-
- -
GC-MS
Commonly done on low resolution (1 dalton) quadrupole instruments in the selected ion ((mass)) mode. e.g. Hewlett-Packard MSD, VG Trio and
MD-800 Finnigan INCOS-60 ShimadzuMD 800, Finnigan INCOS 60, Shimadzu QP-500 etc. CCan be done at hiigh resolutiion; accurate mass
-
What has to be right for successful GC-MS?
Everyy sin ggle time yyou tryy!!
•GC working with correct column in good condition, right gas flows, autosampler working, correct conditions of injection, temp program hot interface no leaks no bleed clean injector clean program, hot interface, no leaks, no bleed, clean injector, clean syringe, clean wash solvents, correct vials and septa ……...
•Good vacuum clean source right source temp and ionising •Good vacuum, clean source, right source temp and ionising conditions, appropriate peak resolution & tune, correct slits, correct gain setting, low instrument noise ……..
• DS interface (noise, threshold) set correctly, correct experiment for the job, instrument in calibration, file structure correct, adequate storage space, no bugs before starting sequence ………
•Samples correctly ordered in sampler, blanks & external standards included, data archived , QUAN set up correctly ….
•Interpretive skill ….
-
-
-
Components of the Mass Spectrometer (1)
•Vacuum System •any collisions of an ion with a gas molecules in its path destroys it --> no MS
•System to convert intact molecules to ions -System to convert intact molecules to ions
THE ION SOURCE
•electron impact (EI), chemical ionisation (volatiles) • electrospray or sputtering (non-volatiles eg proteins, DNA)
•Mass Analyser - To filter by mass (and KE) Mass Analyser To filter by mass (and KE) •Ion Detector and ion current amplifier •Dispp ylay mechanisms and Data Acqquisition Syystem
-
Components of the Mass Spectrometer (2)
•Mass Analyser - To filter by mass (and KE) •si lingle magnett or quaddrupolle -->>
Ion Detector and ion current amplifier
•Display mechanisms and Data Acquisition SystemDisplay mechanisms and Data Acquisition System
-
Formation of the mass sppectrum •Compound ionises in source •Molecular ions fragments as a result of
excess energy impparted by the ionisingggy y electrons (standard energy 70eV) ••Ions pushed from source with repellerIons pushed from source with repeller •Accelerated by high voltage •Ions separated by mass analyser •IIons counttedd andd recorddedd
-
Calibration and leak checkingCalibration and leak checking
P fl k (PFK) i t f•Perfluorokerosene (PFK) - a mixture of fluoroalkanes with ions to > 900 dalton 69, 100, 119, 219, 231 …….. •Hepptacosafluorotributyylamine - a singgle
compound MW 614 with 69, 119, 219 ...
•Background spectrum should look like air;Background spectrum should look like air;
•17,18,28-32 and 40 Da •AArgon usefful to ddetect l t leakksl t t
-
Characteristic ion series
Sili bl ili t ) 207 281•Silicone bleed ( d (silicon iisotopes) 207, 281, 355 • Alkanes 57, 71, 85, 99, 113 ...
••Alkenes 55 69 83 97 111Alkenes 55, 69, 83, 97, 111 …
•Cyclohexanes 83, 97, 111 •Terpanes 123, 149, 191, 205, 217, 231 •Monoaromatics 77 91 105 119 133•Monoaromatics 77, 91, 105, 119, 133 …..
-
o sat o e e a d st uctu e dete e d ee
Appearance of the Mass Sppectrumpp
•Average spectrum has 250 bits of informationg p •Molecular ion and its isotopic abundances •Ionisation energy and structure determine degreegy eg of fragmentation; 70 eV is standard •Fraggment abundances reflect to relative stabilities of the fragment ions - most abundant are the most stable
-
Interppretation of the mass sppectrum
•Identify molecular ion •Assess isotope abundances for:
A elements H and F A+1 elements C, N A+2 elements Si S Cl BrA+2 elements Si, S, Cl, Br
•Determine # rings and double bonds Acyclic saturated hydrocarbons CnH2n+2 •Identifyy ‘characteristic’ ions and low mass series
-
Interppretation of the mass sppectrum
•Identify molecular ion –Molecular Ion corresponds to the loss of one electron from the intact molecule –Molecular ion is an ‘odd electron’ ion –Odd electron ions are generally present and have an even mass unless an odd number of nitrogens
-
Identify:Identify:
1947 sats Molecular Ion? 100 64
Isotopic features?
Ion series?
256
128128
160
96
192192
66
9857 71 85
0 m/z
50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
%
-
Nuclidic Masses and Abundances
Element Mass Isotope Abundance
carbon 12.00000 13 0034 13.0034
98.9 1 11.1
hydrogen 1.007825 2 0140 2.0140
99.985 0 015 0.015
nitrogen 14.00307 15.000115.0001
99.63 0.370.37
oxygen 15.9949 17.9992
99.8 0.2
fluorine 18.9984 100
lfsulfur 31 9720 31.9720 32.9715 33.9679
94 8 94.8 0.8 4.4
-
= 412
100 %
80
60
40
20
0
100 %
80
60
40
20
0
A7NO12A#3-1007 Identify 55
Molecular ion69
Odd electron ions; A+1 or A+2?
60 80 100 120 140 160 180 200 220 240 260 280 300 m/z
55 x10.00
60 80 100 120 140 160 180 200 220 240 260 280 300 m/z
83
low mass series97
#carbons#carbons
111
rings & double bonds
125
69
83
97
111 154
168168
266
266
125 182 196 238
-
1947 sats
57100 57
71
85
55
99
11383
127
141 240155 169 18367 197 211
0 m/z
50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
%%
-
68 sats
100 57 71
85
55
113 12769
99
9797
183
197141
155
1696753 81 253 267 282179 211 225
0 m/z
5050 60 70 80 9090 100 110 120 130 140 150150 160 170 180 190 190 200 210 220 230 240 250 260 270 280 290 30060 70 80 100 110 120 130 140 160 170 180 200 210 220 230 240 250 260 270 280 290 300
%
-
68 sats
100 57 71
85
55 113
69 99 183
127
97 141 155
6753 81 169 197 225 239 253 268
0 m/z
50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
%%
-
1947 sats
5757100
71
85
55
99
69
113
83 127
141 254155 169 183 19767 211 225
0 m/z
50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
%
-
1947 sats
100 57
71
85
281
69 99
83 113
97 127
141 155 169 183 197 211 225 25367 295
0 m/z
5050 60 70 80 9090 100 110 120 130 140 150 150 160 170 170 180 190 200 210 220 230 240 250 260 270 280 290 30060 70 80 100 110 120 130 140 160 180 190 200 210 220 230 240 250 260 270 280 290 300
%
-
1947 sats
100 57
55
97
71
69
83
81
67 111
99
125
53 79 139 153 168 183 207 224 25291 105 239
0
65 119 197131
m/z
5050 60 70 80 9090 100 110 120 130 140 150 150 160 170 170 180 190 200 210 220 230 240 250 260 270 280 290 30060 70 80 100 110 120 130 140 160 180 190 200 210 220 230 240 250 260 270 280 290 300
%
-
•
Standard Interpretation ProcedureStandard Interpretation Procedure • Verify masses (calibration); determine elemental
iti & i + t ticompositions & rings+unsaturations • Mark odd electron ions and verify molecular ion • Study appearance of spectrum molecular stability Study appearance of spectrum, molecular stability,
labile bonds • Identify low mass ion series • Identify neutral fragments, logical mass losses • Postulate structures of low mass ions • P t l t id tit t t i t f t libPostulate identity; test against ref. spectrum or library;
rationalize fragmentation pattern
©McLafferty: Interpretation of Mass Spectra
-
==
αβ-Hopane a fossil hydrocarbon
369
Structure
MW 412 191
369
MW 412
191 %100
Mass spectrum
412 149
123 109
95 81
68
50 100 150 200 250 300 350 400 450 500
412 397
206177
163137 123
369
-
==
CC HOPANEHOPANECC HOPANEHOPANECC3030 HOPANEHOPANECC3030 HOPANEHOPANE369
Structure
MW 412 191
369
MW 412
191 %100
Mass spectrum
412 149
123 109
95 81
68
50 100 150 200 250 300 350 400 450 500
412 397
206177
163137 123
369
-
TriterpanesTriterpanes -- 191 Da191 Da C30 ��
GippslandGippslandC29 ��
C31 �� S
Ts Tm S R C32 �� C33 ��
NW ShelfNW ShelfC29Ts
Dia
Middle EastMiddle East30-nor
-
AGSO Standard 221 Da
File A6MA15C:4
SIM-GCMS: 221.221
Da
Scale Factor: 4 9 Scale Factor: 4.9
100
90
80
70
60
50
40
30
20
10
D44
Int.
Std
.
%
50:00 55:00 1:00:00 1:05:00 1:10:00 1:15:00 TIME (min.)
0
-
d.
AGSO Standard 234 Da
File A6MA15C:4 SIM-GCMS: 234.232 Da S l F t 5 4Scale Factor: 5.4
100 %
90
80
70
60
50
D3
Rec
. Std
30
40
20
10
0
50:00 55:00 1:00:00 1:05:00 1:10:00 1:15:00 TIME (min.)
-
File A6MA15C:4 SIM-GCMS: 217.196 Da Scale Factor: 4.9
0S 20R
%100
ααα
20S
Bi
cad
TC29
βα
20
+C27
αββ
C29
αββ
20R
29
αββ
20S
0S
β 20
S
R 0R0S α 20
R
C28 +
B
4S +
R
20R
C27
βα
20S
C2
αββ
20R
C28
αββ
20
+ B
icad
T1
C27
αββ
C29
βα
20R
C29
ααα
20S
C29
ααα
20
C27
ααα
2
C27
ααα
0R +
RC
28 β
α 20
S, 2
4
α 20
R, 2
4S +
R
C27
βα
20SBic
ad W
C28
α
C28
ααα
20
Bic
ad R
C
C28
βα
C30
βα
2
αα 2
0RC
30 α
α
AGSO Standard 217 Da
90
80
7070
60
50
40
30
20
10
0 48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
TIME (min.)
-
C28
βα
C28
βα
C28
αββ
C28
+ Bi
cad
C27
C29C27
C28
ααα
C27C
27
C30
βα
ααα
20RC29
C29
βα
C29C27
C C
C30
α
AGSO Standard: steranes SIM vs. MRM SIM-GCMS: 217 Da
MRM-GCMS: 400 -> 217 Da
MRM-GCMS: 386 -> 217 Da
MRM-GCMS: 372 -> 217 Da
βα 2
0S
βα 2
0R
20S
, 24S
++R
20R
, 24S
+ RR
ααα
20S
C29
βαα
20S
+C27
ααββ
20R
αβ
β 20
S
ααα
20R
20R
C28
ααα
20S
+ Bi
cad
T 20
Rαβ
β 20
S
T1
20R
+ B
icaad
R
ααα
20S
C29
αββ
200R
αββ
20S
ααα
20R
20S
Bica
d W
-
File A6MA15C:4 SIM-GCMS: 218.203 Da S l F t 4 1Scale Factor: 4.1
AGSO Standard 218 Da
αββ
20R
S C29
αββ
20R
9 αβ
β 20
S
100 %%
80
90
100
C29
0S
C27
C27
αββ
20S
C
60
70
C28
αββ
2
8 αβ
β 20
R
30
40
50 C28
10
20
0
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
TIME (min.)
-
File A6MA15C:4 SIM-GCMS: 191.179 Da S l F t 6 4Scale Factor: 6.4
100 % C24Tet
90
80
70
60
50
40
30
20
10
0
AGSO Standard 191 Da
C23Tri C19Tri
23
C20Tri C21Tri C24Tr
i
+ S
)
S)
C22Tri
C 25
Tri (
R +
C 26
Tri(R
+ S
26:00 28:00 30:00 32:00 34:00 36:00 38:00 40:00 42:00 44:00 46:00 48:00 50:00
TIME (min.)
-
File A6MA15C:4
SIM-GCMS: 191.179
Da
S l F t 25 1Scale Factor: 25.1
100%
90
80
70
60
50
40
30
20
10
0
AGSO Standard 191 Da
C29H
C30H
Compounds 1, 2 and 4 are Oleanoid Triterpanes (see Murray et al. (1997), Geochim. Cosmochim. Acta, in press. Tx is Taraxastane
O or
C30
HC29
Ts
α
Ts Tm
C31H S
C31H R
C32H28H
DiaC29
H+4
d T
γ
30 C
28H
C30
H β
α30
-no
C29
H β
α
C31
H β
α
C32H S
C32H R C33H
S C33H R
C34HSC34HR C35HS C35HR
29,3
0 C
2 C
29 D
ia
C30
H D
25-n
or C
Bic
ad
Bicad W
1,2
+ 28
,3
Tx
50:00 55:00 1:00:00 1:05:00 1:10:00 1:15:00
TIME (min.)
-
File A6MA15C:4 SIM-GCMS: 369.352 Da S l F t 10 3 Scale Factor: 10.3
Bicad T
AGSO Standard 369 Da
%
90
100
W = cis-cis-trans Bicadinane T = trans-trans-trans Bicadinane
70
80 T1,R = isomers of T
50
60
Bicad W
30
40
Bicad T1
10
20 Bicad T1
Bicad R
0
50:00 55:00 1:00:00 1:05:00 1:10:00 1:15:00
TIME (min.)
-
File A6MA15C:4
SIM-GCMS: 123.117
Da
S l F t 100Scale Factor: 100
100
90
80
70
60
50
40
30
20
10
0
8 β(H) H i8 β(H)-Homoddrimane
AGSO Standard 123 Da
%
10:00 14:00 18:00 22:00 26:00 30:00 34:00 38:00
TIME (min.)
-
File A6MA15C:4 SIM-GCMS: 205.194 Da S l F t 10 3 Scale Factor: 10.3
AGSO Standard 205 Da
%
90
100
2MeH
70
80 C31
2
50
60
H
30
40
C31
3M
eH
10
20
0
56:00 58:00 1:00:00 1:02:00 1:04:00 1:06:00
TIME (min.)
-
File A6MA15C:4 SIM-GCMS: 231.212 Da S l F t 2 5
AGSO Standard 231 Da
%
90
100 Scale Factor: 2.5 Bicad T
70
80
Bicad W
50
60
αα 4
Me2
0R
30
40
C31
αα
10
20
0 48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
TIME (min.)
-
GCGC MSMS MSMSGCGC--MSMS--MSMSTrue GC-MS-MS reqquires an instrument with at least two, independently controllable mass selection reggions.
Various configurations possible, e.g. Triple Sector Quadruple “HybridSector Quadruple,“Hybrid” magnet/quadrupole etc. e.g. Autospec-Q, Finnagin MAT 95Q etFinnagin MAT 95Q etc.
Very high sensitivity and selectivity very powerful for biomarker work.
-
C28
βα
C28
βα
C28
αββ
C28
+ Bi
cad
C27
C29C27
C28
ααα
C27C
27
C30
βα
ααα
20RC29
C29
βα
C29C27
C C
C30
α
AGSO Standard: steranes SIM vs. MRM SIM-GCMS: 217 Da
MRM-GCMS: 400 -> 217 Da
MRM-GCMS: 386 -> 217 Da
MRM-GCMS: 372 -> 217 Da
βα 2
0S
βα 2
0R
20S
, 24S
++R
20R
, 24S
+ RR
ααα
20S
C29
βαα
20S
+C27
ααββ
20R
αβ
β 20
S
ααα
20R
20R
C28
ααα
20S
+ Bi
cad
T 20
Rαβ
β 20
S
T1
20R
+ B
icaad
R
ααα
20S
C29
αββ
200R
αββ
20S
ααα
20R
20S
Bica
d W
-
eco d o b o a e o ecu a we t
MRMMRM GCGC MSMSMRMMRM--GCGC--MSMSMetastable Reaction Monitoring GC-MSMetastable Reaction Monitoring GC MS Monitoring of ion reactions (e.g. Molecular-Daughter) by selecting metastable ions in thDaughter) by selecting metastable ions in the first field free region.
Not “true” GCMSMS but allows selective recordingg of biomarker molecular weigght groups (e.g. only C30 steranes cf. all steranes at once)).
-
MRMMRM GCGC MS (2)MS (2)MRMMRM--GCGC--MS (2)MS (2)Metastable Reaction Monitoring GC MSMetastable Reaction Monitoring GC-MS
Higher selectivity and sensitivitHigher selectivity and sensitivity.
Can be done on double focussing highCan be done on double focussing, high resolution instruments such as VG 70E etc but parent ions can only be selected at lobut parent ions can only be selected at low resolution - some interference or “cross talk” between tracebetween traces.
-
%100
e
C28 389 → 234 Da M th d t d d
AGSO Standard
80
90
H)-c
hole
stan
389 → 234 Da 8.6
Method recovery standard
60
70
3-C
D3 -
5α-(
H
30
40
50
10
20
30
0
10
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
-
C27372 → 217 Da372 → 217 Da18.3
%
90
100
27 β
α 20
S AGSO Standard
70
80
90
C2
0R
50
60
C27
βα 2
ααα
20R
β 20
Sαβ
β 20
R
20S
30
40 C27
α
C27
αββ
C27
C
27 α
αα 2
10
20
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
-
C28386 → 217 Da5.2
AGSO St d d %
90
100
βα 2
0S
28 α
ββ 2
0S
0R
{
AGSO Standard
70
80
90 C
28 β
0R
C2
C28
αββ
20
C28
βα
20R
50
60
70
C28
ααα
2
α 20
S
C
{
30
40
50
C28
ααα
10
20
30
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
-
AGSO %
90
100
0R C29
404 → 221 Da GCMS Internal Standard
AGSO Standard
70
80
90
gmas
tane
20404 → 221 Da
13.4
50
60
70
D 4 -
ααα-
sti
30
40
50
10
20
0 48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
-
AGSO Standard %
90
100
βα 2
0SC29 400 → 217 Da
70
80
90
C29
β
βα 2
0R
C29
αββ
20S
ββ
20R
S
400 → 217 Da 13.4
50
60
70
C29
β
C29
ααα
20R
C
C29
α
C29
ααα
20S
30
40
CC
10
20
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
-
R+S
)C
30αβ
β20
(RC
AGSO Standard
%
90
100
20S
C30
βα
20S
C30
βα
20R
C30 414 → 217 Da 0 9
AGSO Standard
70
80
90
30 α
αα 2
0R
C30
ααα
C C0.9
50
60
70 C
30
40
50
10
20
30
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
-
R S+ SAGSO Standard
%
90
100
30 2
α M
e 20
R
4α M
e ββ
20S
β M
e ββ
20R
+
C30 414 → 231 Da 2 2
70
80
90
+ D
ino
C3 +
20S
Me
20R
e 20
S C
30 3
β2.2
50
60
70
4α M
e 20
R +
C30
4α
Me
2 C
30 4
α ββ
20S C
30 3
βMe
30
40 C30
4
3β M
e 20
R
C30
2αM
e 2
10
20 C30
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
-
%
90
100 C31 426 → 205 Da
AGSO Standard
70
80
90
2α M
e
426 → 205 Da 4.7
50
60
70
C31
2
1 3β
Me
30
40
50
C31
10
20
56:00 58:00 1:00:00 1:02:00 1:04:00 1:06:00 0
-
File:A6MA16 #1-986 Acq:17-MAR-1996 00:09:04 GC EI+ MRM Autospec-UltimaQ Sample Text:AGSOSTD 1/2A File Text:Ultra-1, 50m, H2@20psi
E MRM OZOILS STD S:6 F:2
Exp:MRM_OZOILS_STD
Bicad T
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
%
90
100 C30 412 → 369 Da AGSO Standard
70
80
90 100
50
60
70
30
40
50
RT1
10
20
30
Bic
ad R
Bicad W B
icad
0
File:A6MA16
-
AGSO Standard Ts
100 %
90 C27 370 191 D Tm + Bic T1 370 → 191 Da 23.2
ic T
)
Bi
C27
17β
(H)
90
80
7070
60
5050
40
3030
20
1010
0
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00
-
AGSO Standard
%
90
100 C28 384 → 191 Da
70
80
90 384 → 191 Da 7.6
50
60
70 29,30 C28H
30
40
50
C28
H
10
20
30
28,3
0 C
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
-
AGSO Standard %
90
100 C29 H
C29 398 → 191 Da
AGSO Standard
70
80
H398 → 191 Da 40.2
50
60
30
40
C29Ts
10
20
29
C29
Dia
C29H βα
29 D
iane
o
48:00 50:00 52:00 54:00 56:00 58:00 1:00:00 0
C2
-
C30H 100 %
90
80
70
60
50
40
30
20
10
0 56:00 58:00 1:00:00 1:02:00 1:04:00 1:06:00
C30 412 → 191 Da
AGSO Standard
412 → 191 Da 35.4
Compounds 1 - 6 are Oleanoid Triterpanes (see Murray et al. (1997), Geochim. Cosmochim. Acta, in press. Tx is Taraxastane
ia
30 C30H
Oleanoid triterpanes
C30
H D
i
C30H βα
O 30-nor C30H
γ1 2 3 2
4 6
Tx 3 Tx
-
426 → 191 Da
80
70
60
50
40
30
20
10
0 56:00 58:00 1:00:00 1:02:00 1:04:00 1:06:00
%
90
100 C31HS
C31 426 → 191 Da
AGSO Standard
C31HR15.9
C31
Dia
SC
31 D
ia R
-
Note: This trace is from run A6FE24:5
using MRM-OZOILS 50
90
80
7070
60
5050
40
30
20
10
0 45:00 50:00 55:00 1:00:00 1:05:00
AGSO Standard %
90
100 C34HS
C34 468 → 191 Da
using MRM OZOILS_50 AGSO Standard
468 → 191 Da
C34HR
-
-Note: This trace is from run A6FE24:5
using MRM-OZOILS 50 AGSO St d d %
90
100 C35 482 → 191 Da
C35HS using MRM OZOILS_50 AGSO Standard
70
80
482 → 191 Da
50
60 C35HR
30
40
10
20
0 45:00 50:00 55:00 1:00:00 1:05:00
-
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12.458 Molecular Biogeochemistry Fall 2009
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