Feasibility study of superoxide chemical ionization mass spectrometry (O2− CIMS) for real-time gas-phase measurements of per- and polyfluoroalkyl substances (PFAS)

Yufan Hu; Joji W. Sherman; Michael J. Davern; Zane A. Alsebai; Yoonsub Kim; Yue Zhang; Chenyang Bi; Barbara J. Turpin; Jason D. Surratt

doi:10.1039/d5an01352f

Feasibility study of superoxide chemical ionization mass spectrometry (O₂− CIMS) for real-time gas-phase measurements of per- and polyfluoroalkyl substances (PFAS)

Yufan Hu
, Joji W. Sherman
, Michael J. Davern
, Zane A. Alsebai
, Yoonsub Kim
, Yue Zhang
, Chenyang Bi
, Barbara J. Turpin
, Jason D. Surratt

University of North Carolina at Chapel Hill
Department of Environmental Sciences and Engineering
Texas A&M University
Aerodyne Research, Inc.

Research output: Contribution to journal › Article › peer-review

Abstract

Per- and polyfluoroalkyl substances (PFAS) are highly persistent pollutants with known adverse impacts on environmental and public health. Traditional gas-phase PFAS detection approaches often involve labor-intensive sample collection and preparation, while offering low temporal resolution. Alternatively, chemical ionization mass spectrometry (CIMS) allows for real-time airborne PFAS detection at sub-pptv sensitivity. While reagent ion generation often requires hazardous chemicals (e.g., nitric acid, methyl iodide (I⁻), and acetic anhydride), superoxide (O₂⁻) CIMS provides a safer alternative and is better suited for mobile platforms where ventilation, space, and weight are constrained. O₂⁻ CIMS has five main reagent ions (i.e., O₂⁻, (H₂O)O₂⁻, CO₃⁻, (CO₂)O₂⁻, and CO₂(H₂O)O₂⁻) and low-background mass spectra above m/z 200. Thus, it is well suited to the relatively high molecular weights of airborne PFAS. Mass calibration was performed with a 5 : 1 fluorotelomer alcohol (FTOH) permeation tube. Ionization was found to occur mainly through deprotonation or adduct formation. Calibrations for fourteen environmentally- and industrially-relevant PFAS compounds are presented, including FTOHs, fluorotelomer diols, fluorinated sulfonamides, epoxides, and glycol ethers. While perfluoroalkyl carboxylic acids (PFCAs) were not detected, O₂⁻ CIMS offered higher sensitivity and lower detection/quantification limits than I⁻ CIMS for FTOHs; however, it remains a complementary PFAS measurement technique to I⁻ CIMS. Moreover, it yielded distinct fingerprint signals for FTOHs, confirming compound identification. This study demonstrates the utility of O₂⁻ CIMS for real-time airborne PFAS analysis in commonly encountered environments by capturing 6 : 2 FTOH gaseous emissions from fast-food packaging at room temperature, underscoring its strong promise for future development and applications.

Original language	English
Pages (from-to)	3418-3429
Number of pages	12
Journal	Analyst
Volume	151
Issue number	12
DOIs	https://doi.org/10.1039/d5an01352f
State	Published - Jun 15 2026
Externally published	Yes

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title = "Feasibility study of superoxide chemical ionization mass spectrometry (O2− CIMS) for real-time gas-phase measurements of per- and polyfluoroalkyl substances (PFAS)",

abstract = "Per- and polyfluoroalkyl substances (PFAS) are highly persistent pollutants with known adverse impacts on environmental and public health. Traditional gas-phase PFAS detection approaches often involve labor-intensive sample collection and preparation, while offering low temporal resolution. Alternatively, chemical ionization mass spectrometry (CIMS) allows for real-time airborne PFAS detection at sub-pptv sensitivity. While reagent ion generation often requires hazardous chemicals (e.g., nitric acid, methyl iodide (I−), and acetic anhydride), superoxide (O2−) CIMS provides a safer alternative and is better suited for mobile platforms where ventilation, space, and weight are constrained. O2− CIMS has five main reagent ions (i.e., O2−, (H2O)O2−, CO3−, (CO2)O2−, and CO2(H2O)O2−) and low-background mass spectra above m/z 200. Thus, it is well suited to the relatively high molecular weights of airborne PFAS. Mass calibration was performed with a 5 : 1 fluorotelomer alcohol (FTOH) permeation tube. Ionization was found to occur mainly through deprotonation or adduct formation. Calibrations for fourteen environmentally- and industrially-relevant PFAS compounds are presented, including FTOHs, fluorotelomer diols, fluorinated sulfonamides, epoxides, and glycol ethers. While perfluoroalkyl carboxylic acids (PFCAs) were not detected, O2− CIMS offered higher sensitivity and lower detection/quantification limits than I− CIMS for FTOHs; however, it remains a complementary PFAS measurement technique to I− CIMS. Moreover, it yielded distinct fingerprint signals for FTOHs, confirming compound identification. This study demonstrates the utility of O2− CIMS for real-time airborne PFAS analysis in commonly encountered environments by capturing 6 : 2 FTOH gaseous emissions from fast-food packaging at room temperature, underscoring its strong promise for future development and applications.",

author = "Yufan Hu and Sherman, \{Joji W.\} and Davern, \{Michael J.\} and Alsebai, \{Zane A.\} and Yoonsub Kim and Yue Zhang and Chenyang Bi and Turpin, \{Barbara J.\} and Surratt, \{Jason D.\}",

note = "Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry, 2026.",

year = "2026",

month = jun,

day = "15",

doi = "10.1039/d5an01352f",

language = "English",

volume = "151",

pages = "3418--3429",

journal = "Analyst",

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publisher = "Royal Society of Chemistry",

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T1 - Feasibility study of superoxide chemical ionization mass spectrometry (O2− CIMS) for real-time gas-phase measurements of per- and polyfluoroalkyl substances (PFAS)

AU - Hu, Yufan

AU - Sherman, Joji W.

AU - Davern, Michael J.

AU - Alsebai, Zane A.

AU - Kim, Yoonsub

AU - Zhang, Yue

AU - Bi, Chenyang

AU - Turpin, Barbara J.

AU - Surratt, Jason D.

PY - 2026/6/15

Y1 - 2026/6/15

N2 - Per- and polyfluoroalkyl substances (PFAS) are highly persistent pollutants with known adverse impacts on environmental and public health. Traditional gas-phase PFAS detection approaches often involve labor-intensive sample collection and preparation, while offering low temporal resolution. Alternatively, chemical ionization mass spectrometry (CIMS) allows for real-time airborne PFAS detection at sub-pptv sensitivity. While reagent ion generation often requires hazardous chemicals (e.g., nitric acid, methyl iodide (I−), and acetic anhydride), superoxide (O2−) CIMS provides a safer alternative and is better suited for mobile platforms where ventilation, space, and weight are constrained. O2− CIMS has five main reagent ions (i.e., O2−, (H2O)O2−, CO3−, (CO2)O2−, and CO2(H2O)O2−) and low-background mass spectra above m/z 200. Thus, it is well suited to the relatively high molecular weights of airborne PFAS. Mass calibration was performed with a 5 : 1 fluorotelomer alcohol (FTOH) permeation tube. Ionization was found to occur mainly through deprotonation or adduct formation. Calibrations for fourteen environmentally- and industrially-relevant PFAS compounds are presented, including FTOHs, fluorotelomer diols, fluorinated sulfonamides, epoxides, and glycol ethers. While perfluoroalkyl carboxylic acids (PFCAs) were not detected, O2− CIMS offered higher sensitivity and lower detection/quantification limits than I− CIMS for FTOHs; however, it remains a complementary PFAS measurement technique to I− CIMS. Moreover, it yielded distinct fingerprint signals for FTOHs, confirming compound identification. This study demonstrates the utility of O2− CIMS for real-time airborne PFAS analysis in commonly encountered environments by capturing 6 : 2 FTOH gaseous emissions from fast-food packaging at room temperature, underscoring its strong promise for future development and applications.

AB - Per- and polyfluoroalkyl substances (PFAS) are highly persistent pollutants with known adverse impacts on environmental and public health. Traditional gas-phase PFAS detection approaches often involve labor-intensive sample collection and preparation, while offering low temporal resolution. Alternatively, chemical ionization mass spectrometry (CIMS) allows for real-time airborne PFAS detection at sub-pptv sensitivity. While reagent ion generation often requires hazardous chemicals (e.g., nitric acid, methyl iodide (I−), and acetic anhydride), superoxide (O2−) CIMS provides a safer alternative and is better suited for mobile platforms where ventilation, space, and weight are constrained. O2− CIMS has five main reagent ions (i.e., O2−, (H2O)O2−, CO3−, (CO2)O2−, and CO2(H2O)O2−) and low-background mass spectra above m/z 200. Thus, it is well suited to the relatively high molecular weights of airborne PFAS. Mass calibration was performed with a 5 : 1 fluorotelomer alcohol (FTOH) permeation tube. Ionization was found to occur mainly through deprotonation or adduct formation. Calibrations for fourteen environmentally- and industrially-relevant PFAS compounds are presented, including FTOHs, fluorotelomer diols, fluorinated sulfonamides, epoxides, and glycol ethers. While perfluoroalkyl carboxylic acids (PFCAs) were not detected, O2− CIMS offered higher sensitivity and lower detection/quantification limits than I− CIMS for FTOHs; however, it remains a complementary PFAS measurement technique to I− CIMS. Moreover, it yielded distinct fingerprint signals for FTOHs, confirming compound identification. This study demonstrates the utility of O2− CIMS for real-time airborne PFAS analysis in commonly encountered environments by capturing 6 : 2 FTOH gaseous emissions from fast-food packaging at room temperature, underscoring its strong promise for future development and applications.

UR - https://www.scopus.com/pages/publications/105038620133

U2 - 10.1039/d5an01352f

DO - 10.1039/d5an01352f

M3 - Article

C2 - 42132747

AN - SCOPUS:105038620133

SN - 0003-2654

VL - 151

SP - 3418

EP - 3429

JO - Analyst

JF - Analyst

IS - 12

ER -

Feasibility study of superoxide chemical ionization mass spectrometry (O₂− CIMS) for real-time gas-phase measurements of per- and polyfluoroalkyl substances (PFAS)

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