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Title: Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds

Abstract

Recent studies have demonstrated that organic compounds can partition from the gas phase to the walls in Teflon environmental chambers and that the process can be modeled as absorptive partitioning. Here these studies were extended to investigate gas–wall partitioning of organic compounds in Teflon tubing and inside a proton-transfer-reaction mass spectrometer (PTR-MS) used to monitor compound concentrations. Rapid partitioning of C 8–C 14 2-ketones and C 11–C 16 1-alkenes was observed for compounds with saturation concentrations ( c *) in the range of 3×10 4 to 1×10 7µgm -3, causing delays in instrument response to step-function changes in the concentration of compounds being measured. These delays vary proportionally with tubing length and diameter and inversely with flow rate and c *. The gas–wall partitioning process that occurs in tubing is similar to what occurs in a gas chromatography column, and the measured delay times (analogous to retention times) were accurately described using a linear chromatography model where the walls were treated as an equivalent absorbing mass that is consistent with values determined for Teflon environmental chambers. The effect of PTR-MS surfaces on delay times was also quantified and incorporated into the model. The model predicts delays of an hour ormore » more for semivolatile compounds measured under commonly employed conditions. These results and the model can enable better quantitative design of sampling systems, in particular when fast response is needed, such as for rapid transients, aircraft, or eddy covariance measurements. They may also allow estimation of c * values for unidentified organic compounds detected by mass spectrometry and could be employed to introduce differences in time series of compounds for use with factor analysis methods. Best practices are suggested for sampling organic compounds through Teflon tubing.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, CO (United States); Univ. of Colorado, Boulder, CO (United States)
  2. Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, CO (United States); Univ. of Colorado, Boulder, CO (United States); Aerodyne Research, Inc., Billerica, MA (United States)
  3. Cooperative Institute for Research in Environmental Sciences (CIRES), Boulder, CO (United States); National Oceanic and Atmospheric Administration (NOAA), Boulder, CO (United States). Earth System Research Lab.
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1458837
Alternate Identifier(s):
OSTI ID: 1502928
Grant/Contract Number:  
SC0016559
Resource Type:
Published Article
Journal Name:
Atmospheric Measurement Techniques (Online)
Additional Journal Information:
Journal Name: Atmospheric Measurement Techniques (Online); Journal Volume: 10; Journal Issue: 12; Journal ID: ISSN 1867-8548
Publisher:
European Geosciences Union
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES

Citation Formats

Pagonis, Demetrios, Krechmer, Jordan E., de Gouw, Joost, Jimenez, Jose L., and Ziemann, Paul J. Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds. United States: N. p., 2017. Web. doi:10.5194/amt-10-4687-2017.
Pagonis, Demetrios, Krechmer, Jordan E., de Gouw, Joost, Jimenez, Jose L., & Ziemann, Paul J. Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds. United States. doi:10.5194/amt-10-4687-2017.
Pagonis, Demetrios, Krechmer, Jordan E., de Gouw, Joost, Jimenez, Jose L., and Ziemann, Paul J. Mon . "Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds". United States. doi:10.5194/amt-10-4687-2017.
@article{osti_1458837,
title = {Effects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compounds},
author = {Pagonis, Demetrios and Krechmer, Jordan E. and de Gouw, Joost and Jimenez, Jose L. and Ziemann, Paul J.},
abstractNote = {Recent studies have demonstrated that organic compounds can partition from the gas phase to the walls in Teflon environmental chambers and that the process can be modeled as absorptive partitioning. Here these studies were extended to investigate gas–wall partitioning of organic compounds in Teflon tubing and inside a proton-transfer-reaction mass spectrometer (PTR-MS) used to monitor compound concentrations. Rapid partitioning of C8–C14 2-ketones and C11–C16 1-alkenes was observed for compounds with saturation concentrations (c*) in the range of 3×104 to 1×107µgm-3, causing delays in instrument response to step-function changes in the concentration of compounds being measured. These delays vary proportionally with tubing length and diameter and inversely with flow rate and c*. The gas–wall partitioning process that occurs in tubing is similar to what occurs in a gas chromatography column, and the measured delay times (analogous to retention times) were accurately described using a linear chromatography model where the walls were treated as an equivalent absorbing mass that is consistent with values determined for Teflon environmental chambers. The effect of PTR-MS surfaces on delay times was also quantified and incorporated into the model. The model predicts delays of an hour or more for semivolatile compounds measured under commonly employed conditions. These results and the model can enable better quantitative design of sampling systems, in particular when fast response is needed, such as for rapid transients, aircraft, or eddy covariance measurements. They may also allow estimation of c* values for unidentified organic compounds detected by mass spectrometry and could be employed to introduce differences in time series of compounds for use with factor analysis methods. Best practices are suggested for sampling organic compounds through Teflon tubing.},
doi = {10.5194/amt-10-4687-2017},
journal = {Atmospheric Measurement Techniques (Online)},
number = 12,
volume = 10,
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.5194/amt-10-4687-2017

Citation Metrics:
Cited by: 11 works
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