Accuracy Assessment of EPA Protocol Gases Purchased In 1991

ABSTRACT

Fixed-roof tanks are used extensively at manufacturing, waste management, and other facilities to store or process liquids containing volatile organic compounds. Federal and state air standards require the control of organic air emissions from many of these tanks. A common practice used for some fixed-roof tanks that are required to use controls is to vent the tank through an activated carbon canister. When organic vapors are adsorbed on activated carbon, heat is released. Under certain conditions, the temperature of the carbon bed can increase to a level at which the carbon or organic vapors spontaneously ignite, starting a fire in the carbon bed. Bed fires in carbon canisters are not uncommon and can present a significant safety hazard at facilities if proper safety measures are not implemented. This article discusses how carbon adsorber bed fires occur and presents general guidance on safety measures for carbon canisters installed on fixed-roof tanks to reduce the likelihood of a carbon bed fire and to minimize the impact in the event of a fire.     

Microwave regeneration of activated carbon used for removal of solvents from vented air

A microwave regeneration of activated carbon used to remove organic solvents from vented air has been investigated. Methyl ethyl ketone (MEK), acetone, and tetrachloroethylene (TCE) vapors were removed from vented air through adsorption onto granular activated carbon. The saturated carbon was then regenerated in a microwave field, where the solvent was quickly desorbed and recovered from the inner pores of the carbon granules. The microwave-induced regeneration restored the original adsorption capacity and surface area of the activated carbon.     

Microwave Regeneration of Activated Carbon Used for Removal of Solvents from Vented Air

ABSTRACT

A microwave regeneration of activated carbon used to remove organic solvents from vented air has been investigated. Methyl ethyl ketone (MEK), acetone, and tetrachloroethylene (TCE) vapors were removed from vented air through adsorption onto granular activated carbon. The saturated carbon was then regenerated in a microwave field, where the solvent was quickly desorbed and recovered from the inner pores of the carbon granules. The microwave-induced regeneration restored the original adsorption capacity and surface area of the activated carbon.     

Adsorption Characteristics of Activated Carbon and XAD4 Resin for the Removal of Hazardous Organic Solvents

A comparative study has been conducted on adsorption/desorption of six hazardous organic vapors on synthetic resin (XAD4) and activated carbon, using a differential reactor involving the expansion of a quartz spring. While both sorbents can effectively remove the organic vapors, it was observed that at low concentrations activated carbon adsorbed more organic vapor than synthetic resin. At higher, industrial concentrations, the resins adsorbed more vapor as demonstrated by the slopes of the equilibrium isotherms. The resin also showed much higher desorptlon.

The effective Intraparticle diffusion coefficients (D_e) were observed to be strongly dependent on solute concentration. Pore diffusion dominated the adsorption/desorption of the six organic vapors on XAD4 resin. For the carbon system, pore diffusion dominated the adsorption but surface diffusion contributed to the desorptlon process. This is believed to be due to higher Interaction of the adsorbates with activated carbon.     

Impacts of prescribed fires and benefits from their reduction for air quality,health, and visibility in the Pacific Northwest of the United States

Using a WRF-SMOKE-CMAQ modeling framework, we investigate the impacts of smoke from prescribed fires on model performance, regional and loc al air quality, health impacts, and visibility in protected natural environments using three different prescribed fire emission scenarios: 100% fire, no fire, and 30% fire. The 30% fire case reflects a 70% reduction in fire activities due to harvesting of logging residues for use as a feedstock for a potential aviation biofuel supply chain. Overall model performance improves for several performance metrics when fire emissions are included, especially for organic carbon, irrespective of the model goals and criteria used. This effect on model performance is more pronounced for the rural and remote IMPROVE sites for organic carbon and total PM_2.5. A reduction in prescribed fire emissions (30% fire case) results in significant improvement in air quality in areas in western Oregon, northern Idaho, and western Montana, where most prescribed fires occur. Prescribed burning contributes to visibility impairment, and a relatively large portion of protected class I areas will benefit from a reduced emission scenario. For the haziest 20% days, prescribed burning is an important source of visibility impairment, and approximately 50% of IMPROVE sites in the model domain show a significant improvement in visibility for the reduced fire case. Using BenMAP, a health impact assessment tool, we show that several hundred additional deaths, several thousand upper and lower respiratory symptom cases, several hundred bronchitis cases, and more than 35,000 workday losses can be attributed to prescribed fires, and these health impacts decrease by 25–30% when a 30% fire emission scenario is considered.

Implications: This study assesses the potential regional and local air quality, public health, and visibility impacts from prescribed burning activities, as well as benefits that can be achieved by a potential reduction in emissions for a scenario where biomass is harvested for conversion to biofuel. As prescribed burning activities become more frequent, they can be more detrimental for air quality and health. Forest residue-based biofuel industry can be source of cleaner fuel with co-benefits of improved air quality, reduction in health impacts, and improved visibility.     

Pilot Study of Enclosed Thermal Soil Aeration for Removal of Volatile Organic Contamination

During the winter and spring of 1986 sandy soils contaminated with volatile organic chemicals were successfully treated during a pilot study of an enclosed thermal soil aeration process at the McKin Superfund site in Gray, Maine. Excavated soil containing up to 3310 ppm of trichloroethylene (TCE) was fed into a large rotating drum and mixed at 300°F. Aerated soil was then solidified with cement and water and returned to the on-site excavation location. Exhausted air from the enclosed aeration process was treated in a baghouse, a scrubber, and a vapor phase carbon bed prior to atmospheric release. Continuous air monitoring for organic vapors and particulates took place at the site perimeter and for organic vapors at onsite locations. Techniques to minimize uncontrolled volatilization of organic chemicals from the soil during excavation and aeration and to control dust emissions were implemented. Results of this pilot study indicate that concentrations of volatile organic contaminants routinely were reduced to nondetectable levels and achieved site-specific soil performance targets established by the U.S. Environmental Protection Agency. The pilot study was conducted by Canonie Environmental Services Corporation and funded by private companies under order from EPA.     

Adsorption of Automotive Paint Solvents On Activated Carbon: I. Equilibrium Adsorption of Single Vapors

A bench scale system to measure adsorption of organic vapors on activated carbon is described in this report. The system was used to measure the equilibrium adsorption isotherms of n-heptane, n-butanol, and methyl isobutyl ketone at a concentration range of 50 to 900 ppm on a Columbia JXC activated carbon and the adsorption capacity of eleven additional solvents at a concentration of 365 ppm. It is found that the Polyani–Dubinin correlation describes the results well. Using n-heptane as a reference solvent, the mean error in the prediction of equilibrium adsorption capacity is 1.9% and the maximum error 7.2%.     

活性炭吸附室内空气中挥发性有机化合物

活性炭吸附室内空气中挥发性有机化合物的１０％穿透时间与气相浓度及挥发性有机化合物的种类有关,通过对苯、甲苯和丙酮的实验研究,得出了由高浓度估算室内低浓度时炭床１０％穿透时间的经验公式ｔｂ,１＝ｔｂ,ｈ（Ｃ０,１／Ｃ０,ｈ）＾ａ,其中ａ值是与炭床性能及挥发性有机化合物种类有关的参数,可通过实验确定。     

烧结纤维承载活性炭复合材料在苯蒸气脱除中的应用

以8μm的镍纤维和煤基活性炭为原材料,通过抄制和烧结工艺制备了烧结纤维承载活性炭粉末复合材料。为了减轻床层总重量,将这种材料和通常的颗粒状活性炭进行联合装填形成复合层,并进行了苯蒸气的吸附穿透实验。利用Wheeler方程对床层的饱和吸附容量和吸附速率常数进行了测定。结果表明,在相同的测试条件下,联合装填层比单独的颗粒炭装填层具有更好的苯蒸气脱除性能;对两种床层而言,其各自的饱和吸附容量是一个不随比速而变化的常数,而随着气流比速的增加,两种床层的吸附速度都呈增加的趋势。     

用于污水再生利用的生物活性炭床的有机物降解特性

以微生物增殖动力学的基本方程-莫诺方程为出发点,通过氮同位素分析比较了具有同源性微生物的生物陶粒滤床和生物活性炭床的有机物生物降解规律,建立了生物活性炭床的有机物生物降解动力学方程,提出在污水再生利用过程中生物活性炭床符合高基质有机物降解动力学模型,即有机物降解呈一级反应动力学方程。以此方程为基础,分析计算了生物活性炭床沿炭床深度的吸附性能,结果表明,在生物活性炭床中,随生物功能的减弱,生物活性炭床对有机物的吸附能力逐渐加强。     

Partitioning and removal of dioxin-like congeners in flue gases treated with activated carbon adsorption

Activated carbon adsorption is commonly used to control dioxin-like congener (PCDD/Fs and PCBs) emissions. Partitioning of PCDD/Fs and PCBs between vapor and solid phases and their removal efficiencies achieved with existing air pollution control devices (APCDs) at a large-scale municipal waste incinerator (MWI) and an industrial waste incinerator (IWI) are evaluated via intensive stack sampling and analysis. Those two facilities investigated are equipped with activated carbon injection (ACI) with bag filter (BF) and fixed activated carbon bed (FACB) as major PCDD/F control devices, respectively. Average PCDD/F and PCB concentrations of stack gas with ACI+BF as APCDs are 0.031 and 0.006ng-TEQ/Nm(3), and that achieved with FACB are 1.74 and 0.19ng-TEQ/Nm(3) in MWI and IWI, respectively. The results show that FACB could reduce vapor-phase PCDD/Fs and PCBs concentrations in flue gas, while the ACI+BF can effectively adsorb the vapor-phase dioxin-like congener and collect the solid-phase PCDD/Fs and PCBs in the meantime. Additionally, the results of the pilot-scale adsorption system (PAS) experimentation indicate that each gram activated carbon adsorbs 105-115ng-PCDD/Fs and each surface area (m(2)) of activated carbon adsorbs 10-25ng-PCDD/Fs. Based on the results of PAS experimentation, this study confirms that the surface area of mesopore+macropore (20-200A) of the activated carbon is a critical factor affecting PCDD/F adsorption capacity.     

A New Method for the Rapid Determination of Volatile Organic Compound Breakthrough Times for a Sorbent at Concentrations Relevant to Indoor Air Quality

Abstract

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25% relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Validation of an evacuated canister method for measuring part-per-billion levels of chemical warfare agent simulants

The National Institute for Occupational Safety and Health (NIOSH) research on direct-reading instruments (DRIs) needed an instantaneous sampling method to provide independent confirmation of the concentrations of chemical warfare agent (CWA) simulants. It was determined that evacuated canisters would be the method of choice. There is no method specifically validated for volatile organic compounds (VOCs) in the NIOSH Manual of Analytical Methods. The purpose of this study was to validate an evacuated canister method for sampling seven specific VOCs that can be used as a simulant for CWA agents (cyclohexane) or influence the DRI measurement of CWA agents (acetone, chloroform, methylene chloride, methyl ethyl ketone, hexane, and carbon tetrachloride [CCl4]). The method used 6-L evacuated stainless-steel fused silica-lined canisters to sample the atmosphere containing VOCs. The contents of the canisters were then introduced into an autosampler/preconcentrator using a microscale purge and trap (MPT) method. The MPT method trapped and concentrated the VOCs in the air sample and removed most of the carbon dioxide and water vapor. After preconcentration, the samples were analyzed using a gas chromatograph with a mass selective detector. The method was tested, evaluated, and validated using the NIOSH recommended guidelines. The evaluation consisted of determining the optimum concentration range for the method; the sample stability over 30 days; and the accuracy, precision, and bias of the method. This method meets the NIOSH guidelines for six of the seven compounds (excluding acetone) tested in the range of 2.3-50 parts per billion (ppb), making it suitable for sampling of these VOCs at the ppb level.     

Vegetation fire emissions and their impact on air pollution and climate

Gaseous and particulate emissions from vegetation fires substantially modify the atmospheric chemical composition, degrade air quality and can alter weather and climate. The impact of vegetation fire emissions on air pollution and climate has been recognised in the late 1970s. The application of satellite data for fire-related studies in the beginning of the 21th century represented a major break through in our understanding of the global importance of fires. Today the location and extent of vegetation fires, burned area and emissions released from fires are determined from satellite products even though many uncertainties persist. Numerous dedicated experimental and modeling studies contributed to improve the current knowledge of the atmospheric impact of vegetation fires. The motivation of this paper is to give an overview of vegetation fire emissions, their environmental and climate impact, and what improvements can be expected in the near future.     

A new method for the rapid determination of volatile organic compound breakthrough times for a sorbent at concentrations relevant to indoor air quality

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25%) relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach

Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.     

Refining fire emissions for air quality modeling with remotely sensed fire counts: A wildfire case study

This paper examines the use of Moderate Resolution Imaging Spectroradiometer (MODIS) observed active fire data (pixel counts) to refine the National Emissions Inventory (NEI) fire emission estimates for major wildfire events. This study was motivated by the extremely limited information available for many years of the United States Environmental Protection Agency (US EPA) NEI about the specific location and timing of major fire events. The MODIS fire data provide twice-daily snapshots of the locations and breadth of fires, which can be helpful for identifying major wildfires that typically persist for a minimum of several days. A major wildfire in Mallory Swamp, FL, is used here as a case study to test a reallocation approach for temporally and spatially distributing the state-level fire emissions based on the MODIS fire data. Community Multiscale Air Quality (CMAQ) model simulations using these reallocated emissions are then compared with another simulation based on the original NEI fire emissions. We compare total carbon (TC) predictions from these CMAQ simulations against observations from the Inter-agency Monitoring of Protected Visual Environments (IMPROVE) surface network. Comparisons at three IMPROVE sites demonstrate substantial improvements in the temporal variability and overall correlation for TC predictions when the MODIS fire data is used to refine the fire emission estimates. These results suggest that if limited information is available about the spatial and temporal extent of a major wildfire fire, remotely sensed fire data can be a useful surrogate for developing the fire emissions estimates for air quality modeling purposes.     

Modelling pollutants dispersion and plume rise from large hydrocarbon tank fires in neutrally stratified atmosphere

Petrochemical industries normally use storage tanks containing large amounts of flammable and hazardous substances. Therefore, the occurrence of a tank fire, such as the large industrial accident on 11th December 2005 at Buncefield Oil Storage Depots, is possible and usually leads to fire and explosions. Experience has shown that the continuous production of black smoke from these fires due to the toxic gases from the combustion process, presents a potential environmental and health problem that is difficult to assess. The goals of the present effort are to estimate the height of the smoke plume, the ground-level concentrations of the toxic pollutants (smoke, SO₂, CO, PAHs, VOCs) and to characterize risk zones by comparing the ground-level concentrations with existing safety limits. For the application of the numerical procedure developed, an external floating-roof tank has been selected with dimensions of 85 m diameter and 20 m height. Results are presented and discussed. It is concluded that for all scenarios considered, the ground-level concentrations of smoke, SO₂, CO, PAHs and VOCs do not exceed the safety limit of IDLH and there are no “death zones” due to the pollutant concentrations.     

Sample integrity of trace level volatile organic compounds in ambient air stored in SUMMA® polished canisters

Sets of new and used SUMMA® polished stainless steel canisters were tested for storage stability of volatile organic compounds (VOCs). Evacuated canisters were filled at a controlled rate with ambient air containing added concentrations of 15 VOCs (14 chlorinated, one brominated) at < 2 ppbv. Concentrations of VOCs in each canister were then periodically determined during 7-day or 30-day storage periods using simultaneous flame ionization and electron capture detection. No initial decreases in concentrations of target compounds were observed. Statistical analysis of data showed that the relative standard deviation of concentrations of most VOCs in each canister set was 10% or less during the storage periods. For the 7-day tests, the mean change in concentration per day was within ± 3.2 %. These canisters appear suitable as an alternative to other sampling techniques, at least for most of the compounds tested here.     

Effect of advanced oxidants generated via ultraviolet light on a sequentially loaded and regenerated granular activated carbon biofilter

The objective of this research was to investigate a sequentially loaded and regenerated granular activated carbon (GAC) biofilter system and to determine whether regenerative ozonation/advanced oxidation could improve the removal and biodegradation of a volatile organic compound from a contaminated airstream. Bench-scale reactors were constructed to operate in a manner analogous to a commercially available system manufactured by Terr-Aqua Environmental Systems (only with longer contact time). The GAC system consisted of two GAC biofilter beds that operated in a cyclical manner. On a given day, the first GAC bed adsorbed methyl isobutyl ketone from a simulated waste airstream, while the second bed underwent regeneration; then on the next day, the second bed was in the adsorption mode while the first was regenerated. Three bench-scale systems were used to compare the performance under three operating conditions: (1) ozone/ associated oxidant regeneration of a GAC biofilter system that was seeded with microorganisms from a field site, (2) a humid air regeneration of a seeded GAC biofilter, and (3) a humid air regeneration of an unseeded GAC biofilter. For the advanced oxidant regenerated GAC biofilter, a maximum removal efficiency of >95% was achieved with an empty bed contact time of 148 sec and an influent concentration of 125 ppm methyl isobutyl ketone, and 90-95% was achieved at 148-sec empty bed contact time and a 1150-ppm influent.