Formaldehyde Measurements from R/V Brown during TexAQS 2006
Transcript of Formaldehyde Measurements from R/V Brown during TexAQS 2006
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Formaldehyde Measurements from R/V Brown during TexAQS II
Scott C. Herndon, Mark S. Zahniser, Timothy Onasch, Hans Osthoff, Brian Lerner, Dan Welsh-Bon, Jessica Gilman, Roberto Sommariva, Jim Roberts, Ken Aikin, Alan Brewer, Sara Tucker, Tim Bates, Patricia Quinn, Bill Kuster and Eric Williams
HCHO
Photos by Richard Marchbanks and Dan Welshbon
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Formaldehyde (HCHO) Measurement OverviewHouston
Galveston Bay
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Outline
IntroductionHCHO in the urban atmosphereWhy HCHO emissions are important in Urban Air Quality
Analytical ApproachTunable Infrared Differential Absorption SpectroscopyInlet Schematic, Characterization, Performance
Comparison with P3 overflightPrimary & Secondary HCHO
Time Series AnalysisDirect Emissions
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HCHO in the Urban Atmosphere
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HCHO Emission and Influence on O3
pre-sunrise HCHO actsas an efficient HOx source
Lerner et al.
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Ron Brown 2006 Tower Sample Box
Instrument in Deck TrailerTunable Infrared Laser-
Differential Absorption Spectroscopy
Inlet Sampling Schematic
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Dual Quantum Cascade Lasers
HCHO
HCOOH C2H4NH3
LASER 1 (1765 cm-1) LASER 2 (965 cm-1)
Two Wavelength Regions contain 4 decent absorbers
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HCHO Sensitivity: Leg 2HCHO AVERAGED SPECTRUM in MBL
4 Hr AVERAGE SPECTRUM 0.5 ppbABORBANCE NOISE 2e-7 10 ppt
ALLAN PLOT50 ppt @ 30s
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Inlet Characterization ResultsPermeation sources of HCHO and NH3
HCHO: inlet transmissioncomplete and quick
NH3: inlet transmission ok but slow
At-Sea Inlet Characterization (5 mins. of each hour)Even hours: Perm + Zero Air
Odd hours: Standard Addition
Additional Inlet Tests (at sea)
Advice from Osthoff, Roberts, Kuster
Alternate ambient O3and enhanced (120 ppbv) O3
No change in measured HCHO in MBL
With O3 AdditionTotal Flow Variationsdifferent residence timesby factor of 5, saw no difference in diurnal MBL HCHO
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Ron Brown comparison with P3 overflight
Below PBL raw difference is 7.5%
P3 HCHO - Richter, Fried et al.
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HCHO comparison - North vs East
Overflight comparison is short -spatial overlap - amounts to one point comparison
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Acetaldehyde - North vs East
Airmass below PBL where HCHO was elevatedalso has high CH3CHO
de Gouw, Warneke, Welshbon
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1,3 Butadiene Plume
Lerner, Gilman, Kuster et al.
1, 3 Butadiene
overflight
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Primary, Secondary HCHO
Part 2: Exhaust Plume Analysis (w/source attribution)Measure directly emitted HCHO, ratio by dilution tracer CO2
Ship Channel Plume Encounters (Williams et al.)Anchored Ship EmissionsDrilling Platform (gas-flare vs diesel generator)
Part 1: Time-series analysisuntangle directly emitted HCHO from atmospheric production
Houston/Galveston Bay Areadiurnal average & median
Tracer Pair Correlation, CO and O3
‘Primary’ = directly emitted from various sources‘Secondary’ = produced in the atmosphere
HOx sourcecosts an OH, O3 et al.
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Houston/Galveston Bay - Diurnal HCHO
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Diurnal Median vs Average
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Simple HCHO vs CO correlation
How representative is median correlation plot of Houston Ensemble Emissions?
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First Visit to Turning Basin 8/2
Primary vs Secondary HCHO
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Second Visit to Turning Basin 8/11
Primary vs Secondary HCHO
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Plume by Plume Analysis HCHO/CO
30 minute segments in the turning basin analyzed for primary HCHO/CO plume content; 2 - 10 ppt/ppb
Primary vs Secondary HCHO
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Primary vs Secondary HCHOFriedfeld et al. - Tracer Pair (CO w/time lag; O3)
Houston Area: Primary HCHO 37%Possanzini et al. HCHO/Toluene
Rome, Italy: Primary less than 20% in summerLi et al. - Principal Component Analysis
Vancouver: Primary~ 20%Jimenez et al. Tracer Pair (NOx; O3)
Grenoble, France: Primary <20%Garcia et al. - Tracer Pair (CO; glyoxal & CO; O3)
Mexico City Metro. Area: Primary 40%(allowing for ~20% as point source, or area bg.)
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Return to Diurnal - CO, O3
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H2CO Loadings by Combustion Sources
ppb H2CO / ppm CO2Automobiles with functioning Catalytic Converter <0.05
Gasoline “Engine Out” 0.2-0.4
Diesel Heavy Duty <0.03-0.1Compressed Natural Gas ~0.5
high bypass turbine engine(aircraft engines) low throttle 0.9-2.2
take-off <0.02
Ships in HSC ?
Primary HCHO Direct Measurement
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Ship Emissions
despite different inlets, and different computer timesplume attribution is possible (Δt = 3.7s)
Primary HCHO Direct Measurement
Time Series of HCHO and CO2
Williams and Lerner
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Despite challenges, can limits be set for direct HCHO emissions?
Primary HCHO Direct Measurementtentative anticorrelation with target speed
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Two combustion sourcessingle platformlong time seriesdithering wind
Primary HCHO Direct Measurement
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Drilling Platform Flare Fire vs Diesel Generator
Dan Lack Photoacoustic Black Carbon ⇒ER(BC) flare ~ 1/2 diesel
0.9 g HCHO kg-1 CNG fuel*
Primary HCHO Direct Measurement
Diesel Generator contained Fuel Sulfur Content ~2%
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H2CO Loadings by Combustion Sourcesppb H2CO / ppm CO2
Automobiles with functioning Catalytic Converter <0.05
Boston Fleet Traffic 0.03Mexico City Fleet (2002) 0.14Mexico City Fleet (2006) 0.11
Gasoline “Engine Out” 0.2-0.4
Diesel Heavy Duty <0.03-0.1Compressed Natural Gas ~0.5
high bypass turbine engine(aircraft engines) low throttle 0.9-2.2
take-off <0.02
Ships in HSC 0.02-0.151 Flare in Gulf of Mexico prelim analysis ~ 0.6
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Summary and ConclusionsDual QCL TILDAS Performance
- HCHO 1s rms < 250 pptv; 2σ D.L. (1 minute) 75 pptv
- Systematic Error Est. 7% linestrength, 9% total
- No evidence of Inlet effects for marine BL HCHO
- Instrument also measured HCOOH, C2H4, sharp NH3 plumes*
Analysis
-Diurnal time-series suggest substantial photochemical production
- Turning Basin ER (HCHO) 30 min dist. (2-10) 3 ppt ppb-1 CO
-CO, O3 tracer pairs indicate upper limit for HCHO/CO
ER (HCHO) 0.008; (8 ppt ppb-1 CO)
CO, O3 do not capture HCHO temporal profile (poor pair)
- Direct HCHO EF from working ships in HSC/Galv. (g HCHO kg-1 fuel)
- Ship EF is greater than anticipated, more like on-road category
‘diesel working hard’ -- EF < 0.05 * EF(CO)
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Backup Slides
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1,3 Butadiene Emission Inventory
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Anchored Ship Upwind Plume Encounters
Alan Brewer, Hans Osthoffavailable as a movie
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Tentative Inverse Correlation: HCHO with Target Speed
Primary HCHO Direct Measurement
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Diurnal Day in Houston-Galveston Area
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HCHO and HCOOH Spectroscopic Purity
• Limit on cross talk; orthogonal retreivals; first figure of this type; only limit because no measure of HCOOH
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Additional Inlet Tests (at sea)
11:40 PM8/28/2006
11:50 PM 12:00 AM8/29/2006dat
1.2
1.0
0.8
0.6
0.4
0.2
0.0
HC
HO (p
pb)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
HCO
OH
(ppb
)
O3 17 ppb O3 120 ppb
ΔHCOOH +50 pptΔHCHO -20 pptuncertainty 30 ppt (2σ)Alternate ambient O3
and enhanced O3
No significant change with 120 ppb of added O3
Measured HCHO in MBLis not due to O3inlet effects
With O3 Addition
Total Flow Variationsdifferent residence timesby factor of 5, saw no difference in diurnal MBL HCHO
Advice from Ostoff, Roberts, Kuster
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detection limits 10 s = 360 pptv200 s = 66 pptv
• Allan plot and systematic error estimatesInstrument Performance
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HCHO in MBL• Steady state model showing methane-only
production in clean MBL represents measurement
• Maybe figure or mention of the O3 spiking and other inlet tests to show inlet not producing HCHO
• Distill next three slides to one
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Back Trajectories all from the South
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HCHO vs CO in Houston Turning Basin
Primary vs Secondary HCHO
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Drilling Platform Flare Fire vs Diesel Generator
Primary HCHO Direct Measurement