GCxGC-(MS) methods

Pim Leonards
 Outline
• Principles of GCxGC
• Selection of detectors
• PCB, PBDE analysis
• Other examples
Principles of GCxGC •Selection of modulator
•6 different modulators:
•SWEEPER
Selection of proper column combination •LMCS
•Quad N2(l) jet
Injector Detector
•Dual CO2 jet
•Loop CO2
•CFT
Modulator

1st column 2nd column

 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)
 How does it work?
Cryogenic modulator
How does GCxGC work ?
How does GCxGC work ?
How does GCxGC work ?

0s 10 s
1 Separation on the 2nd dimension column
 How does GCxGC work ?

6
6
5
4

3
2 1
0s 10 s
1
 Principle and contour plots

46 min
10 s

2nd
1st
1
0 10 s
43 0
2nd
0s 10 s 43 46
1st
Contour plot
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
GCxGC-μECD
 88
GCxGC-μECD 125 PBDE’s
27 BB153
154 DB-1x007-65HT 2OH-28
74
6OH-47 4OH-42 115
77 98,119 155
49 116 86
6MeO-47 109
51 46,48 42,66 87
66 4’F-27 40,77 102 88 85
71 104 100
me-TBBP-A 25,31 76
55 62 55 99
18 17 16,33 BB52 53 50 106
47
114
44 32 20,35 124
27 19 BB49 81 121
6 12,13 78 120 127 126
4 67 3F-100
33 103 101 125
30 BB101
8 BB15 72 58,79 3F-119 108,123
9
2nd dimension retention time (s)

22 4’F-27
22,37
69,73 6F-47 80 68 4OH-49
2 38 4MeO-49 97,118
36
34 4’F-69 6F-66
11 3 28
1 29 4’F-25
15 26 3’F-28
10 14 7 11 39
00
10 15 20 25 30 35 40
88 9 10 11 12 131,158,140
13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
142 128 185 198
6OH-99 173,190 4’F-208
77 160 138 182 204 205
4’F-160 191
203
154 139 156
66 105 184
181 4’,6F-199 209
168 HBCD 2,4’F-198
192
183
55 166 TBBP-A
139 198
BB169 116
161 141 85
144 100
44 153 159
167 203
138 181
BB153 TBBP-A 144 HBCD 183
33
154
99 153
me-TBBP-A 101
22 PCAs

207
11 208 206

00
45 50 55 60 65 70 80
42 43 4441 4542 4643 4744 4845 4946 5047 5148 5249 5350 5451 5552 5653 1st5754dimension
5855 5956 retention
6057 6158 time6259 (min)
6360 6461 6562 6663 6764 6865 6966 7067 7168 7269 7370 71 72 73
Korytar et al., J Chrom A, 1100 (2005) 200–207
 GCxGC-μECD various contaminants
1111
PCDD/Fs Korytar et al., J. Chromatogr. A, 2005. 1086, 29-44
1010 PCBs
DB-1  LC-50
99 PBBs
PBDEs
2nd dimension retention time (sec)

88 PCDEs
77 OCPs
Toxaphenes
66 PCNs
55 PCDTs
44
33
22 PCAs
11
00 10 20 30 40 50 60 70
10 20 301st 40 50
dimension retention time (min) 60 70
 GCxGC-μECD different column combination
1010 PBDEs
PCBs DB-1  007-65HT
99 PCNs
PCDTs
88
2nd dimension retention time (sec)

PCDEs
77 PBBs
PCDD/Fs
66 Toxaphene
OCPs
55
44
33 PCAs
22
11 Korytar et al., 2005. J. Chromatogr. A, 1086, 29-44

00 10 20 30 40 50 60 70
10 15 20 25 30 1 35
st
40 retention
dimension 45 50 55 60 65 70 75 80
time (min)
 GCxGC-μECD dust sample
DB-1×007-65HT PBDEs

P. Korytar et al. / J. Chromatogr.

A 1086 (2005) 29–44 Polychlorinated alkanes
 Background matrix separation from dioxins
GCxGC-ECD, DB-XLB x LC-50
5D1
2nd dimension retention time [s]

6F3
6D3
4F1 4D1 6F2 6D2
5F1 7F1
5F2

6F1 6D1

7F2
OCDF

6F4

Background matrix
7D1 OCDD

1st dimension retention time [min]

P. Korytar et al. / J. Chromatogr. A 1100 (2005) 200–207

GCxGC-MS
 GCxGC with qMS

• Requirements

fast acquisition
spectral quality: no skewing
Modulator control
Set-up
Dual-jet CO2
modulator

GC

Single quadrupole MS
 Quadrupole MS

High acquisition rates

• short Rf setup time
• fast scanning

Rf setup time: 10.4 ms

Scan rate: 10000 amu/s
Scan width (amu): @ 50Hz: 96
@ 33 Hz: 195
@ 25 Hz: 296
 No skewing
mass ratio plot (m/z 330/326)

0.8

Shimadzu qMS
Mass Ratio

0.6

0.4

0.2

0 2 4 6 8 10

Data point number

 Quality of spectra

P. Korytar et al. / J. Chromatogr. A 1067 (2005) 255–264

 Mass range scanned

P. Korytar et al. / J. Chromatogr. A 1067 (2005) 255–264 259

 GCxGC-qMS
• Fast enough

• Selective enough
– separation of coeluters

• Limited scanning range (300 Da)

• Not sensitive enough in EI

– NCI required
Eel extract GCxGC-qMS
PBDE analysis

P. Korytar et al. / J. Chromatogr. A 1067 (2005) 255–264

 GCxGC ToFMS
• Fast scan speed: 100-500 Hz
• No mass skewing
• Automated search
 GCxGC-ToF-MS, Tern egg
Western Scheldt
Brominated compounds
2nd dimension retention time (sec)

PCBs
PCAs

1st dimension retention time (min)

Screening chemicals in household dust
GCxGC-ToFMS of an hexane extract of dust

Hilton et al., 2010. J. Chrom A, 1217 (2010) 6851–6856

 Chlorinated and brominated
compounds in house dust
Cl and Br compounds
• >10,000 peaks
detected
• 145 compounds
contain chlorine or
bromine

Hilton et al., 2010. J. Chrom A, 1217 (2010) 6851–6856

Other compounds identified in
household dust

Phthalates PAHs

Hilton et al., 2010. J. Chrom A, 1217 (2010) 6851–6856

 GCxGC-AED oil
Sulphur
Carbon

van Stee et al. / J. Chromatogr. A 1019 (2003) 89–99

 Effect-directed analysis (EDA)
Bioassay
Bioassay confirmation

Bioassay
Bioassay
Y x Y
x x
x Y
Y Y
x x
x

complex mixture
of compounds
1st 2nd
Fractionation Fractionation
Chemical
identification
 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

Bioassay activity of the sediment

Houtman et al., 2006, Chemosphere 65, 2244–2252

Active fraction GCxGC-ToFMS
Fraction 4-B Fraction 4-B

Me-PAHs

PAHs

Fraction 5-B Fraction 2

Hormones
PAHs

Houtman et al., 2006, Chemosphere 65, 2244–2252

 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
 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