1. A. Laskin, J. Laskin, Y. Desyaterik
Microscopy and Chemical/Molecular Characterization of Particulates Collected During FLAME-I Experiment
A. Laskin, J. Laskin, Y. Desyaterik

2. Field sampling devices
TRAC
Time resolved sampling of µm particles onto microscopy and microprobe suitable substrates for single particle analysis
CCSEM/EDX
HR TEM
TOF-SIMS
µ-FTIR
STXM/NEXAFS
at LBNL (Mary Gilles)
MOUDI
Size resolved sampling of µm particles
(5-10 impaction stages) onto microscopy and microprobe suitable substrates for single particle analysis
Size resolved bulk samples for solvent extraction
HR TEM
TOF-SIMS
CCSEM/EDX
Solvent extraction for
High-Resolution ESI-MS analysis
STXM/NEXAFS
at LBNL (Mary Gilles)

3. SEM/EDX analysis C P. Pine Needles_Litter_Branches F P. Pine duff
A. Burns dominated by organic/carbonaceous particles
C P. Pine Needles_Litter_Branches
F P. Pine duff
P Southern Pine needles
S Ceanothus

4. SEM/EDX analysis B,D,N Chamise I Utah suniper foliage and stick
B. Burns dominated by soot
B,D,N Chamise
I Utah suniper foliage and stick
J Utah sage rabbit brash

5. SEM/EDX analysis E Rice Straw H Manzanita
C. Burns dominated by Inorganic particles
E Rice Straw
H Manzanita

6. SEM/EDX analysis R Palmetto O Wax Murtle
C. Burns dominated by Inorganic particles
R Palmetto
O Wax Murtle

7. STXM/NEXAFS analysis (M.K. Gilles et al, LBNL)
Relationship between single scattering albedo (ω) and % sp2 hybridization for the FLAME-I fuels and methane soot.
Can we obtain molecular specific information on chemical bonding?

8. Molecular speciation of particulate extracts using LTQ-Orbitrap MS
High-Resolution FT-Orbitrap MS

9. LTQ-Orbitrap ESI - MS Analysis
Resolution: m/Dm=100,000
C28H32ONa+
C25H36O2Na+
C6H10O5Na+
C8H12O6Na+
Figure High-resolution LTQ/Orbitrap spectra obtained by electrospraying methanol extracts of three samples of aerosols from burning of a) pine needles and branches; b) pine duff; c) ceanothus under smoldering conditions.
Pine needles
Figure Comparison of positive (top) and negative (bottom) mass spectra in the range from 400 to 900 amu obtained using methanol extract of smoke particles from pine needles and branches
Positive mode
Negative mode
Pine duff
Ceanothus

10. Interpretation of high-res mass spectra using Kendrick plots
Kendrick Mass = Observed Mass× (Nominal mass of CH2)/ (Exact mass of CH2)
Kendrick Mass Defect = Kendrick Mass - Nominal Mass
Figure Comparison of positive (top) and negative (bottom) mass spectra in the range from 400 to 900 amu obtained using methanol extract of smoke particles from pine needles and branches

11. Interpretation of high-res mass spectra using Kendrick plots
Positive ions
C4H6N2+H+ +(CH2)n=0-8
C11H8N2+H+
C7H10N2+H+
C8H8N2+H+
C11H12N2+H+
C14H24O4+Na+
C14H24O3+Na+
C11H22O3+Na+
C14H14O4+Na+

12. Compounds reported in the literature
Interpretation of high-res mass spectra using Kendrick plots
Positive ions
C4H6N2+H+ +(CH2)n=0-8
C7H10N2+H+
C11H22O3+Na+
C8H8N2+H+
C14H24O3+Na+
C11H12N2+H+
C11H8N2+H+
Compounds reported in the literature
Hildemann et al, EST 1993
C14H24O4+Na+
C14H14O4+Na+

13. Interpretation of high-res mass spectra using Kendrick plots
Negative ions +H +Na
Positive ions

14. Interpretation of high-res mass spectra using Kendrick plots
Negative ions +H +Na
Positive ions
N-containing
heterocyclic
hydrocarbons
M+H+
R-COOH
hydrocarbons
[M-H+]-
M-Na+
R-OH, R-O-R, R-C-R
hydrocarbons containing
multi functional groups
[M-H+]- O

15. LTQ-Orbitrap high-res MS Analysis, Summary
Unambiguous identification of identification of homologous species with of high MW
Option of MS n analysis of selected peaks, molecular structure identification
Option of HPLC separation stage – simplified spectra, quantitative analysis of some selected species
Option of APPI, APCI ionization sources
Tool for understanding and interpretation of other data sets,
STXM/NEXAFS, AMS, etc
Valuable insights for cross-correlation studies of PM optical and hygroscopic properties