Data quality improvement for field-portable gas chromatography-mass spectrometry through the use of isotopic analogues for in-situ calibration
Anthony Qualley
A C , Geoffrey T. Hughes A and Mitchell H. Rubenstein B
A UES, Inc., Air Force Research Laboratory, 711th Human Performance Wing/RHMO, 2510 Fifth Street, Area B, Building 840, Wright-Patterson AFB, OH 45433, USA.
B United States Air Force 711th Wing – Air Force Research Laboratory, 711th Human Performance Wing/RHMO, 2510 Fifth Street, Area B, Building 840, Wright-Patterson AFB, OH 45433, USA.
C Corresponding author. Email: anthony.qualley.ctr@us.af.mil
Environmental Chemistry 17(1) 28-38 https://doi.org/10.1071/EN19134
Submitted: 13 May 2019 Accepted: 7 August 2019 Published: 12 September 2019
Journal Compilation © CSIRO 2020 Open Access CC BY-NC-ND
Environmental context. Quantitative field-based sampling of airborne volatile organics continues to be a challenge because of the absence of laboratory supplies and facilities. Approaches are required to overcome poor data arising from difficulties with calibration of fielded instruments. This method normalises responses across portable thermal desorption gas-chromatography mass spectrometers and requires no advance calibration, enabling accurate and precise use of previously established response factors ported from the laboratory to fielded instruments.
Abstract. Sorbent capture provides a process for collecting airborne volatile organic compounds (VOCs) for analysis by thermal desorption gas chromatography-mass spectrometry (TD-GC-MS). Under typical laboratory conditions, analytical standards are readily available and calibration of instrumentation is a routine process. In contrast, field-portable instruments are standardised using a representative curve prepared on a limited number of instruments and then applied to fielded units. The performance of field-portable TD-GC-MS systems when deployed to multiple remote sites was studied, and a large variability in sensitivity and performance was observed when using the manufacturer-prescribed methods for calibration of instruments and normalisation of the data. This variability was remedied by the implementation of a non-interfering calibration that is pre-incorporated onto the sorbent media. Use of an in-situ calibration curve constructed using stable isotope labelled standards provided robust quantification, accuracy of measurement and diagnostic capabilities for malfunctioning fielded equipment. Pre-incorporation of isotopic analogues onto thermal desorption tubes in advance of field distribution greatly improves the accuracy and reproducibility of analyses and demonstrates, for the first time, definitive quantification of target analytes using field-portable GC-MS in an operational theatre.
References
Bridoux M, Malandain H, Leprince F, Progent F, Machuron-Mandard X (2015). Quantitative analysis of phosphoric acid esters in aqueous samples by isotope dilution stir-bar sorptive extraction combined with direct analysis in real time (DART)-Orbitrap mass spectrometry. Analytica Chimica Acta 869, 1–10.| Quantitative analysis of phosphoric acid esters in aqueous samples by isotope dilution stir-bar sorptive extraction combined with direct analysis in real time (DART)-Orbitrap mass spectrometryCrossref | GoogleScholarGoogle Scholar | 25818134PubMed |
Duhamel N, Slaghenaufi D, Pilkington LI, Herbst-Johnstone M, Larcher R, Barker D, Fedrizzi B (2018). Facile gas chromatography-tandem mass spectrometry stable isotope dilution method for the quantification of sesquiterpenes in grape. Journal of Chromatography A 1537, 91–98.
| Facile gas chromatography-tandem mass spectrometry stable isotope dilution method for the quantification of sesquiterpenes in grapeCrossref | GoogleScholarGoogle Scholar | 29352581PubMed |
Frank S, Hoffman T, Schieberle P (2019). Quantitation of benzene in flavourings and liquid foods containing added cherry-type flavour by a careful work-up procedure followed by a stable isotope dilution assay. European Food Research and Technology
| Quantitation of benzene in flavourings and liquid foods containing added cherry-type flavour by a careful work-up procedure followed by a stable isotope dilution assayCrossref | GoogleScholarGoogle Scholar |
Harshman SW, Dershem VL, Fan M, Watts BS, Slusher GM, Flory LE, Grigsby CC, Ott DK (2015). The stability of Tenax TA thermal desorption tubes in simulated field conditions on the HAPSITE ER. International Journal of Environmental Analytical Chemistry 95, 1014–1029.
| The stability of Tenax TA thermal desorption tubes in simulated field conditions on the HAPSITE ERCrossref | GoogleScholarGoogle Scholar |
Harshman SW, Rubenstein MH, Qualley AV, Fan M, Geier BA, Pitsch RL, Slusher GM, Hughes GT, Dershem VL, Grigsby CC, Ott DK, Martin JA (2017). Evaluation of thermal desorption analysis on a portable GC-MS system. International Journal of Environmental Analytical Chemistry 97, 247–263.
| Evaluation of thermal desorption analysis on a portable GC-MS systemCrossref | GoogleScholarGoogle Scholar |
Inficon (2006). HAPSITE application note – HAPSITE smart portable GCMS: calibration curves for 52 volatile organic compounds in water or soil (Inficon: East Syracuse, NY). Available at http://products.inficon.com/GetAttachment.axd?attaName=9f203c0b-f432-4ab0-bbbb-a3c594a8f0d3 [verified 22 August 2019]
Joint Environmental Surveillance Work Group (2009). Doctrinal definitions for detection, identification, and analysis (version 3.1, 11 August 2009). Available at https://armypubs.army.mil/epubs/DR_pubs/DR_a/pdf/web/ARN12082_ATP%203-37x11%20FINAL%20WEB.pdf [verified 22 August 2019]
Kwak J, Fan M, Geier BA, Grigsby CC, Ott DK (2014). Comparison of sampling probe and thermal desorber in HAPSITE ER for analysis of TO-15 compounds. Journal of Analytical & Bioanalytical Techniques S2, 008
| Comparison of sampling probe and thermal desorber in HAPSITE ER for analysis of TO-15 compoundsCrossref | GoogleScholarGoogle Scholar |
Liao W, Ghabour M, Draper WM, Chandrasena E (2016). Lowering detection limits for 1,2,3-trichloropropane in water using solid phase extraction coupled to purge and trap sample introduction in an isotope dilution GC-MS method. Chemosphere 158, 171–176.
| Lowering detection limits for 1,2,3-trichloropropane in water using solid phase extraction coupled to purge and trap sample introduction in an isotope dilution GC-MS methodCrossref | GoogleScholarGoogle Scholar | 27262687PubMed |
Martin J, Kwak J, Harshman SW, Chan K, Fan M, Geier BA, Grigsby CC, Ott DK (2016). Field sampling demonstration of portable thermal desorption collection and analysis instrumentation. International Journal of Environmental Analytical Chemistry 96, 299–319.
| Field sampling demonstration of portable thermal desorption collection and analysis instrumentationCrossref | GoogleScholarGoogle Scholar |
Rubenstein HM (2017). Focusing agents and methods of using same. Patent pending, application filed 7 March 2017 and accorded serial number 15/451,438.
Sekiguchi H, Matsushita K, Yamashiro S, Sano Y, Seto Y, Okuda T, Sato A (2006). On-site determination of nerve and mustard gases using a field-portable gas chromatograph-mass spectrometer. Forensic Toxicology 24, 17–22.
| On-site determination of nerve and mustard gases using a field-portable gas chromatograph-mass spectrometerCrossref | GoogleScholarGoogle Scholar |
Smith PA, Jackson Lepage CR, Koch D, Wyatt HDM, Hook GL, Betsinger G, Erickson RP, Eckenrode BA (2004). Detection of gas-phase chemical warfare agents using field-portable gas chromatography–mass spectrometry systems: instrument and sampling strategy considerations. Trends in Analytical Chemistry 23, 296–306.
| Detection of gas-phase chemical warfare agents using field-portable gas chromatography–mass spectrometry systems: instrument and sampling strategy considerationsCrossref | GoogleScholarGoogle Scholar |
US Environmental Protection Agency (1999). Compendium Method TO-17 Determination of Volatile Organic Compounds in Ambient Air Using Active Sampling onto Sorbent Tubes, EPA/625/R-96/101b. Available at www3.epa.gov/ttnamti1/files/ambient/airtox/to-17r.pdf [verified 17 February 2016]
