Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

31
Atmospheric Chemistry Measurements – Organics in Air ATMS 360

Transcript of Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Page 1: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Atmospheric Chemistry Measurements ndash Organics in Air

ATMS 360

Organic Chemistry - Carbon Compounds

bull Carbon - C atomic number 6 molecular weight 12

bull Electron configuration 1s22s22p2

bull Tetravalent covalent bonds ndash 4 single bonds (sp3) 2 double bonds (sp2) one triple (sp) plus one single bond

bull Other atoms hydrogen oxygen nitrogen sulfur halogens (Cl F Br)

Compounds

bull Alkanes ndash CnH2n+2 (CH4 C2H6 etc)

bull Alkenes ndash CnH2n (C2H4 etc)

bull Alkynes - CnH2n-2 (C2H2)

bull Aromatic compounds (C6H6 benzene)

bull Polycyclic aromatic hydrocarbons - PAH (naphthalene C10H8)

Models

Methane

Ethane

CH3 ndash CH3

Pentane

Ethylene (Etene)

CH3-CH2-CH2-CH2-CH3

Benzene

Ethanol

CH3CH2OH

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 2: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Organic Chemistry - Carbon Compounds

bull Carbon - C atomic number 6 molecular weight 12

bull Electron configuration 1s22s22p2

bull Tetravalent covalent bonds ndash 4 single bonds (sp3) 2 double bonds (sp2) one triple (sp) plus one single bond

bull Other atoms hydrogen oxygen nitrogen sulfur halogens (Cl F Br)

Compounds

bull Alkanes ndash CnH2n+2 (CH4 C2H6 etc)

bull Alkenes ndash CnH2n (C2H4 etc)

bull Alkynes - CnH2n-2 (C2H2)

bull Aromatic compounds (C6H6 benzene)

bull Polycyclic aromatic hydrocarbons - PAH (naphthalene C10H8)

Models

Methane

Ethane

CH3 ndash CH3

Pentane

Ethylene (Etene)

CH3-CH2-CH2-CH2-CH3

Benzene

Ethanol

CH3CH2OH

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 3: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Compounds

bull Alkanes ndash CnH2n+2 (CH4 C2H6 etc)

bull Alkenes ndash CnH2n (C2H4 etc)

bull Alkynes - CnH2n-2 (C2H2)

bull Aromatic compounds (C6H6 benzene)

bull Polycyclic aromatic hydrocarbons - PAH (naphthalene C10H8)

Models

Methane

Ethane

CH3 ndash CH3

Pentane

Ethylene (Etene)

CH3-CH2-CH2-CH2-CH3

Benzene

Ethanol

CH3CH2OH

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 4: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Models

Methane

Ethane

CH3 ndash CH3

Pentane

Ethylene (Etene)

CH3-CH2-CH2-CH2-CH3

Benzene

Ethanol

CH3CH2OH

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 5: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Pentane

Ethylene (Etene)

CH3-CH2-CH2-CH2-CH3

Benzene

Ethanol

CH3CH2OH

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 6: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Benzene

Ethanol

CH3CH2OH

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 7: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Sources of Organics in Air

bull Anthropogenicndash Incomplete combustion of fossil fuels ndash Biomass burningndash Industrial processesndash Cooking

bull Natural sourcesndash Biogenic emissions (from vegetation)ndash Volcanicndash Evaporation of sea spray

bull Atmospheric reaction products (from VOC SVOC) secondary organic aerosol (SOA)

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 8: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Fossil fuels

Complete combustion

CxHy + (x + y4)O2 xCO2 + y2H2O

eg C5H12 + 8O2 5CO2 + 6H2O

Incomplete CO soot organics and (in air) NOx

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 9: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Biomass Burning

Biomass cellulose hemi-cellulose lignin resins

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 10: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Other sources - testing

Residential wood Combustion

Meat cooking

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 11: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Secondary Organic Aerosol (SOA)bull SOA processes are studied

in photoreactors bull European photoreactor

(EUPHORE) in Valencia Spain is one of the largest (200 m3) and the best-equipped outdoor simulation chamber in the world

bull We are studying atmospheric transformation of diesel emissions under the influence of sunlight ozone hydroxyl radicals that occur during transport in ambient air

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 12: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC

SVOC PM)

Vapor pressure ranges

VOC gt 102 Pa (10-1 Torr)

SVOC 102 and 10-6 Pa (10-1 and 10-8 Torr)

PM lt 10-6 Pa (10-8 Torr)

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 13: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Organic Aerosol bull Organic aerosols are solid or liquid particles

suspended in the atmosphere containing organic carbon

bull Semi-volatile organic compounds (SVOC) - distributed between gas and particle phases ndashreversibly condensable

bull Particle associated organics ndash complex mixture incorporated intoonto particles includes condensed SVOC and non-volatile organic compounds

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 14: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)

bull Particulate Matter (PM)bull Ozonebull NOxbull SO2

bull CObull Lead (Pb)bull Ambient standards established by the US

EPA and reviewed every 5 years

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 15: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Why Particulate Matterbull Health effects particulate matter (fine PM25

and to lesser degree coarse PM10-25) has been associated with adverse health effects at low-to-moderate concentrations

bull NAAQS exist for PM (since 1971) ndash current (since 1997) PM25 annual 15 microgm3 and

24-hr 65 microgm3 PM10 annual 50 microgm3 and 24-hr 150 microgm3

_ announced in September 2006 PM25 annual 15 microgm3 and 24-hr 35 microgm3 PM10 annual only

bull Climate changebull Visibility problem (Haze Rule)

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 16: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Average Ambient PM25 Composition in Urban Areas

EPA STN network

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 17: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Average PM10-25 PM25 and PM01 composition at EPA ldquosupersiterdquo in Los Angeles CA 102001 to 92002

US EPA OAQPS PM Staff Paper June 2005

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 18: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Hazardous Air Pollutants (HAPs)

bull Full list ndash 188 compounds most of them organics

bull The short list ndash 33 air toxics most prevalent in urban area

bull No ambient standards ndash regulation of emissions from sources

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 19: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

VOC SVOC 1 acetaldehyde 20 polychlorinated biphenyls (PCBs) 2 formaldehyde 21 polycyclic organic matter (POM) 3 acrolein 22 hexachlorobenzene 4 acrylonitrile 23 quinoline 5 1 3-butadiene 6 benzene PM 7 carbon tetrachloride 24 diesel particulate matter 8 chloroform 25 coke oven emissions 9 methylene chloride 10 perchloroethylene Inorganic Compounds 11 1 1 2 2 -tetrachloroethane 26 mercury compounds 12 trichloroethylene 27 beryllium compounds 13 vinyl chloride 28 nickel compounds 14 hydrazine 29 cadmium compounds 15 propylene dichloride 30 lead compounds 16 1 3-dichloropropene 31 manganese compounds 17 ethylene dibromide 32 chromium compounds 18 ethylene dichloride 34 arsenic compound s 19 ethylene oxide

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 20: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Measurement Methods

bull Collection of VOC and aerosol samples followed by off-site laboratory analyses

bull VOC collection stainless steel SUMMA canisters Tedlar bags

bull PM and SVOC Filters followed by solid adsorbents Extraction with organic solvents in the laboratory

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 21: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Operational Definitions of SVOC and PM - Associated OC

Filter-Adsorbent (FA) AF

AFDDenuder-Filter-Adsorbent (DFA)

AEElectrostatic precipitator (EA)

Filter-Filter-Adsorbent (FFA)

F1F A

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 22: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Analysis - Chromatography

bull Chromatography is a separation method that relies on differences in partitioning behavior between a flowing mobile phase and a stationary phase to separate the components in a mixture

bull Gas-liquid chromatography (GC) ndashmobile phase is gas (He N2 H2)

bull Liquid chromatography (LC) ndash mobile phase is liquid High performance liquid chromatography (HPLC) utilizes high-pressure pumps to increase the efficiency of the separation

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 23: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Gas Chromatography (GC)

Columns bullPacked columns 1-10 m long 2-4 mm ID (filled with solid support material coated with liquid or solid stationary phase)

bullCapillary columns 10 ndash 60 m long lt1 mm ID (the inner column walls are coated with stationary phase)

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 24: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Detectors for GC and HPLCbull Gas Chromatography detectors

ndash Flame Ionization (FID)- hydrocarbonsndash Thermal Conductivity (TCD) - universalndash Electron Capture (ECD) ndash halogenated organicsndash Photoionization (PID) - aromatics olefinsndash Fourier Transform Infrared (GC-FTIR) ndash all organicsndash Mass Spectrometer (GC-MS) ndash any species

bull HPLC Detectorsndash UV-VIS absorption spectroscopyndash Photo diode-array UV-VISndash Fluorescencendash MS (LC-MS)

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 25: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Sample Inlet

Ion SourceMass

AnalyzerDetector

Data Analysis

Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components

Mass Spectrometer

High vacuum

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 26: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Ion Sourcebull Ionization methods Electron Impact (EI) Chemical

Ionization (CI) Field Ionization (FI) Field Desorption (FD) Fast Atom Bombardment (FAB) Matrix-Assisted Laser Desorption Ionization (MALDI) Electrospray Ionization (ESI) and others

bull EI (unimolecular) bombarding neutral analyte M with high energy (70 eV) electron beam

M + e- M+ + 2e-

bull CI (bimolecular) M interacts with ions from reagent gasM + [BH]+ [M+H]+ + B (proton transfer)M + X+ [M+X]+ (electrophilic addition)M + X+ M+ + X (charge exchange)M + X + [M-A]+ + AX (anion abstraction)

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 27: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Principle of mass analysisWhen the ion beam

experiences a strong magnetic field perpendicular to its direction of motion the ions are deflected in an arc whose radius is inversely proportional to the mass of the ion (mass-to-charge ratios mz) Lighter ions are deflected more than heavier ions By varying the strength of the magnetic field ions of different mass (mz) can be focused progressively on a detector fixed at the end of a curved tube

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 28: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Mass Analyzersbull Types of mass analyzers

ndash magnetic sector (deflection of ion beam separation by momentum)

ndash linear quadrupole (4 rod electrodes the pair of opposite rods are each held at the same potential composed of DC and AC component a mass spectrum is obtained by monitoring the ions passing through the quadrupole filter as the voltages on the rods are varied)

ndash quadrupole ion trap (three-dimensional RF quadrupole field to store ions within defined boundaries)

ndash time-of-flight (TOF uses the differences in transit time through a drift region to separate ions of different masses )

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 29: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Advances in Mass Spectrometrybull Aerosol -MS is the measurement in real-time of

the aerosol composition using a mass spectrometer Almost always the particle size is measured simultaneously with the composition Two approachesndash Single particle MS ndashLaser desorption-ionization MS

Example Aerosol Time of Flight MS (ATOFMS available commercially from TSI Inc)

ndash Thermal desorption aerosol MS Example Aerodyne Aerosol MS available commercially (httpcirescoloradoedu~jjoseamshtmlInfo_AerosolMS)

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 30: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Inlet (1 atm)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

QuadrupoleMass Spectrometer

Thermal Vaporization

ampElectron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation

Aerodynamic Sizing Particle Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31
Page 31: Atmospheric Chemistry Measurements – Organics in Air ATMS 360.

Aerodyne Aerosol Mass Spectrometer (AMS)

100 transmission (60-600 nm) aerodynamic sizing linear mass signalJayne et al Aerosol Science and Technology 331-2(49-70) 2000Jimenez et al Journal of Geophysical Research 108(D7) 8425 doi101029 2001JD001213 2003

  • Atmospheric Chemistry Measurements ndash Organics in Air
  • Organic Chemistry - Carbon Compounds
  • Compounds
  • Models
  • PowerPoint Presentation
  • Slide 6
  • Sources of Organics in Air
  • Fossil fuels
  • Biomass Burning
  • Other sources - testing
  • Secondary Organic Aerosol (SOA)
  • Volatile Semi-Volatile and Particulate Matter Organic Compounds (VOC SVOC PM)
  • Organic Aerosol
  • Criteria Pollutants ndash National Ambient Air Quality Standards (NAAQS)
  • Why Particulate Matter
  • Slide 16
  • Slide 17
  • Hazardous Air Pollutants (HAPs)
  • Slide 19
  • Measurement Methods
  • Slide 21
  • Analysis - Chromatography
  • Gas Chromatography (GC)
  • Detectors for GC and HPLC
  • Mass Spectrometry measures the mass-to-charge ratio (mz) of charged particles to find the composition of a sample by generating a mass spectrum representing the masses of sample components
  • Ion Source
  • Principle of mass analysis
  • Mass Analyzers
  • Advances in Mass Spectrometry
  • Aerodyne Aerosol Mass Spectrometer (AMS)
  • Slide 31

Pat Arnott, ATMS 749 Atmospheric Radiation Transfer Chapter 2: Electromagnetic Theory, Refractive Index, and Definitions of Radiance, Irradiance. Gauss’

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ATMS StyleGuide

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Fourier Transform Infrared (FTIR) Spectrometer Subhashree Mishra ATMS Grad Student, UNR W. P. Arnott Physics, UNR Introduction to Atmospheric Instrumentation.

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Climate (Atms 4600) Professor Anthony R. Lupo Department of Soil, Environmental, and Atmospheric Science University of Missouri Columbia, MO.

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Cardless ATMs - European ATMs 2015 conference in London

Cardless ATMs - European ATMs 2015 conference in London

Connecting ATMS to AMSU Time Series for Long …...Connecting ATMS to AMSU Time Series for Long-Term Monitoring of Climate Change Department of Earth, Ocean and Atmospheric Science

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ORGANICS MANAGEMENT - NERC Organics Mgm… ·  · 2014-07-31through solid waste management . ... Vermicomposting ... Organics management ...

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Atms (Sdbot)

Atms (Sdbot)

California ATMS Testbed

California ATMS Testbed

Pinellas Countywide ATMS Requirements Document · PDF filePinellas Countywide ATMS Requirements Document Prepared for: Pinellas County Metropolitan Planning Organization ... ATMS Functional

Pinellas Countywide ATMS Requirements Document · PDF filePinellas Countywide ATMS Requirements Document Prepared for: Pinellas County Metropolitan Planning Organization ... ATMS Functional

ATMS 749 Atmospheric Radiation Transfer

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Trace organics in sediments inTrace organics in …...Trace organics in sediments inTrace organics in sediments in the lower stretch of Ganges estdthituary and their ecotoxicological

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Integrated MRF and Organics Recycling · 3. Integrated MRF and Organics Recycling Solutions 4. Organics Recycling Recovery – Key Technologies a) Organics Extrusion Press (OREX)

Integrated MRF and Organics Recycling · 3. Integrated MRF and Organics Recycling Solutions 4. Organics Recycling Recovery – Key Technologies a) Organics Extrusion Press (OREX)

External Users Manual - National Oceanic and Atmospheric ...External Users Manual . for NPP ATMS . Compiled by . NOAA Center for Satellite Applications and Research (STAR) NOAA Office

External Users Manual - National Oceanic and Atmospheric ...External Users Manual . for NPP ATMS . Compiled by . NOAA Center for Satellite Applications and Research (STAR) NOAA Office

Pat Arnott, ATMS 749 Atmospheric Radiation Transfer Chapter 12: Scattering and Absorption by Particles Summary of Scattering Regimes: Note Particle Sizes.

Pat Arnott, ATMS 749 Atmospheric Radiation Transfer Chapter 12: Scattering and Absorption by Particles Summary of Scattering Regimes: Note Particle Sizes.

CONT ATMS 2011

CONT ATMS 2011

Cash Machines (ATMs)

Cash Machines (ATMs)

ATMS User Guide - the ICE · ATMS User Guide v1.5 – 26-Mar-2013 4 1 Overview ICE’s Authorized Trader Management System (ATMS) is provided …

ATMS User Guide - the ICE · ATMS User Guide v1.5 – 26-Mar-2013 4 1 Overview ICE’s Authorized Trader Management System (ATMS) is provided …

Seasonal weather forecasting: - the motivations - the capabilities - the atmospheric physics involved J.D. McAlpine ATMS 611, autumn 2010 Class project.

Seasonal weather forecasting: - the motivations - the capabilities - the atmospheric physics involved J.D. McAlpine ATMS 611, autumn 2010 Class project.

ATMS Arterial

ATMS Arterial