Quantifying Uncontrolled Landfill Gas Emissions from Two Florida ...

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The two scanning ORS instruments were deployed on top of each measurement area, in opposite corners of the landfill cells. Each instrument was used to scan to two five-mirror VRPM configurations. Path-integrated concentration data were collected along each beam path in the configuration. These data were input into the VRPM algorithm with wind data (collected concurrently) to produce an emissions plume map and downwind emissions flux value. More information on the VRPM algorithm can be found in Appendix A of this document. 1.4 Total NMOC Measurements Concentrations of NMOC were determined from samples of landfill gas collected from the gas header pipe at each site. The samples were collected using an adapted version of EPA Method 0040 – Sampling of Principal Organic Hazardous Constituents from Combustion Sources Using Tedlar Bags. This modified Method 0040 used the same analytical technique detailed in the method, but used the samples collected in a Summa canister. Analysis of VOC concentrations was done by Research Triangle Park Laboratories, Inc. using EPA Method TO-15, Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specially-Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) as seen in the Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, Second Edition (EPA 625/R-96/010b), and EPA Method 25-C, Determination of Nonmethane Organic Compounds in Landfill Gas. Landfill gases were also measured using a landfill gas monitor for the measurement of methane, carbon dioxide, oxygen, nitrogen, and hydrogen sulfide. Table 1-1 presents a list of target compounds for the GC/MS analysis. The list includes compounds identified as landfill gas constituents in Compilation of Air Pollutant Emission Factors, AP-42 (U.S. EPA, 1997). 1.5 Total and Organo-Mercury Measurements Total and organo- mercury samples were collected at a location in the vicinity of a gas header pipe at each site. The total mercury samples were collected using an iodated charcoal trap as a sorbent. A backup tube was also present to assess any breakthrough. Additional samples were collected to analyze concentrations of organo-mercury (monomethyl and dimethyl). The methods, developed by Frontier Geosciences, involve drawing a measured volume of sample gas through different adsorbers, at a draw rate of approximately 400 L/min. The method used to collect samples for monomethylmercury (MMM) used a condenser train consisting of several water impingers in an ice bath. Dimethylmercury (DMM) is collected on a carbotrap cartridge. Samples were recovered, digested, and analyzed for mercury by cold-vapor atomic fluorescence spectroscopy (CVAFS). Total mercury sorbent tubes were also collected from the landfills and analyzed by a modified SW-846 Method 7473, “Mercury in Solids and Solutions by Thermal Decomposition, Mercury Amalgamation, and Atomic Adsorption Spectroscopy” and CFR Part 60 Method 30B, “Determination of Total Vapor Phase Mercury Emissions from Coal-Fired Combustion Sources Using Carbon Sorbent Tubes.” Samples were analyzed using the Lumex RA-915+ Zeeman spectrometer with a RP-M324 decomposition furnace attachment cell. No mercury amalgamation was necessary due to the sensitivity of the instrument. The iodated carbon samples were loaded into a quartz combustion boat and inserted into a decomposition furnace at 775 deg C. The mercury species are converted to elemental mercury and detected by the Zeeman atomic 1-7
adsorption spectrometer. The analyzed is calibrated using NIST certified HgCl2 standards from SCP Sciences. Elemental mercury spiking of the carbon tubes were performed using an impinger containing a stannous chloride solution. The mercury standard is dispensed into the impinger and the elemental mercury is pulled through the glassware system onto the iodated carbon. The elemental mercury spike is used to assess the recovery the mercury from the carbon tubes. 1.6 Elemental Mercury Measurements Elemental mercury measurements were collected in the vicinity of a gas header pipe at both sites using a Lumex RA-915+ instrument. The Lumex instrument is considered to be ideally suited to quantify and screen landfill gas samples for elemental mercury. This instrument has been used by U.S. EPA, industry, and academic groups to quantify elemental mercury in indoor air and to estimate elemental mercury emissions in industrial process flue gases. The Lumex RA-915+ mercury analyzer produces real-time mercury concentration measurements by performing atomic absorption spectrometry (at 253.7 nm wavelength) on elemental mercury atoms in a continuously extracted gas stream. It achieves the low detection limit of 2 ng/m 3 by using a multi-path absorption cell, which has an effective optical path of approximately 10 meters. Using the Zeeman Effect, selectivity is achieved using high frequency modulation of light polarization (ZAAS-HFM). For landfill gases, where mercury concentrations are expected to be high, it may be beneficial to use the shorter-path-length cell (6.25 cm) and at the lower sample flow rate (5.0 lpm), to take advantage of the detection limit of approximately 320 ng/m 3 and higher linear calibration range. Table 1-1. Target Compound List Compound AP-42 Value a (ppmv) Compound AP-42 Value (ppmv) Benzene 1.91 Ethylene dichloride 0.41 Butane 5.03 Hexane 6.57 Carbonyl sulfide 0.49 Methane N/A Chloromethane 1.21 Methyl isobutyl ketone 1.87 Dichlorodifluoromethane 15.7 Methylene chloride 14.3 Ethane 889 Propylene dichloride 0.18 Ethyl chloride 1.25 Tetrachloroethene 3.73 Fluorotrichloromethane 0.76 Trichlorethylene 2.82 Pentane 3.29 Vinyl chloride 7.34 Propane 11.1 Vinylidene chloride 0.20 Acetone 7.01 Ethanol 27.2 Acrylonitrile 6.33 Methyl ethyl ketone 7.09 Carbon disulfide 0.58 2-Propanol 50.1 Carbon tetrachloride 0.004 1,4-Dichlorobenzene 0.21 Chlorobenzene 0.25 Ethyl benzene 4.61 Chloroform 0.03 Xylenes 12.1 Dimethyl sulfide 7.82 Hydrogen sulfide 35.5 Ethylene dibromide N/A = not available 0.001 Methyl mercaptan 2.49 a U.S. Environmental Protection Agency, Compilation of Air Pollutant Emission Factors, AP-42, Volume 1: Stationary Point and Area Sources, 5 th ed., Chapter 2.4, Office of Air Quality Planning and Standards, US EPA, Research Triangle Park, NC, 1997. Available at: http://www.epa.gov/ttn/chief/ap42/ch02/final/c02s04.pdf 1-8
Page 1 and 2: Quantifying Uncontrolled Landfill G
Page 3 and 4: Foreword The U.S. Environmental Pro
Page 5 and 6: 3.1.3 Total Site Methane Emissions
Page 7 and 8: List of Tables Table 1-1. Target Co
Page 9 and 10: Table 3-28. Calculated Methane Flux
Page 11 and 12: Table C-6. Methane Concentrations (
Page 13 and 14: List of Figures Figure 1-1. Map of
Page 15 and 16: Executive Summary Waste decompositi
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Page 19 and 20: instrument (IMACC, Inc.). Figures 1
Page 21 and 22: Figure 1-3. Scanning Boreal GasFind
Page 23: wind direction data are collected n
Page 27 and 28: Table 1-2. Schedule of Work Perform
Page 29 and 30: Figure 2-2. Detail of measurement c
Page 31 and 32: corners of the cell, respectively.
Page 33 and 34: 2.2.3 Background Measurements Backg
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Page 37 and 38: was aligned on the mirror targets i
Page 39 and 40: methane concentrations measured alo
Page 41 and 42: Figure 3-3 Summary of ORS measureme
Page 43 and 44: Table 3-5. Calculated methane flux
Page 45 and 46: Table 3-7. Calculated methane flux
Page 47 and 48: cell to the base. The following equ
Page 49 and 50: Table 3-9. Results of TO-15 analysi
Page 51 and 52: Table 3-10. Results of C1 to C6 and
Page 53 and 54: Table 3-14. Monomethyl Mercury Conc
Page 55 and 56: 3.2 Landfill Site #2 3.2.1 Control
Page 63 and 64: 3.2.2 Bioreactor Cell 3.2.2.1 Febru
Page 69 and 70: Based on the calculations presented
Page 71 and 72: Table 3-34. Results for C1 to C6 an
Page 73 and 74: Table 3-38. Monomethyl Mercury Conc
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3.3 Gas and Mercury Sampling Result
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Site #1 with a level of 83 ppmv. Th
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The surveys also found significant
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Monomethyl mercury concentrations i
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5.1 Equipment Calibration Chapter 5
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The R 2 value was used to assess th
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the measured path-integrated methan
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5.2.7 DQI Check of Total Mercury Sa
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Site #1 5.4 Site #2 77.9 Completene
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U.S. Environmental Protection Agenc
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d f e c b PDCs Y X a 2 12( y)( z) (
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When the VRPM configuration consist
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Table B-3. Distance, and Horizontal
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Table B-7. Distance, and Horizontal
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APPENDIX C Path-Averaged Methane Co
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Table C-3. Methane Concentrations (
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Table C-11. Methane Concentrations
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