% lower than summer EF. Primary and secondary lagoons (～37) and open-lot corrals (～63%) in summer, and open-lot corrals (～95%) in winter were the highest contributors to NH₃ emissions for the open-lot dairy. These EF estimates using the FC protocol and real-time analyzer were lower than many previously reported EFs estimated based on nitrogen mass balance and nitrogen content in manure. The difference between the overall emissions from each season was due to ambient temperature variations and loading rates of manure on GLAS. There was spatial variation of NH₃ emission from the open-lot earthen corrals due to variable animal density within feeding and shaded and dry divisions of the open lot. This spatial variability was attributed to dispirit manure loading within these areas.     

Idle Emissions from Heavy-Duty Diesel Vehicles: Review and Recent Data

Abstract

Heavy-duty diesel vehicle idling consumes fuel and reduces atmospheric quality, but its restriction cannot simply be proscribed, because cab heat or air-conditioning provides essential driver comfort. A comprehensive tailpipe emissions database to describe idling impacts is not yet available. This paper presents a substantial data set that incorporates results from the West Virginia University transient engine test cell, the E-55/59 Study and the Gasoline/Diesel PM Split Study. It covered 75 heavy-duty diesel engines and trucks, which were divided into two groups: vehicles with mechanical fuel injection (MFI) and vehicles with electronic fuel injection (EFI). Idle emissions of CO, hydrocarbon (HC), oxides of nitrogen (NO_x), particulate matter (PM), and carbon dioxide (CO₂) have been reported. Idle CO₂ emissions allowed the projection of fuel consumption during idling. Test-to-test variations were observed for repeat idle tests on the same vehicle because of measurement variation, accessory loads, and ambient conditions. Vehicles fitted with EFI, on average, emitted [~20 g/hr of CO, 6 g/hr of HC, 86 g/hr of NO_x, 1 g/hr of PM, and 4636 g/hr of CO₂ during idle. MFI equipped vehicles emitted ~35 g/hr of CO, 23 g/hr of HC, 48 g/hr of NO_x, 4 g/hr of PM, and 4484 g/hr of CO₂, on average, during idle. Vehicles with EFI emitted less idleCO, HC, and PM, which could be attributed to the efficient combustion and superior fuel atomization in EFI systems. Idle NO_x, however, increased with EFI, which corresponds with the advancing of timing to improve idle combustion. Fuel injection management did not have any effect on CO₂ and, hence, fuel consumption. Use of air conditioning without increasing engine speed increased idle CO₂, NO_x, PM, HC, and fuel consumption by 25% on average. When the engine speed was elevated from 600 to 1100 revolutions per minute, CO₂ and NO_x emissions and fuel consumption increased by >150%, whereas PM and HC emissions increased by ~100% and 70%, respectively. Six Detroit Diesel Corp. (DDC) Series 60 engines in engine test cell were found to emit less CO, NO_x, and PM emissions and consumed fuel at only 75%of the level found in the chassis dynamometer data. This is because fan and compressor loads were absent in the engine test cell.     

Correlating Emissions with Time and Temperature to Predict Worst-Case Emissions from Open Liquid Area Sources

Abstract

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry’s law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H₂S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H₂S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85–90 °F), the constant emission rate underestimated odor impact significantly (by 73%).     

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.     

A Transition-Flow Reactor Tube for Measuring Trace Gas Concentrations

Dry deposition contributes significantly to the acidification of ecosystems. However, difficulties in measuring dry deposition of reactive gases and fine particles make routine direct monitoring impractical. An alternate approach is to use the “concentration monitoring” method in which dry deposition flux is estimated as the product of measured concentration and estimated deposition velocity. A sampling system that performs over the period of 6 hours to 7 days, depending on atmospheric concentrations, has been developed. It consists of a Teflon cyclone to exclude particles larger than about 2 μm, selective solid adsorption media for reactive gases—some of which are sampled from a transition flow to avoid possible bias from particle evaporation, a particle filter, and a final gas adsorption filter to collect the remaining trace gas. The sampler Is the first reported application of transition flow mass transfer for the collection and quantitative measurement of trace atmospheric gases. Laboratory and field tests have shown that the sampler performs well for HNO₃(g).     

Abatement of Ammonia and Hydrogen Sulfide Emissions from a Swine Lagoon Using a Polymer Biocover

ABSTRACT

The purpose of this research was to determine the efficiency of a polymer biocover for the abatement of H₂S and NH₃ emissions from an east-central Missouri swine lagoon with a total surface area of 7800 m². The flux rate of NH₃, H₂S, and CH₄ was monitored continuously from two adjacent, circular (d = 66 m) control and treatment plots using a nonintrusive, micrometeorological method during three independent sampling periods that ranged between 52 and 149 hr. Abatement rates were observed to undergo a temporal acclimation event in which NH₃ abatement efficiency improved from 17 to 54% (p = <0.0001 to 0.0005) and H₂S abatement efficiency improved from 23 to 58% (p < 0.0001) over a 3-month period. The increase in abatement efficiency for NH₃ and H₂S over the sampling period was correlated with the development of a stable anaerobic floc layer on the bottom surface of the biocover that reduced mass transfer of NH₃ and H₂S across the surface. Analysis of methanogenesis activity showed that the biocover enhanced the rate of anaerobic digestion by 25% when compared with the control. The biocover-enhanced anaerobic digestion process was shown to represent an effective mechanism to counteract the accumulation of methanogenic substrates in the biocovered lagoon.     

A Passive Flux Denuder for Evaluating Emissions of Ammonia at a Dairy Farm

Abstract

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH₃), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH₃ from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH₃ flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH₃ flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH₃ emissions.     

Divided Combustion Chamber Gasoline Engines A Review for Emissions and Efficiency

To facilitate the distinction among different engine types, this paper indicates first a general classification of gasoline engines. This classification contains the group of stratified charge engines, and shows that, within this group, the divided combustion chamber engine type constitutes a major subdivision. Three characteristic designs of this type of engine are described in some detail, and fuel economy and emission results are presented. Data obtained with one of these engines indicate excellent fuel consumptions, showing at light loads values close to those achieved by Diesel engines. Data also show that automobiles equipped with another of the engines described in the paper have passed, with ample margin, the 1975 Federal Emission Standards, without added devices for exhaust gas treatment, while maintaining satisfactory fuel economy. Some aims that should be pursued in order to achieve, simultaneously, both the optimal fuel economy and emission reduction potential of the stratified engine are outlined. It is concluded that substantial improvements should yet be expected if the proven advantages of the divided combustion chamber engine are recognized and sufficient efforts are applied for further development.     

Spatial Variation in Acidic Sulfate and Ammonia Concentrations within Metropolitan Philadelphia

Abstract

Acidic sulfate concentrations were measured in metropolitan Philadelphia during the summers of 1992 and 1993, as part of a continuing effort to characterize particle concentrations in urban environments. Sampling was performed simultaneously at eight sites located within and around metropolitan Philadelphia. Sites were selected based on their population density and on their distance and direction from the city center. Air pollution sampling was conducted every other day during the summer of 1992 and every day during the summer of 1993. All samples were collected for 24-h periods beginning at 9 a.m. (EDT). All acidic sulfate and ammonia samples were collected using modified Harvard-EPA Annular Denuder Systems (HEADS).

In this paper, we examine the spatial variation in acidic sulfate and ammonia concentrations within the metropolitan Philadelphia area. We also identify factors that may influence their variation and develop models to predict their concentrations. Outdoor sulfate (SO₄ ^2?) concentrations were uniform within metropolitan Philadelphia; however, aerosol strong acidity (H⁺) concentrations varied spatially. This variation generally was independent of wind direction, but was related to local factors, such as the NH₃ concentration, population density, and distance from the center of the city. Physico-chemical models, which were developed using data collected during the summer of 1992, were excellent predictors of 24-h and mean summertime H⁺ concentrations measured during the summer of 1993. Models accounted for 78% of the variation in 24-h H⁺ levels. Results suggest that a single stationary ambient (SAM) monitor would be sufficient to estimate SO₄ ^2? exposures for populations living in Philadelphia. For H⁺, however, multiple monitoring sites or models should be used to determine the outdoor H+ exposures of populations living in urban environments, although a single SAM site may provide an excellent index of H⁺ variation over time.     

Evaluation of a Test Method for Measuring Indoor Air Emissions from Dry-Process Photocopiers

ABSTRACT

A large chamber test method for measuring indoor air emissions from office equipment was developed, evaluated, and revised based on the initial testing of four dry-process photocopiers. Because all chambers may not necessarily produce similar results (e.g., due to differences in sink effects, temperature and humidity control, air exchange, pollutant monitoring, and measurement biases), a preliminary four-laboratory evaluation of the revised test method was conducted. To minimize variability, the evaluation used a single dry-process photocopier that was shipped to each of the four laboratories along with supplies (i.e., toner and paper).

The results of this preliminary four-laboratory evaluation demonstrate that the test method was used successfully in the different chambers to measure emissions from dry-process photocopiers. Differences in chamber design and construction appeared to have had minimal effect on the results for the volatile organic compounds (VOCs). Perhaps more important than the chamber itself is the sample analysis as identified by duplicate samples that were analyzed by a different laboratory. Percent relative standard deviation (%RSD) was used to provide a simplistic view of interlaboratory precision for this evaluation. Excluding problems with suspected analytical bias observed from one of the laboratories, the precision was excellent for the VOCs with RSDs of less than 10% in most cases. Less precision was observed among the laboratories for aldehydes/ketones (RSD of 23.2% for formaldehyde). The precision for ozone emission rates among three of the laboratories was excellent (RSD of 7.9%), but emission rates measured at the fourth laboratory were much higher.     

Comparison of Analytical Techniques for Measuring Hydrocarbon Emissions from the Manufacture of Fiberglass-Reinforced Plastics

ABSTRACT

Research Triangle Institute and the U.S. Environmental Protection Agency conducted several projects to measure hydrocarbon emissions associated with the manufacture of fiberglass-reinforced plastics. The purpose of these projects was to evaluate pollution prevention techniques to reduce emissions by altering raw materials, application equipment, and operator technique. Analytical techniques were developed to reduce the cost of these emission measurements. Emissions from a small test mold in a temporary total enclosure (TTE) correlated with emissions from full-size production molds in a separate TTE. Gravimetric mass balance measurements inside the TTE generally agreed to within ± 30 % with total hydrocarbon (THC) measurements in the TTE exhaust duct. Pure styrene evaporation tests served as quality control checks for THC measurements and generally agreed to within ± 5 %.     

Simultaneous Control of PCDD/PCDF,HCI and NOX Emissions from Municipal Solid Waste Incinerators with Ammonia Injection

This article Introduces a technology for the simultaneous control of the emissions of PCDD/ PCDF, hydrochloric acid (HCI) and nitrogen oxides (NO_x) from municipal solid waste (MSW) Incinerators. The technology uses ammonia as the control medium for all three pollutants. In this paper, the theoretical basis of the technology Is discussed. In addition, a bench-scale experiment proving the theory Is described and the practical application of the theory Is presented. Finally, further steps which are being taken to develop the technology for commercial application are detailed.     

On a Strategy for Reducing Short-range Daytime Ground Level Concentrations Due to Emissions from Very Tall Stacks

Abstract

Airborne fine particle sulfur data from the summer intensive of Project MOHAVE (Measurement of Haze and Visual Effects) was analyzed by the Receptor Model Applied to Patterns in Space (RMAPS) model, a novel multivariate receptor-oriented model that applies to secondary and primary species. The sulfur data from 17 sites were found to be well predicted by three spatial patterns interpreted as sources along the valley of the Colorado River; transport from sources located to the southwest; and transport from sources located to the southeast. The model was tested by using parameters derived from the 17-site data set to apportion sulfur for six sites that were not part of the original data set. The sulfur apportionment for these six sites was in agreement with the original apportionment and the physical interpretation of the spatial patterns given above. The effects of systematic and random error on the sulfur apportionment were estimated. The amount of sulfur associated with the Colorado River valley sources was rather insensitive to both types of error. For the two sites in the Grand Canyon National Park, the fraction of total particulate sulfur from the Colorado River valley source is estimated to be in the range of 27-65% at Meadview and 11-28% at Hopi Point.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

Taxing Emissions: A Theoretical Note

This report contains a short theoretical proof for the non-optima lity of a uniform emission tax. A method recently suggested for finding the optimal level of a uniform tax is criticized. An alternative tax system that could be either uniform or non-uniform that is gradually increasing over time is suggested instead. The paper is aimed at stimulating discussions on theoretical and empirical grounds on the feasibility and efficiency of the suggested tax.