Evaluation of Parts-per-billion Organic Cylinder Gases for Use as Audits During Hazardous Waste Trial Burn Tests

A repository of 14 gaseous organic compounds at parts-per-billion levels (7-430 ppb) in compressed gas cylinders has been established by the Environmental Protection Agency. This repository was established to provide audit materials for use in conducting performance audits to assess the accuracy and precision of principal organic hazardous constituent (POHC) measurements, especially those performed during hazardous waste trial burn tests. Five- and nine-component mixtures In a balance gas of nitrogen were prepared in aluminum cylinders for use in the performance audit program. The five-component mixtures contain carbon tetrachloride, chloroform, perchloroethylene, vinyl chloride, and benzene. The ninecomponent mixtures contain trichloroethylene, 1,2-dichloroethane, 1,2-dibromoethane, acetonitrile, trichlorofjuoromethane, dichlorodifluoromethane, bromomethane, methyl ethyl ketone and 1,1,1-trichloroethane.

Studies of all 14 gaseous organic compounds were performed to determine the stability of the compounds and the feasibility of using them in performance audits. Results indicate that ail of the 14 compounds were adequately stable to be used as reliable audit materials. Also, the estimation of specific uncertainties associated with the analysis of these audit materials and how those uncertainties are used to assign a total uncertainty to the final analyte concentration for 14 organics Is described.

Subsequent to completion of the stability studies, several performance audits were conducted using the repository gases to assess the accuracy and precision of the volatile organic sampling train (VOST) and bag measurement methods. The audit results indicate that laboratories can use these methods to analyze POHC with accuracy usually to within ± 50 percent of the audit concentrations.     

Performance Audit Results for Volatile POHC Measurements

Audit materials containing principal organic hazardous constituents (POHCs) have been developed by EPA for use by federal, state, and local agencies or their contractors to assess the accuracy of measurement methods used during RCRA trial burn tests. Audit materials are currently available for 27gaseous organics in five, six, seven, and nine-component mixtures at parts-per-billion levels (7 to 10,000 ppb) in compressed gas cylinders in a balance gas of nitrogen. The criteria used for the selection of 27 gaseous organic compounds is described.

Stability studies indicate that all of the organics tested (with the exception of ethylene oxide and propylene oxide below 10 ppb levels) are stable enough to be used as reliable audit materials.

Subsequent to completion of the stability studies, 89 performance audits have been conducted with the audit materials to assess the accuracy of the Volatile Organic Sampling Train (VOST) and bag measurement methods during or prior to RCRA trial burn tests. A summary of the audits conducted for each POHC and the measurement system audited is shown in this paper. The audit results obtained with audit gases during RCRA trial burn tests are generally within ±50 percent of the audit concentrations.     

Investigation of adsorption characteristics of four toxic gases (nitric oxide,nitrogen dioxide,sulfur dioxide,and hydrogen chloride) on the inner surface of nickel-coated manganese steel cylinders and aluminum cylinders

To develop standard toxic gas mixtures, it is essential to identify adsorption characteristics of each toxic gas on the inner surface of a gas cylinder. Thus, this study quantified adsorbed amounts of the four toxic gases (nitric oxide [NO], nitrogen dioxide [NO₂], sulfur dioxide [SO₂], and hydrogen chloride [HCl]) on the inner surface of aluminum cylinders and nickel-coated manganese steel cylinders. After eluting adsorbed gases on the inside of cylinders with ultrapure water, a quantitative analysis was performed on an ion chromatograph. To evaluate the reaction characteristics of the toxic gases with cylinder materials, quantitative analyses of nickel (Ni), iron (Fe), and aluminum (Al) were also performed by inductively coupled plasma optical emission spectrometry (ICP-OES). It was found that the amounts of NO, NO₂, and SO₂ adsorbed on the inner surface of aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio, whereas the signal for most heavy metal elements were below their respective detection limits. This study found that the amounts of HCl adsorbed on the inner surface of nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas Ni (86 μmol) and Fe (28 μmol) were detected in the same cylinders. It was revealed that the adsorption mainly took place via the reaction of HCl with inner surface material of nickel-coated manganese steel cylinders. On the other hand, in the case of aluminum cylinders, the amounts of the adsorption were determined to be less than 1% at the level of HCl 100 μmol/mol mixing ratio, whereas most of Ni, Fe, and Al were detected at levels similar to their limits of detection. As a result, this study found that aluminum cylinders are more suitable for preparing HCl gas mixtures than nickel-coated manganese steel cylinders.

Implications: To develop a standard toxic gas mixture, it is essential to understand the adsorption characteristics of each toxic gas inside a gas cylinder. It was found that the amounts of NO, NO₂, and SO₂ adsorbed inside aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio. The amounts of HCl adsorbed inside nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas those inside aluminum cylinders were less than 1%, indicating that aluminum cylinders are more suitable for preparing HCl gas mixtures.     

Evaluation of Selected Gaseous Halocarbons for Use in source Test Performance Audits

A repository of 38 gaseous organic compounds in compressed gas cylinders has been established by EPA. This repository was established to provide standards for source test performance audits, that is, quantitative quality assurance tests. Among these compounds are ten halogenated organic species, which are the focus of this paper.

Stability studies of all ten compounds have been performed to determine the feasibility of using them as performance audit standards. Results indicate that all of the halocarbons tested are adequately stable to be used as reliable audit standards.

Subsequent to completion of stability studies, four of the ten halocarbons were used in source test performance audits. Results are available at this time for two of the four compounds; the results show agreement within 10% of the concentrations previously established by Research Triangle Institute.     

Summary of POHC Audit Results Using VOST and Bag Methods During RCRA Trial Burns

Audit materials containing Principal Organic Hazardous Constituents (POHCs) have been developed by EPA for use by Federal, State, and Local agencies or their contractors to assess the accuracy of measurement methods used during RCRA trial burn tests. Audit materials are currently available for 27 gaseous organics in five-, six-, seven-, and nine-component mixtures at ppb levels (7 to 10,000 ppb) in compressed gas cylinders in a balance gas of nitrogen. The logic used in selecting 27 gaseous organic compounds as audit materials and how these audit materials are successfully used in performance audits is described. Stability studies indicate that all of the organics tested (with the exception of ethylene oxide and propylene oxide below 10 ppb levels) are stable enough to be used as reliable audit materials. As of January 1990, 215 performance audits have been conducted to assess the accuracy of Volatile Organic Sampling Train (VOST) and bag measurement methods during or prior to RCRA trial burn tests. A summary of the audits conducted for each POHC, the measurement system audited, and the frequency of audits is described. The audit results obtained with audit gases are generally within ±50% of the audit concentrations.     

Development of a standard reference material containing 22 chlorinated hydrocarbon gases at 1 μmol/mol in nitrogen

A gas standard mixture containing 22 chlorinated hydrocarbons in high purity nitrogen was prepared using a two-step weighing method and a gasifying apparatus developed in-house. The concentration of each component was determined using a gas chromatograph with flame ionization detection (GC/FID). Linear regression analysis of every component was performed using the gas standard mixture with concentrations ranging from 1 to 10 μmol/mol, showing the complete gasification of volatile organic compound (VOCs) species in a selected cylinder. Repeatability was also examined to ensure the reliability of the preparation method. In addition, no significant difference was observed between domestic treated and imported treated cylinders, which were conducive to reduction of the cost of raw materials. Moreover, the results of stability testing at different pressures and long-term stability tests indicated that the gas standard at 1 μmol/mol level with relative expanded uncertainties of 5% was stable above 2 MPa for a minimum of 12 months. Finally, a quantity comparison was conducted between the gas standard and a commercial gas standard from Scott Specialty Gases (now Air Liquide America Specialty Gases). The excellent agreement of every species suggested the favorable accuracy of our gas standard. Therefore, this reference material can be applied to routine observation of VOCs and for other purposes.     

Evaluation of Sample Recovery of Malodorous Livestock Gases from Air Sampling Bags,Solid-Phase Microextraction Fibers,Tenax TA Sorbent Tubes,and Sampling Canisters

Abstract

Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75–μm solid–phase microextraction fibers, polyvinyl fluo–ride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b–diphenylene–oxide polymer resin (Tenax TA) tubes, and standard 6–L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p–cresol, indole, 4–ethylphenol, and 2'–aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5– and 24–hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in–house–made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N–dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.     

Total fuel-cycle analysis of heavy-duty vehicles using biofuels and natural gas-based alternative fuels

Heavy-duty vehicles (HDVs) present a growing energy and environmental concern worldwide. These vehicles rely almost entirely on diesel fuel for propulsion and create problems associated with local pollution, climate change, and energy security. Given these problems and the expected global expansion of HDVs in transportation sectors, industry and governments are pursuing biofuels and natural gas as potential alternative fuels for HDVs. Using recent lifecycle datasets, this paper evaluates the energy and emissions impacts of these fuels in the HDV sector by conducting a total fuel-cycle (TFC) analysis for Class 8 HDVs for six fuel pathways: (1) petroleum to ultra low sulfur diesel; (2) petroleum and soyoil to biodiesel (methyl soy ester); (3) petroleum, ethanol, and oxygenate to e-diesel; (4) petroleum and natural gas to Fischer-Tropsch diesel; (5) natural gas to compressed natural gas; and (6) natural gas to liquefied natural gas. TFC emissions are evaluated for three greenhouse gases (GHGs) (carbon dioxide, nitrous oxide, and methane) and five other pollutants (volatile organic compounds, carbon monoxide, nitrogen oxides, particulate matter, and sulfur oxides), along with estimates of total energy and petroleum consumption associated with each of the six fuel pathways. Results show definite advantages with biodiesel and compressed natural gas for most pollutants, negligible benefits for e-diesel, and increased GHG emissions for liquefied natural gas and Fischer-Tropsch diesel (from natural gas).     

A Combustion Method for the Determination of Solvent Vapors at Low Concentrations in Air

The nitrogen-containing products of smog chamber reactions have been the subject of much controversy. Concern has arisen over nitrogen products because of the almost universally poor nitrogen balance reported for irradiated mixtures of hydrocarbons and nitrogen oxides. Some possible nitrogen-containing products, such as molecular nitrogen, nitrous oxide, and nitroolefins have been investigated and shown to be unimportant. The nitrogen products most often measured are peroxyacetyl nitrate and residual nitrogen dioxide. These two products rarely comprise more than 70% of the initial nitrogen at the end of an experiment, and often account for less than 50%. Previous experiments in which total nitrate was determined in the gas phase and on the vessel walls at the end of irradiation have shown very good nitrogen balances. The assumption has been made that the nitrate arises from nitric acid formed on the walls by adsorbed N₂O₅.

In the work reported here, all major nitrogen-containing compounds have been monitored continuously for the first time. Nitric oxide and nitrogen dioxide have been monitored by chemilumines-cence and automated Saltzman techniques. Methyl, ethyl, and peroxyacetyl nitrate have been determined by gas chromatogra-phy. Two methods, one continuous and one integrated, have been specially developed to measure nitric acid both in the smog chambers and in the atmosphere. Continuous determination of these compounds yields good nitrogen balances throughout the irradiations.

Profiles of the nitrogen-containing species from irradiated HC/ NO_x mixtures are discussed in terms of nitrogen products and nitrogen balance. Differences in product distribution for different hydrocarbon systems are also considered. Using rate information from the nitrogen compound profiles, important reactions leading to nitrogen-containing products are identified. Interference with the chemiluminescent technique by HON0₂, PAN, and C₂H₅ONO₂ is discussed.     

Determination of three cresol isomers in sewage sludge by solid-liquid extraction with low temperature purification and gas chromatography-mass spectrometry

Abstract

Cresols are chemical contaminants derivative from phenol which can be found in sewage sludge. However, little attention has been given to monitoring these compounds in environmental matrices in the literature. Thus, the objective of this study was to develop a simple method based on solid-liquid extraction with low temperature purification for determining three cresol isomers in sludge. The quantification of these compounds was performed by gas chromatography coupled to mass spectrometry with a previous derivatization step. After a detailed study, the cresol recovery was higher than 91%, with relative standard deviation lower than 12% and a limit of quantification of 20?μg kg^?1. Linearity was achieved between 10 and 90?μg L^?1 (R² > 0.98) with the standard solutions prepared in matrix extracts due to the trouble caused by the matrix effect. The proposed method was applied with success for monitoring cresols in sewage sludge samples coming from six different wastewater treatment plants. All samples showed contamination by cresols, mainly p-cresol with values between 32.3 and 516.9?μg kg^?1. The majority of the analyzed samples showed a total sum of the isomers higher than the maximum residue limit established by Brazilian legislation (160?μg kg^?1).     

Performance of a Semi-Industrial Scale Gasification Process for the Destruction of Polychlorinated Biphenyls

Abstract

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO₂ 18%, and CH₄ 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spec-trometry. The coplanar PCBs congeners 77, 105, 118, 156/157, and 167 were detected in the syngas at concentrations <2 ×10^?7 mg/m³ (at 298 K, 1 atm, dry basis, 7% O₂). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was >99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 ×10^?6 ng-toxic equivalent (TEQ)/m³ and 7.1 × 10^?6 ng-TEQ/m³ (at 298 K, 1 atm, dry basis, 7% O₂) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH₄).     

Theory and laboratory study of a tall passive chamber for measuring gas fluxes at soil surface

A tall passive flux chamber with a height significantly greater than its horizontal dimensions is proposed for measuring fluxes of volatile organic compounds (VOCs) at the soil surface. The main feature of this tall chamber is the presence of a vertical concentration gradient of the target gas in the chamber. The emission and transport behavior of the target gas in the soil-chamber system are analyzed using the diffusion theory. A mathematical model is developed to estimate the flux from the soil into the tall chamber, providing the target gas establishes a detectable vertical concentration gradient in the chamber. To obtain the data required for calculating flux, only two gas concentrations (C1 and C2) at two heights (h1 and h2) within the chamber need to be measured at the end of a short chamber placement time (tp). To evaluate the applicability of the tall chamber for measuring flux, several laboratory tests have been conducted, using CH2Cl2 and CH3Br as the target gases. The results indicate that the proposed tall chamber has promising potential as a method for measuring fluxes of VOCs at the soil surface.     

Trace analysis of dissolved polychlorinated organic compounds in the water of the Yangtse River (Nanjing, China)

Eighteen organochlorine contaminants from the water samples of the Yangtse River have been qualitatively and quantitatively analyzed. The analysis of polychlorinated organic compounds (PCOCs) extracted by C18 Solid Phase Extract (SPE) was performed using HP6890 gas chromatograph coupled by ECD detector. The analytical results demonstrate that the analytical methods are reliable based on the fact that most of the recoveries for the targeted compounds are 60-90%. Most of the concerned contaminants, i.e. chlorinated pesticides and PCBs were found in the water samples of the Yangtse River, but their concentration was very low, <2.97 ng l(-1), which is far less than 1 microg l(-1)--the standard of drinking water of China. It is apparent that the PCOCs were in high concentration during the dry season, and in low concentration during the rainy season. The situation of PCOCs contamination in the water of the Yangtse River in 1999 was greatly improved in comparison with 10 years ago.     

Destruction of halogen-containing pesticides by means of detonation combustion

Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine—2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine—herbicide; (2) bromophos—O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate—insecticide; (3) chloridazon—5-amino-4-chloro-2-phenylopyridazin-3(2H)-one—herbicide; (4) linuron—3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea—herbicide; (5) metoxychlor—1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane—insecticide and acaricide; and (6) trichlorfon—dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate—insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method.     

Identification of Selected Hormonally Active Agents and Animal Mammary Carcinogens in Commercial and Residential Air and Dust Samples

ABSTRACT

In order to characterize typical indoor exposures to chemicals of interest for research on breast cancer and other hormonally mediated health outcomes, methods were developed to analyze air and dust for target compounds that have been identified as animal mammary carcinogens or hormonally active agents and that are used in commercial or consumer products or building materials. These methods were applied to a small number of residential and commercial environments to begin to characterize the extent of exposure to these classes of compounds. Phenolic compounds, including nonylphenol, octylphenol, bisphenol A, and the methoxychlor metabolite 2,2-bis (p-hydroxyphenyl)-1,1,1-trichloroethane (HPTE), were extracted, derivatized, and analyzed by gas chromatography/mass spectrometry (GC/MS)–selective ion monitoring (SIM). Selected phthalates, pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) were extracted and analyzed by GC/MS-SIM. Residential and workplace samples showed detectable levels of twelve pesticides in dust and seven in air samples. Phthalates were abundant in dust (0.3524 μg/g) and air (0.005-2.8 μg/m³). Nonylphenol and its mono- and di-ethoxylates were prevalent in dust (0.82-14 μg/g) along with estrogenic phenols such as bisphenol A and o-phenyl phenol. In this 7-sample pilot study, 33 of 86 target compounds were detected in dust, and 24 of 57 target compounds were detected in air. In a single sample from one home, 27 of the target compounds were detected in dust and 15 in air, providing an indication of chemical mixtures to which humans are typically exposed.     

Direct GLC Coulometric Analysis of Kraft Mill Gases

A new bromine, microcoulometric titration cell has been used with a commercially-available microcoulometer for the detection and analysis of sulfur-containing gases in various kraft mill emissions. Separation of the constituents of the gaseous mixtures emitted from mill sources including the recovery furnace, digestors, evaporators, lime kiln, and dissolvers was accomplished on an 8-ft, 3/16 in. stainless steel column packed with 10% Triton X-305 on 60–80 mesh Chromosorb G, DMCS-treated. The column was isothermally operated at 30°C for 4–6 mins and then rapidly raised to 70°C The exact program was varied with the type of sample analyzed. Each source gas was initially screened by direct injection of 0.01–0.1 ml of gas to determine whether or not disproportionately large concentrations of one or more components were present. Appropriate sample volumes were then selected to provide “on-scale” recorder peaks for the major constituents. Elution times for the major constituents were observed so that these compounds could be vented at the proper time following injection of large sample volumes (up to 10 ml) for detection and analysis of minor constituents. Venting of the high concentration compounds was necessary when analyzing large volume samples to maintain near equilibrium titration conditions in the microtitration cell.     

Hydrocarbon Measurements During the 1992 Southern Oxidants Study Atlanta Intensive: Protocol and Quality Assurance

Abstract

A major component of the Southern Oxidants Study (SOS) 1992 Atlanta Intensive was the measurement of atmospheric nonmethane hydrocarbons. Ambient air samples were collected and analyzed by a network of strategically located automated gas chromatography (GC) systems (field systems). In addition, an extensive canister sampling network was deployed. Combined, more than 3000 chromatograms were recorded. The SOS science team targeted for quantitative analysis 56 compounds which may be substantial contributors to ozone formation or used as air mass tracers. A quality assurance program was instituted to ensure that good measurements were being made throughout the network for each target compound. Common, high-quality standards were used throughout the network. The performance of individual field systems was evaluated during the intensive through the analysis of challenge mixtures. This methodology helped to identify and correct analytical problems as they arose.     

Measurements of biogenic VOC emissions: sampling,analysis and calibration

We describe an experimental system and techniques for sampling and analyzing biogenic emissions of volatile organic compounds (VOC). The system uses a Teflon chamber to enclose a single branch of a tree. Temperature, photosynthetic active radiation (PAR), relative humidity and carbon dioxide concentration are continuously monitored with a time resolution of five minutes. VOCs are sampled on tubes containing solid adsorbents (Tenax TA and Carbotrap) with a time resolution of 1 h. Composition and concentration of VOC emissions are measured with a gas chromatographic system equipped with a flame ionization detector (FID) for quantitative and a mass spectrometer (MS) for qualitative analysis. To calibrate the system, a diffusion source was built to produce standard mixtures of up to 36 different compounds with mixing ratios at low concentrations and high accuracy. The diffusion rates were monitored over 17 months and showed variations between 0.2 and 7.6% for monoterpenes (expect for α-phellandrene, α-terpinene and γ-terpinene) and between 10.6 and 22.6% for sesquiterpenes. FID response factors calculated from calibration measurements were corrected using correction factors based on the effective carbon number concept. The individual response factors of 23 compounds were combined to a mean response factor (RF_m) with a value of 23,100 μV s ng⁻¹ and a standard deviation of 9%. The system described here was used to measure VOC emission rates of Scots pine (Pinus sylvestris) in 1998 and 1999.     

Removal of nitric oxide in a biotrickling filter under thermophilic condition using Chelatococcus daeguensis

The development of a thermophilic biotrickling ?lter (BTF) system to inoculate a newly isolated strain of Chelatococcus daeguensis TAD1 for the effective treatment of nitric oxide (NO) is described. A bench-scale BTF was run under high concentrations of NO and 8% O₂ in thermophilic aerobic environment. A novel aerobic denitrifier Chelatococcus daeguensis TAD1 was isolated from the biofilm of an on-site biotrickling filter and it showed a denitrifying capability of 96.1% nitrate removal rate in a 24 h period in aerobic environment at 50 °C, with no nitrite accumulation. The inlet NO concentration fluctuated between approximately 133.9 and 669.6 mg m-3 and kept on a steady NOx removal rate above 80% in an oxygen stream of 8%. The BTF system was able to consistently remove 80–93.7% NO when the inlet NO was 535.7 mg m-3 in an oxygen stream of 2–20%. The biological removal efficiency of NO at 50 °C is higher than that at 25 °C, suggesting that the aerobic denitri?er TAD1 display well denitrification performance under thermophilic condition. Starvation for 2, 4 and 8 days resulted in the re-acclimation times of Chelatococcus daeguensis TAD1 ranging between 4 and 16 hours. A longer recovery time than that for weekend shutdown will be required when a longer starvation occurs. The results presented here demonstrate the feasibility of biotrickling ?lter for the thermophilic removal of NOx from gas streams.

Implications A novel denitrifier Chelatococcus daeguensis TAD1 was isolated from an on-site biotrickling filter in aerobic environment at 50 °C. To date, C. daeguensis has not been previously reported to be an aerobic denitrifier. In this study, a thermophilic biotrickling ?lter system inoculated with Chelatococcus daeguensis TAD1 for treatment of nitric oxide is developed. In coal-fired power plants, influent flue gas stream for nitrogen oxides (NO_x) removal typically exhibit temperatures between 50 and 60 °C. Traditionally, cooling gases to below 40 °C prior to biological treatment is inevitable, which is costly. Therefore, the application of thermophilic microorganisms for the removal of nitric oxide (NO) at this temperature range would offer great savings and would greatly extend the applicability of biofilters and biotrickling filters. Until now there has not been any study published about thermophilic biological treatment of NO under aerobic condition.     

A Life-Cycle Comparison of Alternative Automobile Fuels

ABSTRACT

We examine the life cycles of gasoline, diesel, compressed natural gas (CNG), and ethanol (C₂H₅OH)-fueled internal combustion engine (ICE) automobiles. Port and direct injection and spark and compression ignition engines are examined. We investigate diesel fuel from both petroleum and biosources as well as C₂H₅OH from corn, herbaceous bio-mass, and woody biomass. The baseline vehicle is a gasoline-fueled 1998 Ford Taurus. We optimize the other fuel/powertrain combinations for each specific fuel as a part of making the vehicles comparable to the baseline in terms of range, emissions level, and vehicle lifetime. Life-cycle calculations are done using the economic input-output life-cycle analysis (EIO-LCA) software; fuel cycles and vehicle end-of-life stages are based on published model results.

We find that recent advances in gasoline vehicles, the low petroleum price, and the extensive gasoline infrastructure make it difficult for any alternative fuel to become commercially viable. The most attractive alternative fuel is compressed natural gas because it is less expensive than gasoline, has lower regulated pollutant and toxics emissions, produces less greenhouse gas (GHG) emissions, and is available in North America in large quantities. However, the bulk and weight of gas storage cylinders required for the vehicle to attain a range comparable to that of gasoline vehicles necessitates a redesign of the engine and chassis. Additional natural gas transportation and distribution infrastructure is required for large-scale use of natural gas for transportation. Diesel engines are extremely attractive in terms of energy efficiency, but expert judgment is divided on whether these engines will be able to meet strict emissions standards, even with reformulated fuel. The attractiveness of direct injection engines depends on their being able to meet strict emissions standards without losing their greater efficiency. Biofuels offer lower GHG emissions, are sustainable, and reduce the demand for imported fuels. Fuels from food sources, such as biodiesel from soybeans and C₂H₅OH from corn, can be attractive only if the co-products are in high demand and if the fuel production does not diminish the food supply. C₂H₅OH from herbaceous or woody biomass could replace the gasoline burned in the light-duty fleet while supplying electricity as a co-product. While it costs more than gasoline, bioethanol would be attractive if the price of gasoline doubled, if significant reductions in GHG emissions were required, or if fuel economy regulations for gasoline vehicles were tightened.