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Real-Time Air Measurements of Halogenated Organics by Chemical Ionization Mass Spectrometry: PFAS, Chloramines, and Nitryl Chloride
Real-Time Air Measurements of Halogenated Organics by Chemical Ionization Mass Spectrometry: PFAS, Chloramines, and Nitryl Chloride
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202105102
- ISBN
- 9798291555491
- DDC
- 543
- 서명/저자
- Real-Time Air Measurements of Halogenated Organics by Chemical Ionization Mass Spectrometry: PFAS, Chloramines, and Nitryl Chloride
- 발행사항
- [Sl] : The University of North Carolina at Chapel Hill, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 161 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-02, Section: B.
- 주기사항
- Advisor: Surratt, Jason D.
- 학위논문주기
- Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2025.
- 초록/해제
- 요약Iodide Chemical Ionization Mass Spectrometry (I-CIMS) is a demonstrated analytical tool for real-time gas-phase analysis. In recent years, it has been demonstrated to be sensitive to select classes of per- and polyfluoroalkyl substances (PFAS), which are widespread anthropogenic pollutants with a myriad of associated adverse health effects. Additionally, many of the sources of PFAS remain unknown, due in large part to a lack of real-time analytical methods. Though I-CIMS is known to detect selected classes of PFAS, there is no widely accepted calibration method, and the factors which can influence quantification are unknown. This dissertation involves the development of a novel calibration apparatus for manual injection of liquid standards (CAMILS) to enable real-time measurements of airborne PFAS using ICIMS. The CAMILS method is shown to have excellent linearity (R20.999) and provide sensitivities that align well with previously reports. Calibrations are then applied to make measurements of PFAS released from various consumer goods, including microwave popcorn and rain jackets. An occupational inhalation exposure assessment for floor wax workers is presented as well, with careful consideration of biotransformation products of inhaled PFAS and several modeled scenarios are presented to mimic expected exposure from floor waxing in other settings, such as schools. Lastly, I-CIMS is deployed in a 5-week field campaign to make ambient air measurements in Fayetteville, North Carolina. Though I-CIMS did not detect any PFAS during the campaign, nitryl chloride, dichloramine, and trichloramine were detected, each of which are photochemical precursors to chlorine atom, a powerful atmospheric oxidant. Significant spatiotemporal trends in these three compounds are reported as well, with detection occurring only at nighttime in the absence of photolysis reactions. Nitryl chloride concentrations are shown to be heavily influenced by regional road brining, whereas chloramine perturbations are likely a result of water treatment processes at a fluoropolymer manufacturing plant. These measurements advance our knowledge of the widely understudied inland sources of tropospheric chlorine atom precursors. This dissertation represents an important advance in the ability to make I-CIMS measurements of PFAS, identifying indoor sources of PFAS, and exploring the unique spatiotemporal dependencies of photochemical precursors to atmospheric chlorine.
- 일반주제명
- Analytical chemistry
- 일반주제명
- Geophysics
- 일반주제명
- Atmospheric chemistry
- 일반주제명
- Environmental science
- 키워드
- Airborne
- 키워드
- Chloramine
- 키워드
- Forever chemical
- 키워드
- Real-time
- 기타저자
- The University of North Carolina at Chapel Hill Chemistry
- 기본자료저록
- Dissertations Abstracts International. 87-02B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■020 ▼a9798291555491
■035 ▼a(MiAaPQ)AAI32236144
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a543
■1001 ▼aDavern, Michael John.
■24510▼aReal-Time Air Measurements of Halogenated Organics by Chemical Ionization Mass Spectrometry: PFAS, Chloramines, and Nitryl Chloride
■260 ▼a[Sl]▼bThe University of North Carolina at Chapel Hill▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a161 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-02, Section: B.
■500 ▼aAdvisor: Surratt, Jason D.
■5021 ▼aThesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2025.
■520 ▼aIodide Chemical Ionization Mass Spectrometry (I-CIMS) is a demonstrated analytical tool for real-time gas-phase analysis. In recent years, it has been demonstrated to be sensitive to select classes of per- and polyfluoroalkyl substances (PFAS), which are widespread anthropogenic pollutants with a myriad of associated adverse health effects. Additionally, many of the sources of PFAS remain unknown, due in large part to a lack of real-time analytical methods. Though I-CIMS is known to detect selected classes of PFAS, there is no widely accepted calibration method, and the factors which can influence quantification are unknown. This dissertation involves the development of a novel calibration apparatus for manual injection of liquid standards (CAMILS) to enable real-time measurements of airborne PFAS using ICIMS. The CAMILS method is shown to have excellent linearity (R20.999) and provide sensitivities that align well with previously reports. Calibrations are then applied to make measurements of PFAS released from various consumer goods, including microwave popcorn and rain jackets. An occupational inhalation exposure assessment for floor wax workers is presented as well, with careful consideration of biotransformation products of inhaled PFAS and several modeled scenarios are presented to mimic expected exposure from floor waxing in other settings, such as schools. Lastly, I-CIMS is deployed in a 5-week field campaign to make ambient air measurements in Fayetteville, North Carolina. Though I-CIMS did not detect any PFAS during the campaign, nitryl chloride, dichloramine, and trichloramine were detected, each of which are photochemical precursors to chlorine atom, a powerful atmospheric oxidant. Significant spatiotemporal trends in these three compounds are reported as well, with detection occurring only at nighttime in the absence of photolysis reactions. Nitryl chloride concentrations are shown to be heavily influenced by regional road brining, whereas chloramine perturbations are likely a result of water treatment processes at a fluoropolymer manufacturing plant. These measurements advance our knowledge of the widely understudied inland sources of tropospheric chlorine atom precursors. This dissertation represents an important advance in the ability to make I-CIMS measurements of PFAS, identifying indoor sources of PFAS, and exploring the unique spatiotemporal dependencies of photochemical precursors to atmospheric chlorine.
■590 ▼aSchool code: 0153.
■650 4▼aAnalytical chemistry
■650 4▼aGeophysics
■650 4▼aAtmospheric chemistry
■650 4▼aEnvironmental science
■653 ▼aAirborne
■653 ▼aChemical Ionization Mass Spectrometry
■653 ▼aChloramine
■653 ▼aForever chemical
■653 ▼aPer- and polyfluoroalkyl substances
■653 ▼aReal-time
■690 ▼a0486
■690 ▼a0768
■690 ▼a0371
■690 ▼a0373
■71020▼aThe University of North Carolina at Chapel Hill▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g87-02B.
■790 ▼a0153
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17359327▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.


