The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Correlating emissions with time and temperature to predict worst-case emissions from open liquid area sources

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 degrees F), the constant emission rate underestimated odor impact significantly (by 73%).     

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%).     

Sulfur Gas Emissions From Stored Flue Gas Desulfurization Sludges

The emissions of volatile sulfur-containing compounds from 13 flue gas desulfurization (FGD) sludge field storage sites have been characterized. Sulfur gas emissions from the sludge surfaces were determined by measuring the sulfur gas enhancement of sulfur-free sweep air passing through a dynamic emission flux chamber placed over selected sampling sites. Samples of the enclosure sweep air were cryogenically concentrated in surface-deactivated Pyrex “U” traps. Analyses were conducted by wall-coated, open-tubular, capillary column, cyrogenic gas chromatography using a sulfur-selective, flame photometric detector. Several major variables associated with FGD sludge production processes were examined in relation to the measured range and variations in sulfur fluxes including: (a) the sulfur dioxide scrubbing reagent used, (b) sludge sulfite oxidation, (c) “unfixed” or “fixed” FGD sludge, and (d) ponding or landfill storage. The composition and concentration of the measured sulfur gas emissions were found to vary with the type of sludge, the effectiveness of rainwater drainage from the landfill surface, the method of impoundment, and the sulfate/sulfite ratio of the sludge. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide were identified in varying concentrations and ratios in the FGD sludge emissions. In addition, up to four unidentified organo- sulfur compounds were found in the emissions from four FGD sludges. The sulfur flux from one FGD storage pond was analyzed by gas chromatography-single ion monitoring mass spectrometry. In addition to the four identified sulfur compounds, this flux contained large concentrations of benzene, toluene, and α-pinene. The measured, total sulfur emissions ranged from less than 0.01 to nearly 0.3 kg of sulfur per day for an equivalent 100 acre (40.5 hectare) sludge impoundment surface.     

Air Levels and Mutagenicity of PM-10 in an Indoor Ice Arena

Abstract

Hazardous waste sites and industrial facilities contain area sources of fugitive emissions. Emission rate measurements or estimates are necessary for air pathway assessments for these sources. Emission rate data can be useful for the design of emission control and remediation strategies as well as for predictive modeling for population exposure assessments. This paper describes the use of a direct emission measurement approach – the enclosure approach using an emission isolation flux chamber – to measure emission rates of various volatile organic compounds (VOCs) from contaminated soil and water. A variety of flux chamber equipment designs and operating procedures have been employed by various researchers. This paper contains a review of the design and operational variables that affect the accuracy and precision of the method. Guidance is given as to the optimum flux chamber design and operating conditions for various types of emission sources. Also presented is a generic quality control program that gives the minimum number of duplicate, blank, background, and repeat samples that should be performed.     

Air emission flux from contaminated dredged materials stored in a pilot-scale confined disposal facility

A pilot-scale field simulation was conducted to estimate the air emissions from contaminated dredged material stored in a confined disposal facility (CDF). Contaminated dredged material with a variety of organic chemicals, obtained from Indiana Harbor Canal, was used in the study. It was placed in an outdoor CDF simulator (i.e., a lysimeter of dimensions 4 ft x 4 ft x 2 ft). A portable, dynamic flux chamber was used to periodically measure emissions of various polynuclear aromatic hydrocarbons (PAHs). A weather station was set up to monitor and record the meteorological conditions during the experiment. The fluxes of several PAHs were monitored over time for 6 1/2 months. Initial 6-hr average fluxes varied from 2 to 20 ng/cm2/hr for six different PAHs. The flux values declined rapidly for all compounds soon after placement of the dredged material in the CDE Chemical concentrations derived from flux values were generally of low magnitude compared with ambient standards. Data obtained from the experiment were compared against those predicted using models for air emissions. Model simulations showed that initially the flux was largely from exposed pore water from saturated (wet) sediment, whereas the long-term flux was controlled by diffusion through the pore air of the unsaturated sediment. Model predictions generally overestimated the measured emissions. A rainfall event was simulated, and the dredged material was reworked to simulate that typical of a CDF operation. Increased flux was observed upon reworking the dredged material.     

A passive flux denuder for evaluating emissions of ammonia at a dairy farm

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 has required active 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.     

The Recovery of Ammonia and Hydrogen Sulflde from Ground-Level Area Sources Using Dynamic Isolation Flux Chambers: Bench-Scale Studies

Abstract

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH₃) and hydrogen sulflde (H₂S) from dynamic isolation flux chambers. H₂S (80–4000 ppb) and NH₃ (5000–40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H₂S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H₂S could be recovered during the given sampling period. NH₃ emissions exhibited similar behavior between concentrations of 5000–40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH₃ sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH₃ or H₂S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH₃ and H₂S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH₃ and H₂S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the full-scale sensitivity of the gas sensing equipment. The use of 46–90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

A Simple Field Method to Determine Mercury Volatilization from Soils (3 pp)

Background Estimations of gaseous mercury volatilization from soils are often complex, stationary and expensive. Our objective was to develop a mobile and more simple, easy to handle and more cost-effective field method allowing rapid estimates of potential Hg emissions from soils. Methods. The study site is located in Germany, about 100 kilometers south-westerly of Berlin and influenced by the river Elbe and its tributary Saale river. The site is representative for a lot of other floodplain locations at the river Elbe and highly polluted with Hg and other heavy metals. For our study we developed a system consisting of a glass chamber gas, two gold traps, a battery operated pump and a gas meter. Adsorbed total gaseous mercury (TGM) in the gold traps was determined by use of atomic absorption spectrometry (AAS). Results and Discussion. In contrast to the common used flux chambers we designed a chamber without inlet and named it gas suck up chamber (GSC). TGM fluxes determined with the GSC showed a very close linear correlation (r = 0.993) between the TGM content in the gold traps and the corresponding pumped gas volume. The TGM adsorbed, increased proportional with increasing gas volume indicating homogenous concentrations of gaseous mercury in the soil air sucked. In contrast to the commonly used dynamic flux chamber with the aim of precisely measuring actual fluxes of Hg from a defined soil area, we focused on developing of a measurement system which will allow rapid estimates of potential Hg emissions of a site. Earlier research at the study site indicated a high potential for releasing volatile Hg from the soil to the atmosphere. Indeed, due to the high Hg content of the soil significant amounts of TGM could be detected and no shortage was reached. Conclusion. Our initial measurements are still too few in number neither to generalize the achieved results nor discuss controlling factors and processes. However, we are pleased to communicate that the developed GSC is well suited to become an effective sampling set up to rapidly estimate the magnitude of Hg volatilization from soils. Outlook. Further measurements at other polluted locations are necessary to verify the GSC method. In addition the use of a mercury analyzer instead of gold traps is planned for faster risk assessments.     

Emissions of organic compounds from produced water ponds II: Evaluation of flux chamber measurements with inverse-modeling techniques

In this study, the authors apply two different dispersion models to evaluate flux chamber measurements of emissions of 58 organic compounds, including C2–C11 hydrocarbons and methanol, ethanol, and isopropanol from oil- and gas-produced water ponds in the Uintah Basin. Field measurement campaigns using the flux chamber technique were performed at a limited number of produced water ponds in the basin throughout 2013–2016. Inverse-modeling results showed significantly higher emissions than were measured by the flux chamber. Discrepancies between the two methods vary across hydrocarbon compounds and are largest in alcohols due to their physical chemistries. This finding, in combination with findings in a related study using the WATER9 wastewater emission model, suggests that the flux chamber technique may underestimate organic compound emissions, especially alcohols, due to its limited coverage of the pond area and alteration of environmental conditions, especially wind speed. Comparisons of inverse-model estimations with flux chamber measurements varied significantly with the complexity of pond facilities and geometries. Both model results and flux chamber measurements suggest significant contributions from produced water ponds to total organic compound emission from oil and gas productions in the basin.

Implications: This research is a component of an extensive study that showed significant amount of hydrocarbon emissions from produced water ponds in the Uintah Basin, Utah. Such findings have important meanings to air quality management agencies in developing control strategies for air pollution in oil and gas fields, especially for the Uintah Basin in which ozone pollutions frequently occurred in winter seasons.     

Evaluation of VOC emission measurement methods for paint spray booths

Interest in regulations to control solvent emissions from automotive painting systems is increasing, especially in ozone nonattainment areas. Therefore, an accurate measurement method for VOC emissions from paint spray booths used in the automotive industry is needed to ascertain the efficiency of the spray booth capture and the total emissions. This paper presents the results of a laboratory study evaluating potential VOC sampling and analytical methods used in estimating paint spray booth emissions, and discusses these results relative to other published data. Eight test methods were selected for evaluation. The accuracy of each sampling and analytical method was determined using test atmospheres of known concentration and composition that closely matched the actual exhaust air from paint spray booths. The solvent mixture to generate the test atmospheres contained a large proportion of polar, oxygenated hydrocarbons such as ketones and alcohols. A series of identical tests was performed for each sampling/analytical method with each test atmosphere to assess the precision of the methods. The study identified significant differences among the test methods in terms of accuracy, precision, cost, and complexity.     

Nitrous oxide emission from an agricultural field: Comparison between measurements by flux chamber and micrometerological techniques

The soil in a drained fjord area, reclaimed for arable farming, produced N₂O mainly at 75–105 cm depth, just above the ground water level. Surface emissions of N₂O were measured from discrete small areas by closed and open-flow chamber methods, using gas chromatographic analysis and over larger areas by integrative methods: flux gradient (analysis by FTIR), conditional sampling (analysis by TDLAS), and eddy covariance (analysis by TDLAS). The mean emission of N₂O as determined by chamber procedures during a 9-day campaign was 162–202 μg N₂ONm⁻²h⁻¹ from a wheat stubble and 328–467 μg N₂ONm⁻² h⁻¹ from a carrot field. The integrative approaches gave N₂O emissions of 149–495 μg N₂ONm⁻² h⁻¹, i.e. a range similar to those determined with the chamber methods. Wind direction affected the comparison of chamber and integrative methods because of patchiness of the N₂O emission over the area. When a uniform area with a single type of vegetation had a dominant effect on the N₂O gradient at the sampling mast, the temporal variation in N₂O emission determined by the flux gradient/FTIR method and chamber methods was very similar, with differences of only 18% or less in mean N₂O emission, well below the variation encountered with the chamber methods themselves. A detailed comparison of FTIR gradient and chamber data taking into account the precise emission footprint showed good agreement. It is concluded that there was no bias between the different approaches used to measure the N₂O emission and that the precision of the measurements was determined by the spatial variability of the N₂O emission at the site and the variability inherent in the individual techniques. These results confirm that measurements of N₂O emissions from different ecosystems obtained by the different methods can be meaningfully compared.     

Comparison of emission rate values for odour and odorous chemicals derived from two sampling devices

Field and laboratory measurements identified a complex relationship between odour emission rates provided by the US EPA dynamic emission chamber and the University of New South Wales wind tunnel. Using a range of model compounds in an aqueous odour source, we demonstrate that emission rates derived from the wind tunnel and flux chamber are a function of the solubility of the materials being emitted, the concentrations of the materials within the liquid; and the aerodynamic conditions within the device – either velocity in the wind tunnel, or flushing rate for the flux chamber. The ratio of wind tunnel to flux chamber odour emission rates (OU m^?2 s) ranged from about 60:1 to 112:1. The emission rates of the model odorants varied from about 40:1 to over 600:1.These results may provide, for the first time, a basis for the development of a model allowing an odour emission rate derived from either device to be used for odour dispersion modelling.     

Evaluation of VOC Emission Measurement Methods for Paint Spray Booths

Abstract

Interest in regulations to control solvent emissions from automotive painting systems is increasing, especially in ozone nonattainment areas. Therefore, an accurate measurement method for VOC emissions from paint spray booths used in the automotive industry is needed to ascertain the efficiency of the spray booth capture and the total emissions. This paper presents the results of a laboratory study evaluating potential VOC sampling and analytical methods used in estimating paint spray booth emissions, and discusses these results relative to other published data. Eight test methods were selected for evaluation. The accuracy of each sampling and analytical method was determined using test atmospheres of known concentration and composition that closely matched the actual exhaust air from paint spray booths. The solvent mixture to generate the test atmospheres contained a large proportion of polar, oxygenated hydrocarbons such as ketones and alcohols. A series of identical tests was performed for each sampling/analytical method with each test atmosphere to assess the precision of the methods. The study identified significant differences among the test methods in terms of accuracy, precision, cost, and complexity.     

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 1--conventional lagoon and spray technology for waste treatment

Ammonia (NH3) fluxes from waste treatment lagoons and barns at two conventional swine farms in eastern North Carolina were measured. The waste treatment lagoon data were analyzed to elucidate the temporal (seasonal and diurnal) variability and to derive regression relationships between NH3 flux and lagoon temperature, pH and ammonium content of the lagoon, and the most relevant meteorological parameters. NH3 fluxes were measured at various sampling locations on the lagoons by a flowthrough dynamic chamber system interfaced to an environmentally controlled mobile laboratory. Two sets of open-path Fourier transform infrared (FTIR) spectrometers were also used to measure NH3 concentrations for estimating NH3 emissions from the animal housing units (barns) at the lagoon and spray technology (LST) sites. Two different types of ventilation systems were used at the two farms. Moore farm used fan ventilation, and Stokes farm used natural ventilation. The early fall and winter season intensive measurement campaigns were conducted during September 9 to October 11, 2002 (lagoon temperature ranged from 21.2 to 33.6 degrees C) and January 6 to February 2, 2003 (lagoon temperature ranged from 1.7 to 12 degrees C), respectively. Significant differences in seasonal NH3 fluxes from the waste treatment lagoons were found at both farms. Typical diurnal variation of NH3 flux with its maximum value in the afternoon was observed during both experimental periods. Exponentially increasing flux with increasing surface lagoon temperature was observed, and a linear regression relationship between logarithm of NH3 flux and lagoon surface temperature (T1) was obtained. Correlations between lagoon NH3 flux and chemical parameters, such as pH, total Kjeldahl nitrogen (TKN), and total ammoniacal nitrogen (TAN) were found to be statistically insignificant or weak. In addition to lagoon surface temperature, the difference (D) between air temperature and the lagoon surface temperature was also found to influence the NH3 flux, especially when D > 0 (i.e., air hotter than lagoon). This hot-air effect is included in the statistical-observational model obtained in this study, which was used further in the companion study (Part II), to compare the emissions from potential environmental superior technologies to evaluate the effectiveness of each technology.     

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.     

Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions

To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere-including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.     

Characterization of Emissions of Volatile Organic Compounds from Interior Alkyd Paint

ABSTRACT

Alkyd paint continues to be used indoors for application to wood trim, cabinet surfaces, and some kitchen and bathroom walls. Alkyd paint may represent a significant source of volatile organic compounds (VOCs) indoors because of the frequency of use and amount of surface painted. The U.S. Environmental Protection Agency (EPA) is conducting research to characterize VOC emissions from paint and to develop source emission models that can be used for exposure assessment and risk management. The technical approach for this research involves both analysis of the liquid paint to identify and quantify the VOC contents and dynamic small chamber emissions tests to characterize the VOC emissions after application. The predominant constituents of the primer and two alkyd paints selected for testing were straight-chain alkanes (C9–C12); C8–C9 aromatics were minor constituents. Branched chain alkanes were the predominant VOCs in a third paint. A series of tests were performed to evaluate factors that may affect emissions following application of the coatings. The type of substrate (glass, wallboard, or pine board) did not have a substantial impact on the emissions with respect to peak concentrations, the emissions profile, or the amount of VOC mass emitted from the paint. Peak concentrations of total volatile organic compounds (TVOCs) as high as 10,000 mg/m³ were measured during small chamber emissions tests at 0.5 air exchanges per hour (ACH). Over 90% of the VOCs were emitted from the primer and paints during the first 10 hr following application. Emissions were similar from paint applied to bare pine board, a primed board, or a board previously painted with the same paint. The impact of other variables, including film thickness, air velocity at the surface, and air-exchange rate (AER) were consistent with theoretical predictions for gas-phase, mass transfer-controlled emissions. In addition to the alkanes and aromatics, aldehydes were detected in the emissions during paint drying. Hexanal, the predominant aldehyde in the emissions, was not detected in the liquid paint and was apparently an oxidation product formed during drying. This paper summarizes the results of the product analyses and a series of small chamber emissions tests. It also describes the use of a mass balance approach to evaluate the impact of test variables and to assess the quality of the emissions data.     

The influence of dynamic chamber design and operating parameters on calculated surface-to-air mercury fluxes

Dynamic Flux Chambers (DFCs) are commonly applied for the measurement of non-point source mercury (Hg) emissions from a wide range of surfaces. A standard operating protocol and design for DFCs does not exist, and as a result there is a large diversity in methods described in the literature. Because natural and anthropogenic non-point sources are thought to contribute significantly to the atmosphere Hg pool, development of accurate fluxes during field campaigns is essential. The objective of this research was to determine how differences in chamber material, sample port placement, vertical cross sectional area/volume, and flushing flow rate influence the Hg flux from geologic materials. Hg fluxes measured with a Teflon chamber were higher than those obtained using a polycarbonate chamber, with differences related to light transmission and substrate type. Differences in sample port placement (side versus top) did not have an influence on Hg fluxes. When the same flushing flow rate was applied to two chambers of different volumes, higher fluxes were calculated for the chamber with the smaller volume. Conversely, when two chambers with different volumes were maintained at similar turnover times, the larger volume chamber yielded higher Hg fluxes. Overall, the flushing flow rate and associated chamber turnover time had the largest influence on Hg flux relative to the other parameters tested. Results from computational fluid dynamic (CFD) modeling inside a DFC confirm that the smaller diffusion resistance at higher flushing flows contributes to the higher measured flux. These results clearly illustrate that differences in chamber design and operation can significantly influence the resulting calculated Hg flux, and thus impact the comparability of results obtained using DFC designs and/or operating parameters. A protocol for determining a flushing flow rate that results in fluxes less affected by chamber operating conditions and design is proposed. Application of this protocol would provide a framework for comparison of data from different studies.     

Biogenic Sulfur Gas Emissions from Soils in Eastern and Southeastern United States

Data are presented for the first systematic measurements of biogenic sulfur gas flux from the major soil orders within the eastern and southeastern United States. Sulfur flux samples were collected and analyzed on-site during the fall of 1977, spring and summer of 1978 and summer of 1979. A total of 27 sampling locales in 17 states were examined. Eight additional sites were visited in 1980.

At some locales, two to four soils were examined, providing an even broader sampling of the soil orders. Three of the locales were revisited two or three times during the course of the study to establish the influence of seasonal climatology upon the measured emission rates and chemical composition of the sulfur flux mixtures.

The sulfur gas enhancement of sulfur-free sweep air passing through dynamic emission flux chambers placed over selected sampling areas was determined by combined cryogenic enrichment sampling and wall-coated, open tubular, capillary column, cryogenic gas chromatography (WCOT/GC) using a sulfur selective, flame photometric detector (FPD).

Sulfur gas mixtures varied with soil order, ambient temperature, insolation, soil moisture, cultivation, and vegetative cover. Statistical analyses indicated strong temperature and soil order relationships for sulfur emissions from soils.

Fluxes ranged from 0.001 g to 1940 g of total sulfur as S/m²/yr. The calculated mean annual sulfur flux, weighted by soil order, was 0.03 g S/m²/yr for the study land area, or 110,872 metric tons (mT). The estimated annual average sulfur flux increased from 65 mT per 6400 km² for the land grids in the northernmost east-west grid tier to an average 1800 mT for the land grids in the southern Florida grid tiers.

This systematic sampling of major soils provides a much broader data base for estimating biogenic sulfur flux than previously reported for isolated intertidal sites, and presents the first sulfur flux estimates for inland soils which make up approximately 93% of the land of the eastern United States.