GCxGC-(MS) methods · PDF filespectral quality: no skewing . Modulator control Single...
Transcript of GCxGC-(MS) methods · PDF filespectral quality: no skewing . Modulator control Single...
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GCxGC-(MS) methods
Pim Leonards
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Outline
• Principles of GCxGC
• Selection of detectors
• PCB, PBDE analysis
• Other examples
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Injector Detector
Modulator
1st column 2nd column
•Selection of modulator •6 different modulators:
•SWEEPER •LMCS •Quad N2(l) jet •Dual CO2 jet •Loop CO2
•CFT
Selection of proper column combination
Principles of GCxGC
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Selection 1st and 2nd dimension GC columns
• 1st dimension
– Apolar type phases:
DB-1, DB-5, CP-Sil 8 type of columns
2nd dimension
-Polar type and phase selective phases:
DB-XLB (proprietary) fused-silica
007-65HT (65% phenyl-methylpolysiloxane)
LC-50 (50% liquid crystalline-methylpolysiloxane)
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How does it work? Cryogenic modulator
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How does GCxGC work ?
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How does GCxGC work ?
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How does GCxGC work ?
Separation on the 2nd dimension column
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How does GCxGC work ?
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Principle and contour plots
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Contour plot
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Detectors for GCxGC systems
• Fast scanning detectors
• Acquisition rate >20 Hz
• Low dead volume detectors
Commercial equipment
• GCxGC-FID
• GCxGC-ECD
• GCxGC-qMS
• GCxGC-ToF-MS
• GCxGC-AED not commercial available
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GCxGC-μECD
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4MeO-49
4OH-42
3F-100
6F-66 4’F-69
2OH-28
BB52
BB49
4’F-27
BB15
1 4’F-25 3’F-28
BB101
6OH-47
4OH-49
154
me-TBBP-A
BB153
6OH-99
144 161
168
153
TBBP-A
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131,158,140
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HBCD
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BB169
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4’,6F-199 2,4’F-198
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3F-119
6MeO-47
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183 181
PCAs
HBCD
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139
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TBBP-A
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me-TBBP-A
GCxGC-μECD 125 PBDE’s DB-1x007-65HT
Korytar et al., J Chrom A, 1100 (2005) 200–207
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PCDTs
PCAs
GCxGC-μECD various contaminants
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Korytar et al., J. Chromatogr. A, 2005. 1086, 29-44
DB-1 LC-50
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GCxGC-μECD different column combination
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PBDEs
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OCPs
PCAs
DB-1 007-65HT
Korytar et al., 2005. J. Chromatogr. A, 1086, 29-44
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GCxGC-μECD dust sample PBDEs
Polychlorinated alkanes P. Korytar et al. / J. Chromatogr. A 1086 (2005) 29–44
DB-1×007-65HT
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Background matrix separation from dioxins
4F1 4D1 5F1
5F2
5D1
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OCDD
OCDF
1st dimension retention time [min]
2nd d
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GCxGC-ECD, DB-XLB x LC-50
P. Korytar et al. / J. Chromatogr. A 1100 (2005) 200–207
Background matrix
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GCxGC-MS
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GCxGC with qMS
• Requirements
fast acquisition
spectral quality: no skewing
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Modulator control
Single quadrupole MS
Dual-jet CO2 modulator
GC
Set-up
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Quadrupole MS
Rf setup time: 10.4 ms
Scan rate: 10000 amu/s
Scan width (amu): @ 50Hz: 96
@ 33 Hz: 195
@ 25 Hz: 296
High acquisition rates • short Rf setup time • fast scanning
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No skewing mass ratio plot (m/z 330/326)
0
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Data point number
Mas
s R
atio
Shimadzu qMS
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Quality of spectra
P. Korytar et al. / J. Chromatogr. A 1067 (2005) 255–264
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Mass range scanned
P. Korytar et al. / J. Chromatogr. A 1067 (2005) 255–264 259
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GCxGC-qMS
• Fast enough
• Selective enough – separation of coeluters
• Limited scanning range (300 Da)
• Not sensitive enough in EI – NCI required
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Eel extract GCxGC-qMS PBDE analysis
P. Korytar et al. / J. Chromatogr. A 1067 (2005) 255–264
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GCxGC ToFMS
• Fast scan speed: 100-500 Hz
• No mass skewing
• Automated search
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GCxGC-ToF-MS, Tern egg Western Scheldt
PCBs
PCAs
Brominated compounds
1st dimension retention time (min)
2n
d d
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sio
n r
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(sec
)
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Screening chemicals in household dust GCxGC-ToFMS of an hexane extract of dust
Hilton et al., 2010. J. Chrom A, 1217 (2010) 6851–6856
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Chlorinated and brominated compounds in house dust
• >10,000 peaks detected
• 145 compounds contain chlorine or bromine
Hilton et al., 2010. J. Chrom A, 1217 (2010) 6851–6856
Cl and Br compounds
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Other compounds identified in household dust
PAHs Phthalates
Hilton et al., 2010. J. Chrom A, 1217 (2010) 6851–6856
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GCxGC-AED oil
Sulphur
Carbon
van Stee et al. / J. Chromatogr. A 1019 (2003) 89–99
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Bioassay
Bioassay
Bioassay
Effect-directed analysis (EDA)
x Y
x
x
x x
Y
Y
Y
complex mixture of compounds
x x Y
1st Fractionation
2nd Fractionation
Chemical identification
Bioassay confirmation
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Combined sample treatment scheme
chemical and bioassay analysis
Houtman et al. 2006 •Sediment sample from a harbour •Bioassays
•Dioxin like compounds (DR-CALUX) •Estrogenic compounds (ER-CALUX)
•Chemical identification •GC-MS •GCxGC-ToFMS
Houtman et al., 2006, Chemosphere 65, 2244–2252
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Bioassay activity of the sediment
Houtman et al., 2006, Chemosphere 65, 2244–2252
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Active fraction GCxGC-ToFMS
Houtman et al., 2006, Chemosphere 65, 2244–2252
Fraction 4-B Fraction 4-B
Fraction 5-B Fraction 2
PAHs
Me-PAHs
PAHs Hormones
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Identified compounds and explained bioassay activity
• 76% of the estrogenic activity was explained by 17α-, 17β-estradiol and estrone
• 38% of dioxin-like activity explained by PAHs
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Summary
• GCxGC is a powerful separation technique
• Separation of interfering compounds and matrix
• GCxGC is especially suitable for the separation of complex mixtures
• GCxGC combined with mass spectrometry can be used for the identification of “new” flame retardants