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Organic Chemistry - Carbon Compounds. Carbon - C, atomic number 6, molecular weight 12 Electron configuration: 1s 2 2s 2 2p 2 Tetravalent – 4 single bonds (sp 3 ); 2 double bonds (sp 2 ) one triple (sp) plus one single bond Other atoms: hydrogen, oxygen, nitrogen, sulfur, halogens (Cl, F, Br).

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organic chemistry carbon compounds
Organic Chemistry - Carbon Compounds
  • Carbon - C, atomic number 6, molecular weight 12
  • Electron configuration: 1s22s22p2
  • Tetravalent – 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
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
Models

Ethane

Methane

slide5

Ethanol

Benzene

sources of organics in air
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)
secondary organic aerosol soa
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
voc svoc and pm
VOC, SVOC and 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)

hazardous air pollutants haps
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
criteria pollutants national ambient air quality standards naaqs
Criteria Pollutants – National Ambient Air Quality Standards (NAAQS)
  • Particulate Matter (PM)
  • Ozone
  • NOx
  • SO2
  • CO
  • Lead (Pb)
why particulate matter
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)
slide17

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

organic aerosol
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
measurement methods
Measurement Methods
  • Collection of VOC and aerosol samples followed by off-site laboratory analyses
  • VOC collection: stainless steel SUMMA canisters
  • PM and SVOC: Filters followed by solid adsorbents
slide20

Filter-Adsorbent (FA)

F

A

Filter-Filter-Adsorbent (FFA)

F1

F

A

D

E

Denuder-Filter-Adsorbent (DFA)

F

A

A

Electrostatic precipitator (EA)

Operational Definitions of SVOC and PM - Associated OC

analysis chromatography
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.
slide23
Examples of "hyphenated techniques" include gas and liquid chromatography with mass spectrometry (GC-MS and LC-MS), Fourier-transform infrared spectroscopy (GC-FTIR), and photo diode-array UV-VIS absorption spectroscopy (HPLC-UV-VIS).

HPLC - liquid chromatography that utilizes high-pressure pumps to increase the efficiency of the separation