Experiment: 2014 FIXCIT Study_20140104_1-hydroxy-2-hydroperoxy ISOPOOH/hydrogen peroxide_Hydroxyl radical_No Seed_Blank H2O2 + hv (low-NO "near" bag) and ISOPOOH calibrations

Experiment

Name: 2014 FIXCIT Study_20140104_1-hydroxy-2-hydroperoxy ISOPOOH/hydrogen peroxide_Hydroxyl radical_No Seed_Blank H2O2 + hv (low-NO "near" bag) and ISOPOOH calibrations
Date: 2014-01-04

Organization
2014 FIXCIT Study

Chamber
Seinfeld chambers

Experiment Set
FIXCIT experiments

Goals
Control for chemistry related to chamber so as to tease out chamber artifacts. Secondary stuff: calibrate multiple CIMS for ISOPOOH, understand fragmentation of ISOPOOH in the PTR-MS, check ISOPOOH interference on TD-LIF, NO CL, GC-FID.

Summary
NOTE that H2O2 + hv blank and ISOPOOH calibrations were carried out in separate bags, but individual instruments switched sampling between the bags Instruments mostly sampling empty chamber by 9:20am. PTR-MS noted a large signal of acetone, which seemed to decay away to background at least by lunch time. H2O2 was added to the chamber. Before instruments were allowed to sample, the chamber volume seemed low. Additional air was added for ~20 minutes to start with a relatively full bag. Sampling in the dark with H2O2 proceeded as usual by 11:30am. Dark sampling took longer than usual due to the instruments being taken off the bag to sample ISOPOOH standard bags. Lights on proceeded as usual. About three hours in, the chamber volume was checked. Volume seemed okay to run for another 2 hours. After the volume check, the temperature in the chamber was ramped up to a safe 33C to test temperature effects. Nitrate CIMS, TD-LIF reported increases in signals. Lights turned off, and after about 10 mnutes, the temperature was ramped back down to 25C. Concurrently, ISOPOOH standards were shared. The first ISOPOOH standard bag (Bag 1) was a bit leaky, but made it to the CF3O- CIMS, then moved on and was depleted by NO3- CIMS. A second bag (Bag 2) was prepped which, again, went first to the CF3O- CIMS, and then moved on to the A-/I- CIMS. Bag 2 then headed to NO3- CIMS. A lunch break was taken, and the round-robin continued: GC-CIMS, PTR-MS (+ cold trapping tests), NO-C mmmm,L, TD-LIF, and finally GC-FID.

Additional Notes
Instrument Status: TD LIF - up PTRMS - up GTHOS - up LIF OHR - up CRM OHR - down, waiting on parts NO CL - up GLY LIP - down [laser broken] FOR LIF - down I/A CIMS - up NCIMS - up RHTO3 - up GC FID - up AMS - up TQC1 - up TQC2 - up TOFCIMS - up Bag Additions: H2O2, ~2ppm (110 uL 50% H2O2), diluted somewhat by extra addition of air Timeline (UTC, hrs): 17:00 - chamber is full, and disconnected from exhaust. 17:00 - sampling began 17:30 - all instruments measuring on chamber background 17:40 - all instruments off chamber 17:49 - H2O2 injection began 18:56 - H2O2 injection stopped 19:00 - air injection into chamber 19:24 - stopped air injection 19:24 - instruments told to start sampling on chamber 19:33 - all instruments sampling on bag 20:25 - all UV lights on (1-6) 23:28 - all lights off to check chamber volume, low but not crazy 23:31 - all lights back on (1-6) 23:32 - started ramping chamber temperature to 33C 23:40 - chamber temperature confirmed to be 33C 24:48 - all UV lights off 25:00 - started ramping chamber to 25C 25:06 - temperature @ 27C and work lights turned on 25:20 - end of experiment, air injection starts 26:14 - bag full 18:40 - CF3O- CIMS measures Bag 1 18:56 - Bag 1 heads to NO3- CIMS, and is depleted by NO3- CIMS 19:50 - CF3O- CIMS measures Bag 2 20:00 - Bag 2 heads to I- CIMS 20:10 - Bag 2 heads to NO3- CIMS 20:21 - Bag 2 is given a rest so people can eat 22:26 - Bag 2 is given to CF3O- CIMS for GC run 22:48 - Bag 2 is given to PTR-MS for cold trap testing 23:05 - Approximate start of cold trap tests with PTR-MS (Liu et al, 2013) 23:37 - Bag 2 is given to CF3O- CIMS for a repeat GC run 24:05 - Bag 2 is given to TD-LIF to sample 24:17 - Bag 2 is given to NO-CL to sample 26:30 - Bag 2 resampled by CIMS CF3O-

Experiment Details

Categories:

  • Blank/Control
Temperature: 24-33
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: 2.0e6 (molecules_per_cubic_centimeter)
RO2 Main Fate: HO2
RO2 Lifetime: (Seconds)
Pressure: 750

Data Sets

ID Instrument File  
1064 TOF-AMS (Low Resolution) 20140104_AMS.csv
1065 GTHOS_OH 20140104_OH.csv
1066 GTHOS_HO2 20140104_HO2.csv
1067 NO-CL FIX-NCAR_NO_CL-NO_Chamber_20140104_RA.csv
1068 RHTO3NOx FIX-CIT-RHTO3NOx_Chamber_20140104_RA.csv
1069 NO3-TOF-CIMS 20140104_NO3CIMS.csv
1070 OHR-LIF 20140104_LIFOHR.csv
1071 CF3O TripleQ-CIMS 20140104_TRIPCIMSmerge.csv
1095 TD-LIF D20140104_TDLIF.csv
1096 CF3O-TOF-CIMS 20140104_TOFCIMSmerge.csv
1322 I-TOF-CIMS 20140104_ICIMS.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 (1.05 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
1-hydroxy-2-hydroperoxy ISOPOOH
  • Alcohol
  • Alkene
  • Hydroperoxide
 250 Parts Per Billion
hydrogen peroxide (784) 2 Parts Per Million

20140104_expTimeline.csv Timeline

UTC_hr Action
17:00 chamber is full and disconnected from exhaust.
17:00 sampling began
17:30 all instruments measuring on chamber background
17:40 all instruments off chamber
17:49 H2O2 injection began
18:40 CF3O- CIMS measures Bag 1
18:56 H2O2 injection stopped
18:56 Bag 1 heads to NO3- CIMS and is depleted by NO3- CIMS
19:00 air injection into chamber
19:24 stopped air injection
19:24 instruments told to start sampling on chamber
19:33 all instruments sampling on bag
19:50 CF3O- CIMS measures Bag 2
20:00 Bag 2 heads to I- CIMS
20:10 Bag 2 heads to NO3- CIMS
20:21 Bag 2 is given a rest so people can eat
20:25 all UV lights on (1-6)
22:26 Bag 2 is given to CF3O- CIMS for GC run
22:48 Bag 2 is given to PTR-MS for cold trap testing
23:05 Approximate start of cold trap tests with PTR-MS (Liu et al 2013)
23:28 all lights off to check chamber volume... low but not crazy
23:31 all lights back on (1-6)
23:32 started ramping chamber temperature to 33C
23:37 Bag 2 is given to CF3O- CIMS for a repeat GC run
23:40 chamber temperature confirmed to be 33C
24:05 Bag 2 is given to TD-LIF to sample
24:17 Bag 2 is given to NO-CL to sample
24:48 all UV lights off
25:00 started ramping chamber to 25C
25:06 temperature @ 27C and work lights turned on
25:20 end of experiment air injection starts
26:14 bag full
26:30 Bag 2 resampled by CIMS CF3O-

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: