Experiment: 2014 FIXCIT Study_20140201_OZONE/CYCLOHEXANE_Ozone_No Seed_Characterization of GTHOS artifact with O3, HO2, and cyclohexane, 30% humidity, no seeds

Experiment

Name: 2014 FIXCIT Study_20140201_OZONE/CYCLOHEXANE_Ozone_No Seed_Characterization of GTHOS artifact with O3, HO2, and cyclohexane, 30% humidity, no seeds
Date: 2014-02-01

Organization
2014 FIXCIT Study

Chamber
Seinfeld chambers

Experiment Set
FIXCIT experiments

Goals
Test if the HO2 + O3 reaction contributes to the GTHOS artifact, at two RH conditions.

Summary
Injections went smoothly. For the CF3O- CIMS, the products that were produced were mostly formic acid, H2O2, and HMHP. Ozone was constant over the course of ~ 2 h, even with lights on, and decreased immediately upon the injection of formaldehyde. Cyclohexane did not appear to react at all throughout the experiment, and the cyclohexane hydroperoxide (m/z 201 on CF3O- CIMS) was not observed. HMHP was assumed to have been produced from the HCHO + HO2 reaction, as described by Niki et al, Chem Phys Lett, 1980. There was a step-function increase of the cyclohexane signal in the GC-FID from the injection of formaldehyde. This additional signal was steady throughout the reaction, so we think there might have been some cyclohexane still left in the injection line that got injected in with the formaldehyde, and so this should not be regarded as a GC interference at the cyclohexane retention time by formaldehyde (which did not show up in the NO3 + formaldehyde experiments). The addition of water vapor decreased the HMHP signal greater than the dilution ratio, as marked by O3, indicating the HMHP signal may have a water sensitivity. Ozone did not further react away after the addition of water.

Additional Notes
Instrument Status: GTHOS - up RHTO3 - up GC FID - up TQC1 - up TQC2 - up TOFCIMS - up Bag Additions: Ozone ~ 600 ppb Cyclohexane ~ 50 ppb Water vapor, RH ~ 30% Timeline (UTC, hrs): 17:00 - GTHOS measuring 17:20 - RH/T/O3/NOx measuring 17:25 - GC-FID measuring, CIMS measuring 17:31 - Ozone injection started 19:08 - Stopped ozone injection 19:16 - Injected ozone for another 10 min 19:35 - Injected cyclohexane (5.4 uL) 19:47 - Done filling bag 20:32 - Lights on (100%) 21:50 - Added HCHO with flushing (13.8 Torr, 6 L bulb, ~ 4 ppm in the bag) 22:15 - HCHO injection stopped 23:20 - Started humidifying 24:00 - Stopped humidifying (RH ~ 31%) 24:30 - Lights off 25:40 - Started flushing

Experiment Details

Categories:

  • Instrument/Chamber characterization
Temperature: 25
Relative Humidity: 31
Seeded Experiment: No
Fuchs Adjusted Surface Area:
Condensation sink rate coefficient: 31
Reaction type:
Oxidant Name: Ozone
Initial Oxidant Concentration Value: 600 (parts_per_billion)
RO2 Main Fate: Not Sure
RO2 Lifetime: (Seconds)
Pressure: 750 Torr

Data Sets

ID Instrument File  
1318 GTHOS_OH 20140201_OH.csv
1319 GTHOS_HO2 20140201_HO2.csv
1320 GC-FID FIX-CIT-GCFID-VOCs_Chamber_20140201_RA.csv
1321 RHTO3NOx FIX-CIT-RHTO3NOx_Chamber_20140201_RA.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

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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
OZONE (24823) 600 Parts Per Billion
CYCLOHEXANE (8078)
  • Alkane
 50 Parts Per Billion

20140201_expTimeline.csv Timeline

UTC_hr Action
17:00 GTHOS measuring
17:20 RH/T/O3/NOx measuring
17:25 GC-FID measuring, CIMS measuring
17:31 Ozone injection started
19:08 Stopped ozone injection
19:16 Injected ozone for another 10 min
19:35 Injected cyclohexane (5.4 uL)
19:47 Done filling bag
20:32 Lights on (100%)
21:50 Added HCHO with flushing (13.8 Torr, 6 L bulb, ~ 4 ppm in the bag)
22:15 HCHO injection stopped
23:20 Started humidifying
24:00 Stopped humidifying (RH ~ 31%)
24:30 Lights off
25:40 Started flushing

Citations
Cite this experiment: Publication associated with this experiment:

Characterizations
Light Flux Characterizations:
2013-12-16 (#17)
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: