Experiment: 2014 FIXCIT Study_20140130_PINONALDEHYDE/Pinonic acid/Methyl nitrite_Hydroxyl radical_No Seed_Pinonaldehyde + OH, moderate NO, dry, no seeds

Experiment

Name: 2014 FIXCIT Study_20140130_PINONALDEHYDE/Pinonic acid/Methyl nitrite_Hydroxyl radical_No Seed_Pinonaldehyde + OH, moderate NO, dry, no seeds
Date: 2014-01-30

Organization
2014 FIXCIT Study

Chamber
Seinfeld chambers

Experiment Set
FIXCIT experiments

Goals
Explore the gas-phase chemistry of pinonaldehyde when HO2, NO, and NO2 are all present.

Summary
Synthesized pinonaldehyde was added through a heated line for a few hours to get enough into the bag. This was the first time we had injected pinonaldehyde and learned that next time, we shouldn't heat the injection line or the bulb because that facilitates the oxidation of pinonaldehyde to pinonic acid. Thus both were injected at initial mixing ratios of ~ 15 ppb (with a fair amount of uncertainty) to ~ 10-20 ppb pinonic acid (also with uncertainty). The pinonic acid is expected to react with OH about 4 times slower than pinonaldehyde, although there is a channel for the production of pinonic acid from the pinonaldehyde photooxidation as well. After initiating OH oxidation by methyl nitrite photolysis, CF3O- CIMS observed that almost all of the carbon ended up as the PAN of pinonaldehyde (which Geoff calls"PiPAN"). Perhaps due to the high formation of the PiPAN, we observed high amounts of nucleated organic aerosol (~ 40 ug/m3 at the end of the experiment). At the end of the experiment, most of the pinonaldehyde was gone, but more than half of the pinonic acid was left (perhaps because it's produced as well as lost through OH oxidation). We injected methyl nitrite twice, to replenish the OH. At the end, lights were turned off and the bag was flushed within 20 minutes.

Additional Notes
Instrument Status: TD LIF - up PTRMS - up GTHOS - up LIF OHR - up CRM OHR - up NO CL - up GLY LIP - up FOR LIF - up I/A CIMS - up NCIMS - up RHTO3 - up GC FID - up AMS - up TQC1 - up TQC2 - up TOFCIMS - up Bag Additions: Pinonaldehyde ( > 95% purity), ~ 15 ppb (may be revised) Pinonic acid = 10 - 20 ppb (may be revised) CH3ONO ~ 45 ppb (first addition) ; ~ 250 ppb (second addition) Timeline (UTC, hrs): 17:45 - Far bag capped 18:00 - Injecting pinonaldehyde, heating bath at 60 degC 19:30 - Switched to heating with heat gun 20:20 - Added more pinonaldehyde 21:00 - Stopped heating all-together 22:00 - Mostly everyone is sampling now 22:12 - Added methyl nitrite (CH3ONO 1.602 torr in 500 mL @ 22 degC) 22:27 - Stopped injection, pulsed mixing air 22:30 - UV lights on (10% intensity) 24:55 - Lights off 24:58 - Added methyl nitrite (CH3ONO 8.03 torr in 500 mL @ 22 degC) 25:20 - UV lights on (10% intensity) 26:20 - Lights off 26:43 - Flushing Far bag

Experiment Details

Categories:

  • Gas phase chemical reaction
Temperature: 26
Relative Humidity: 5
Seeded Experiment: No
Fuchs Adjusted Surface Area:
Condensation sink rate coefficient: 5
Reaction type:
Oxidant Name: Hydroxyl radical
Initial Oxidant Concentration Value: 3.5e6 (molecules_per_cubic_centimeter)
RO2 Main Fate: NO
RO2 Lifetime: (Seconds)
Pressure: 750 Torr

Data Sets

ID Instrument File  
1307 TOF-AMS (Low Resolution) 20140130_AMS.csv
1308 GTHOS_OH 20140130_OH.csv
1309 GTHOS_HO2 20140130_HO2.csv
1310 NO-CL FIX-NCAR_NO_CL-NO_Chamber_20140130_RA.csv
1311 RHTO3NOx FIX-CIT-RHTO3NOx_Chamber_20140130_RA.csv
1312 CF3O TripleQ-CIMS 20140130_TRIPCIMSmerge.csv
1313 TOF-AMS (High Resolution) 20140130_HRAMS.csv
1314 PTR-TOF-MS 20140130_PTRTOFMS.csv
1315 TD-LIF D20140130_TDLIF.csv
1316 GLY-LIP 20140130_GLYLIP.csv
1317 CF3O-TOF-CIMS 20140130_TOFCIMSmerge.csv

Data Set plots
Choose a file: Choose the X-Axis:

Experiment Set Details

Name: FIXCIT experiments
Time format and units: Seconds past midnight
Description:
The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative study at the atmospheric chambers of Caltech during January 2014. FIXCIT is the laboratory component of SOAS, and is aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. A series of chamber experiments was conducted to investigate the oxidation of isoprene, α-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX). Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized, enabling study of the oxidation mechanisms and instrument responses for these compounds.

Collaborators:

  • Allen H. Goldstein UC Berkeley
  • William H. Brune Penn State University
  • Ronald C. Cohen UC Berkeley
  • Delphine K. Farmer Colorado State University
  • Manjula R. Canagaratna Aerodyne
  • Douglas R. Worsnop Aerodyne
  • Jose L. Jimenez University of Colorado Boulder
  • Frank N. Keutsch Harvard
  • Saewung Kim UC Irvine
  • Alex B. Guenther UC Irvine
  • John E. Mak SUNY Stonybrook
  • Geoffrey S. Tyndall NCAR
  • Denise D. Montzka NCAR
  • Andrew J. Weinheimer NCAR
  • Alam Hasson Fresno State

Download

Download this Experiment (1.9 MB)

Contacts

Principal investigators:

Paul O. Wennberg
Phone: 626 395 2447
E-mail: wennberg@caltech.edu
OrcID: 0000-0002-6126-3854

John H. Seinfeld
Phone: 626-395-4635
E-mail: seinfeld@caltech.edu
OrcID: 0000-0003-1344-4068

John D. Crounse
Phone: 626-395-8655
E-mail: crounjd@caltech.edu
OrcID: 0000-0001-5443-729X

Tran B Nguyen
Phone: 5307525987
E-mail: tbn@ucdavis.edu
OrcID: 0000-0001-9206-4359

Data Manager:

Tran B. Nguyen
Phone: 5307525987
E-mail: tbn@ucdavis.edu

Reactants

Reactant Compound type Concentration Concentration units
PINONALDEHYDE (17616)
  • Aldehyde
  • Ketone
 15 Parts Per Billion
Pinonic acid (10130)
  • Ketone
  • Organic acid
 15 Parts Per Billion
Methyl nitrite (12231)
  • NOx
 45 Parts Per Billion

20140130_expTimeline.csv Timeline

UTC_hr Action
17:45 Far bag capped
18:00 Injecting pinonaldehyde; heating bath at 60 degC
19:30 Switched to heating with heat gun
20:20 Added more pinonaldehyde
21:00 topped heating all-together
22:00 Mostly everyone is sampling now
22:12 Added methyl nitrite (CH3ONO 1.602 torr in 500 mL @ 22 degC)
22:27 Stopped injection; pulsed mixing air
22:30 UV lights on (10% intensity)
24:55 Lights off
24:58 Added methyl nitrite (CH3ONO 8.03 torr in 500 mL @ 22 degC)
25:20 UV lights on (10% intensity)
26:20 Lights off
26:43 Flushing Far bag

Citations
Cite this experiment: Publication associated with this experiment:

Characterizations
Light Flux Characterizations:
2013-12-16 (#19)
Particle Loss Characterizations:
(None)
Vapor Loss Characterizations:
(None)

Chamber Details

Name: Seinfeld chambers
Volume in cubic meters: 22
Shape: Rectangular Prism
Surface area in cubic meters: 48
Flow Mode: Batch
Flow through rate in liters per minute:
Body Material: Teflon
Body thickness: 2
Replacement date:
Replacement frequency: As needed
Cleaning method: Flushing with air Flushing with air with UV lights on Oxidation
o3 background: < 0.5 ppb
nox background: 40 ppt
Particle background in micrograms per cubic meter: < 0.01 ug/m3
Air filtration method: Custom filtration canisters to remove NOx, hydrocarbons, water, particles, ozone, SOx from pressurized ambient air.
Mixing method: 1
Mixing method material: Pulsed air jets, manually actuated
Temparature Control: Yes
Temparature measurements recorded: Yes
Temparature range (min degrees celcius): 10
Temparature range (max degrees celcius): 45
Humidity Control: Yes
Humidity Measurements Recorded: Yes
Relative humidity range (min percent): 4
Relative humidity range (max percent): 90
Particle experiment capability: 1
Lights: Yes
Light source type(s): UV black lamps (350 nm centered)
Supplemental information: https://www.worldscientific.com/doi/abs/10.1142/9789813147355_0001
Additional Notes: