Atmospheric Chemistry

Measurements – Organics in Air

ATMS 360
 Organic Chemistry - Carbon
Compounds
• Carbon - C, atomic number 6, molecular
weight 12
• Electron configuration: 1s22s22p2
• Tetravalent, covalent bonds – 4 single
bonds (sp3); 2 double bonds (sp2) one
triple (sp) plus one single bond
• Other atoms: hydrogen, oxygen, nitrogen,
sulfur, halogens (Cl, F, Br)
 Compounds
• Alkanes – CnH2n+2 (CH4, C2H6, etc)
• Alkenes – CnH2n (C2H4, etc)
• Alkynes - CnH2n-2 (C2H2)
• Aromatic compounds (C6H6, benzene)
• Polycyclic aromatic hydrocarbons - PAH
(naphthalene, C10H8)
 Models
CH3 – CH3

Ethane

Methane
 Ethylene (Etene)

Pentane

CH3-CH2-CH2-CH2-CH3
 CH3CH2OH

Ethanol

Benzene
 Sources of Organics in Air
• Anthropogenic:
– Incomplete combustion of fossil fuels
– Biomass burning
– Industrial processes
– Cooking
• Natural sources
– Biogenic emissions (from vegetation)
– Volcanic
– Evaporation of sea spray
• Atmospheric reaction products (from VOC,
SVOC), secondary organic aerosol (SOA)
Fossil fuels

Complete combustion:
CxHy + (x + y/4)O2 xCO2 + y/2H2O
e.g. 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)
• SOA processes are studied
in photoreactors
• European photoreactor
(EUPHORE) in Valencia,
Spain, is one of the largest
(200 m3) and the best-
equipped outdoor simulation
chamber in the world
• 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: > 102 Pa (10-1 Torr)

SVOC: 102 and 10-6 Pa; (10-1 and

10-8 Torr)

PM: < 10-6 Pa (10-8 Torr)

 Organic Aerosol
• Organic aerosols are solid or liquid particles
suspended in the atmosphere containing
organic carbon
• Semi-volatile organic compounds (SVOC) -
distributed between gas and particle phases –
reversibly condensable
• Particle associated organics – complex
mixture, incorporated into/onto particles;
includes condensed SVOC and non-volatile
organic compounds
 Criteria Pollutants – National Ambient
Air Quality Standards (NAAQS)
• Particulate Matter (PM)
• Ozone
• NOx
• SO2
• CO
• Lead (Pb)
• Ambient standards established by the US
EPA and reviewed every 5 years
 Why Particulate Matter?
• Health effects: particulate matter (fine, PM2.5
and to lesser degree, coarse PM10-2.5) has
been associated with adverse health effects at
low-to-moderate concentrations
• NAAQS exist for PM (since 1971):
– current (since 1997): PM2.5 annual 15 µg/m3 and
24-hr 65 µg/m3; PM10 annual 50 µg/m3 and 24-hr
150 µg/m3
_ announced in September 2006: PM2.5 annual 15

µg/m3 and 24-hr 35 µg/m3; PM10 annual only

• Climate change
• Visibility problem (Haze Rule)
Average Ambient PM2.5 Composition in Urban Areas

EPA STN network

Average PM10-2.5,
PM2.5, and PM0.1
composition at EPA
“supersite” in Los
Angeles, CA,
10/2001 to 9/2002

US EPA OAQPS PM Staff

Paper, June 2005
 Hazardous Air Pollutants (HAPs)
• Full list – 188 compounds, most of them
organics
• The short list – 33 air toxics, most
prevalent in urban area
• No ambient standards – regulation of
emissions from sources
VOC
1. acetaldehyde
2. formaldehyde
3. acrolein
4. acrylonitrile
5. 1, 3-butadiene
6. benzene
7. carbon tetrachloride
8. chloroform
9. methylene chloride
10. perchloroethylene
11. 1, 1, 2, 2-tetrachloroethane
12. trichloroethylene
13. vinyl chloride
14. hydrazine
15. propylene dichloride
16. 1, 3-dichloropropene
17. ethylene dibromide
18. ethylene dichloride
19. ethylene oxide
SVOC
20. polychlorinated biphenyls (PCBs)
21. polycyclic organic matter (POM)
22. hexachlorobenzene
23. quinoline
PM
24. diesel particulate matter
25. coke oven emissions
Inorganic Compounds
26. mercury compounds
27. beryllium compounds
28. nickel compounds
29. cadmium compounds
30. lead compounds
31. manganese compounds
32. chromium compounds
34. arsenic compounds
 Measurement Methods
• Collection of VOC and aerosol
samples followed by off-site
laboratory analyses
• VOC collection: stainless steel
SUMMA canisters, Tedlar bags
• 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) F A

Filter-Filter- F F1 A
Adsorbent (FFA)

Denuder-Filter- D F A
Adsorbent (DFA)

Electrostatic precipitator
E A
(EA)
 Analysis - Chromatography
• 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
• Gas-liquid chromatography (GC) –mobile phase
is gas (He, N2, H2)
• Liquid chromatography (LC) – mobile phase is
liquid. High performance liquid
chromatography (HPLC) utilizes high-pressure
pumps to increase the efficiency of the
separation.
Gas Chromatography (GC)

Columns:
•Packed columns, 1-10 m long, 2-4 mm ID (filled with
solid support material coated with liquid or solid
stationary phase)
•Capillary columns, 10 – 60 m long, <1 mm ID (the
inner column walls are coated with stationary phase)
 Detectors for GC and HPLC
• Gas Chromatography detectors:
– Flame Ionization (FID)- hydrocarbons
– Thermal Conductivity (TCD) - universal
– Electron Capture (ECD) – halogenated organics
– Photoionization (PID) - aromatics, olefins
– Fourier Transform Infrared (GC-FTIR) – all organics
– Mass Spectrometer (GC-MS) – any species
• HPLC Detectors:
– UV-VIS absorption spectroscopy
– Photo diode-array UV-VIS
– Fluorescence
– MS (LC-MS)
Mass Spectrometry measures the mass-to-charge ratio
(m/z) of charged particles to find the composition of a
sample by generating a mass spectrum representing the
masses of sample components.
Mass Spectrometer:

Sample Inlet

High vacuum

Mass Detector
Ion Source
Analyzer

Data
Analysis
 Ion Source
• 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..

• EI (unimolecular): bombarding neutral analyte M with high

energy (70 eV) electron beam
M + e- M+· + 2e-

• CI (bimolecular): M interacts with ions from reagent gas

M + [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 analysis
When 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 m/z). Lighter ions are
deflected more than
heavier ions. By varying the
strength of the magnetic
field, ions of different mass
(m/z) can be focused
progressively on a detector
fixed at the end of a curved
tube
 Mass Analyzers
• Types of mass analyzers:
– magnetic sector (deflection of ion beam, separation
by momentum);
– 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);
– quadrupole ion trap (three-dimensional RF
quadrupole field to store ions within defined
boundaries);
– time-of-flight (TOF, uses the differences in transit
time through a drift region to separate ions of different
masses ).
Advances in Mass Spectrometry
• "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 approaches:
– Single particle MS –Laser desorption-ionization MS.
Example: Aerosol Time of Flight MS (ATOFMS,
available commercially from TSI, Inc.)
– Thermal desorption aerosol MS. Example Aerodyne
Aerosol MS, available commercially
(http://cires.colorado.edu/~jjose/ams.html#Info_AerosolMS).
 Aerodyne Aerosol Mass Spectrometer (AMS)

Particle Beam Aerodynamic Sizing Particle

Generation Composition
Quadrupole
Mass Spectrometer

Chopper

TOF Thermal
Region Vaporization
&
Aerodynamic Electron
Lens Impact
(2 Torr) Ionization
Particle Inlet (1 atm) Turbo Turbo Turbo
Pump Pump Pump

100% transmission (60-600 nm), aerodynamic sizing, linear mass signal.

Jayne et al., Aerosol Science and Technology 33:1-2(49-70), 2000.
Jimenez et al., Journal of Geophysical Research, 108(D7), 8425, doi:10.1029 / 2001JD001213, 2003.
 Aerodyne Aerosol Mass Spectrometer (AMS)

100% transmission (60-600 nm), aerodynamic sizing, linear mass signal.

Jayne et al., Aerosol Science and Technology 33:1-2(49-70), 2000.
Jimenez et al., Journal of Geophysical Research, 108(D7), 8425, doi:10.1029 / 2001JD001213, 2003.