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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 Spectrometr...
Real-Time Air Measurements of Halogenated Organics by Chemical Ionization Mass Spectrometry: PFAS, Chloramines, and Nitryl Chloride

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자료유형  
 학위논문 서양
최종처리일시  
20260202105102
ISBN  
9798291555491
DDC  
543
저자명  
Davern, Michael John.
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  
Chemical Ionization Mass Spectrometry
키워드  
Chloramine
키워드  
Forever chemical
키워드  
Per- and polyfluoroalkyl substances
키워드  
Real-time
기타저자  
The University of North Carolina at Chapel Hill Chemistry
기본자료저록  
Dissertations Abstracts International. 87-02B.
전자적 위치 및 접속  
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■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.

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