Laboratory Investigation of Wildfire Smoke Interference with Ozone Analyzers. Richard M. Payton EPA Region 8
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1 Laboratory Investigation of Wildfire Smoke Interference with Ozone Analyzers Richard M. Payton EPA Region 8
2 Possible Real World Ozone Interference 5 Lostwood National Wildlife Refuge, North Dakota May 11-13, Zion Nat. Park & Saint George, Utah O3, June 25-27, 26 5 [O3], ppb [PM2.5], µg/m3 4 Span Check Power Failure 1 O3 PM2.5 1 [O3], ppb 3 2 5/11/6 : 5/11/6 12: 5/12/6 : 5/12/6 12: 5/13/6 : 5/13/6 12: 5/14/6 : Time 1 Zion National Park St. George O3 6/25/6 : 6/25/6 12: 6/26/6 : 6/26/6 12: 6/27/6 : 6/27/6 12: 6/28/6 : Date and Time
3 Smoke Interference with Ozone Analyzers Historical studies have demonstrated VOC interference in UV Ozone analyzers relative to Chemiluminescent Fedreal Reference Method EPA-454/C--2: 25 ppb of o-cresol results on 2.7 ppb of ozone interference; 24 ppb of o-nitrotoluene results in 6 ppb of ozone interference (low humidity conditions) Anecdotal evidence of smoke interference in UV instruments Ameliorated by inlet filter (particles) Huntzicker and Johnson, Env. Sci. and Tech., November 1979 attributed high ozone readings in aircraft and laboratory to rapidly changing concentrations between measurement and reference cycles in Dasibi ozone analyzers The current project attempts to quantify interference effects for a variety of natural wildfire fuel materials
4 Experiment Configuration Smoke Chamber Thermo/R&P Model 14 PM2.5 TEOM Combustion Source Exhaust Ozone Generator Particle Filter Particle Filter Sampling Manifold Particle Filter Particle Filter Particle Filter USFS Thermo 56 Chemiluminescent API 4/MnO2 Scrubber API 4/Heated Scrubber AP! 265a NO Chemi Analyzer Dasibi 13PC (2) MnO2
5 Sampling Inlets Manifold Inlet Equipment Room TEOM
6 Control/Equipment Room
7 Equipment Thermo Model 56 Portable Chemiluminescent Ozone Analyzer Reference Method Teledyne API Model 265a NO Chemiluminescent Ozone Analyzer Non-Equivalent Method Teledyne API 4 UV Ozone Analyzer with MnO 2 Scrubber Teledyne APE 4 UV Ozone Analyzer with Heated Metal Scrubber Dasibi 13PC UV Ozone Analyzers (2) with MnO 2 Scrubbers Ruprecht and Patashnic (Thermo) Model 14 Tapered Element Oscillating Microbalance PM 2.5 Analyzer Also CO, NOx, THC, Scattering, and various aerosol analyzers operated by other investigators
8 Lodgepole Pine Sample
9 Sample Combustion
10 Wax Myrtle Sampling Run TEOM Conventional Scrubbers Calibrations Chemiluminescents Calibrations
11 5-min Average Wax Myrtle Data Zero Corrected Wax Myrtle Data Ignition 13: [O3], ppb [PM2.5], g/m3 O3 Ethylene API MnO2 API HMS API NO Chemi DASIBI C DASIBI D TEOM, Zeroed /8/26 13:4 6/8/26 13:5 6/8/26 14: 6/8/26 14:1 Time 6/8/26 14:2 6/8/26 14:3 6/8/26 14:4 6/8/26 14:5
12 Wax Myrtle Ozone Interference vs. PM2.5 Wax Myrtle Impact on Ozone, Burn O 5 4 Transient Period, [PM2.5] lags ozone 1:55 3 2: 2:5 1:5 2:1 Delta [O3], ppb 2 1 O3 Ethylene O3MnO2 O3 heated O3 chem DASIBI C DASIBI D [PM2.5]
13 Interference vs PM2.5, Transient Removed Wax Myrtle Impact on Ozone, Burn O 3 25 Delta [O3], ppb O3 Ethylene O3MnO2 O3 heated O3 chem DASIBI C DASIBI D Linear (DASIBI C) Linear (DASIBI D) Linear (O3MnO2) Linear (O3 heated) Linear (O3 chem) [PM2.5]
14 Delta [O3], ppb Dasibi 13PC Response to Smoke, all Fuels Mean of All Runs: 5 ppb Interference/1 µg/m 3 PM 2.5 Range of Slopes: 1 to 11 ppb/1 µg/m 3 O 3 Interference as a function of Smoke PM2.5 Density [PM2.5], µg/m3 O3 Ethylene Das C, Ponderosa A Das D Ponderosa A Dac C Ponderosa C Das D Ponderosa C Das C Chamise D Das D Chamise D Das C Rice Straw E Das D Rice Straw E Das C Pine Duff F Das D Pine Duff F Das C Alaskan Duff G Das C Manzanita H Das D Manzanita H Das C Rabbit and Sage J Das D Rabbit and Sage L Das C Pine Needles L Das D Pine Needles L Das C Rain Forest, M Das D Rain Forest, M Das C Chamise, N
15 API 4, Conventional Scrubber Mean of All Runs: 2.4 ppb Interference/1 µg/m 3 PM 2.5 Range of Slopes: 1 to 12 ppb/1 µg/m 3 Delta [O3], ppb API 4 O 3 Interference, MnO 2 Scrubber [PM2.5], µg/m3 O3 Ethylene Pine Smoke Ponderosa Chamise Rice Straw Pine Duff Tundra Duff Manzanita Sage and Rabbit Brush Pine Needles Tropical Foliage Chamise Wax Myrtle Southern Pine Tropical Sticks Palmetto Ceocanthus Linear (Pine Smoke) Linear (Ponderosa) Linear (Chamise) Linear (Rice Straw) Linear (Pine Duff) Linear (Tundra Duff) Linear (Manzanita) Linear (Sage and Rabbit Brush) Linear (Pine Needles) Linear (Tropical Foliage) Linear (Chamise) Linear (Wax Myrtle) Linear (Southern Pine) Linear (Tropical Sticks) Linear (Palmetto) Linear (Ceocanthus)
16 API 4 with Heated Metal Scrubbers Mean of All Runs: 3.3 ppb Interference/1 µg/m 3 PM 2.5 Range of Slopes: 1 to 5 ppb/1 µg/m 3 Slope with Original Heater 3.3 ppb/1 µg/m 3 PM 2.5 Slope with Improved Heater 1 ppb/1 µg/m 3 PM 2.5 Delta [O3] API 4 O 3 Interference, Heated Metal Scrubbers [PM2.5], µg/m3 O3 Ethylene Pine Smoke, conventional HMS Ponderosa, conventional HMS Chamise, conventional HMS Rice Straw, conventional HMS Pine Duff, conventional HMS Tundra Duff, conventional HMS Manzanita, conventional HMS Wax Myrtle, improved HMS Southern Pine, improved HMS Tropical Sticks, improved HMS Palmett, improved HMS Ceocanthus, improved HMS Linear (Pine Smoke, conventional HMS) Linear (Ponderosa, conventional HMS) Linear (Chamise, conventional HMS) Linear (Rice Straw, conventional HMS) Linear (Pine Duff, conventional HMS) Linear (Tundra Duff, conventional HMS) Linear (Manzanita, conventional HMS) Linear (Wax Myrtle, improved HMS) Linear (Southern Pine, improved HMS) Linear (Tropical Sticks, improved HMS) Linear (Palmett, improved HMS) Linear (Ceocanthus, improved HMS)
17 API 265a NO Chemiluminescent Interference Mean of All Runs: -.5 ppb Interference/1 µg/m 3 PM 2.5 Range of Slopes: -.7 to 2 ppb/1 µg/m 3 Some Systematic Degradation throughout Experiment API 265a NO Chemiluminescent O3 Interference Delta [O3] [PM2.5], µg/m3 O3 Ethylene Pine Smoke Ponderosa Chamise Rice Straw Pine Duff Tundra Duff Manzanita Sage and Rabbit Brush Pine Needles Tropical Foliage Wax Myrtle Southern Pine Tropical Sticks Palmetto Ceocanthus Linear (Pine Smoke) Linear (Ponderosa) Linear (Chamise) Linear (Rice Straw) Linear (Pine Duff) Linear (Tundra Duff) Linear (Manzanita) Linear (Sage and Rabbit Brush) Linear (Pine Needles) Linear (Tropical Foliage) Linear (Wax Myrtle) Linear (Southern Pine) Linear (Tropical Sticks) Linear (Palmetto) Linear (Ceocanthus)
18 Dasibis with and without Inlet Filters Inlet Filtration Significantly Reduces Interference Effects of Particle Filtration [O3], ppb Unfiltered PM [PM2.5], µg/m3 Dasibi C, No Inlet Filter Dasibi D, With Inlet Filter TEOM PM2.5 (Estimated) 5 With 3-5 Negative Interference 16: 17:2 18:4 2: 21:2 Time -3
19 Data Collection Issues: TEOM Overload Test Run Interference TEOM Datalogger Full Scale: -1 to 9 g/m Zero Corrected Delta [O3] O3 Ethylene O3MnO2 O3 heated O3 chem DASIBI C DASIBI D Series /4/26 15:36 6/4/26 16:48 6/4/26 18: 6/4/26 19:12 6/4/26 2:24 6/4/26 21:36 6/4/26 22:48 Time
20 TEOM Overload Test Run Interference Estimated TEOM Response 19 Zero Corrected Delta [O3] O3 Ethylene O3MnO2 O3 heated O3 chem DASIBI C DASIBI D Series /4/26 15:36 6/4/26 16:48 6/4/26 18: 6/4/26 19:12 6/4/26 2:24 6/4/26 21:36 6/4/26 22:48 Time
21 TEOM Overload on 1 st Chamise Run, TEOM Filter Swap on Juniper Run TEOM and Ozone Data, All Runs 1 9 Chamise Juniper /3/6 : 6/4/6 : 6/5/6 : 6/6/6 : 6/7/6 : 6/8/6 : 6/9/6 : [O3], ppb 6/1/6 : PM2.5, g/m3 O3MnO2 O3 heated O3 chem DASIBI C DASIBI D O3 Ethylene TEOM PM2.5-2 Time
22 Conclusions and Future Plans Smoke interference with UV analyzers was observed in all test runs Smoke needed to be reasonably dense (> 7 µg/m 3 of PM 2.5 ) to induce significant interference Interference seemed to decrease as the smoke aged Inlet filters significantly decrease observed interference Future Analysis Regress [O 3 ] with [CO], [NO x ] and THC Address differing instrument response times Ozone analyzers respond to smoke more quickly than TEOM Ozone interference peak precedes PM 2.5 Peak 6 minute TEOM averaging time, vs. seconds for ozone analyzers Plan to Provide PM2.5 Data from TEOM to CSU FLAME server in the near future
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