APPI- and APCI-GC/MS-MS for Petroleum and Environmental ...αββ 20R-cholestane ααα...
Transcript of APPI- and APCI-GC/MS-MS for Petroleum and Environmental ...αββ 20R-cholestane ααα...
APPI- and APCI-GC/MS-MS for Petroleum and
Environmental Applications
Vlad Lobodin, PhD
1
National High Magnetic Field Laboratory, Tallahassee, FL
Future Fuels Institute, Florida State University, Tallahassee, FL
Annual crude oil production:
The World Crude Oil Production
~ 30 billion bbl
~ 5,000,000,000 m3
~ 5 km3
World Crude Oil Production by M bbl/day
Energy Fuels, 2010, 24 (3), pp 1788–1800 “Forecasting World Crude Oil Production Using Multicyclic Hubbert Model”
Predicated “Oil peak” in 2014.
River Thames (London)
The World Crude Oil Production
Average Water Discharge: ~ 2,000,000,000 m3 / year
The Word Crude Oil Production: ~ 5,000,000,000 m3 / year
Gerald Herbert, AP
April 20, 2010
April 22, 2010
Gerald Herbert, AP
NASA
May 24, 2010
~5 million barrels of crude oil have
leaked from the Macondo well
Michael Spooneybarger, AP
Pensacola Beach, Florida June 23, 2010
the inside of tarballs is saturated
with less weathered petroleum
compounds
Tarballs collected from beach
400 600 800 1000 m/z
Macondo Wellhead Oil
13,700 ± 80 Peaks ≥ 6σ
(+) ESI 9.4 FT-ICR MS
Pensacola Beach
32,232 ± 488 Peaks ≥ 6σ
(+) ESI 9.4 FT-ICR MS
High Resolution FT-ICR
Mass Spectrometry: 20 < C# < 100
Biomarker Region
Biomarker Region
1920
6920
16920
11920
8
6
4
2
0
1920
6920
16920
11920
8
6
4
2
0
1st Dimension
Retention Time
(seconds)
2nd Dimension
Retention Time
(seconds)
Pensacola Beach
Macondo Wellhead Oil
Comprehensive Two-dimensional
Gas Chromatography (GC×GC)
C8-C37, Volatiles
m/z 500.5 500.4 500.3
N1O1
N1
O1S113C1
N1O1
N1
N1O1 N1S1
A) Macondo Well Oil
10 Peaks across 250 mDa
O113C1 O2
13C1 N1O2
H1C113C1 O1
13C1
O213C1
N1O2
N1O3 O313C1
B) Pensacola Beach
32 Peaks across 250 mDa
(+) ESI 9.4 T FT-ICR MS
C14H30
C16H34
C18H38
C25H52
C30H62
C20H42
50ºC(3 min)- 3ºC/min- 300ºC
GC/MS of “Macondo crude oil” NIST 2779
(Total Ion Chromatogram)
GCxGC/TOF-MS of “Macondo crude oil” NIST 2779
9.4 Tesla
FT-ICR MS
14.5 Tesla
FT-ICR MS
FT-ICR FACILITIES
1. Carbon Number
2. Heteroatom Composition
3. Aromaticity
m/z 704.53510
[C50H72S1]+•
800 700 600 500 400
*
m/z
m/Δm50%
100 - 400 ppb
DBE = C – H
2
N
2 + + 1
McLafferty & Turecek Int. Mass Spectra, 1993
[Z = -2(DBE) + n + 2]
Carbon Number
DB
E
S1 Class
Relative Abundance (% total)
40
30
20
10
0 20 40 60 80
Workflow for High Resolution “Petroleomics”
S CH3
Isomeric structure for S-compounds
S
CH3
C1-dibenzothiophenes (4 isomers)
S
CH3
S
CH3
1-methyl-dibenzothiophene 4-methyl-dibenzothiophene 3-methyl-dibenzothiophene 2-methyl-dibenzothiophene
C1-benzothiophenes (6 isomers)
C2-dibenzothiophenes (26 isomers):
22 dimethyl-dibenzotiophene isomers and 4 ethyl-dibenzotiophene isomers
S
CH3
S
CH3
2-methyl-
benzothiophene
S
CH3
S
CH3
3-methyl-
benzothiophene
4-methyl-
benzothiophene
5-methyl-
benzothiophene
S CH3
6-methyl-
benzothiophene
S
CH3
7-methyl-
benzothiophene
Benzonaphthotiophenes
S
S S Benzo[b]naphtho[1,2-d]thiophene Benzo[b]naphtho[2,3-d]thiophene Benzo[b]naphtho[2,1-d]thiophene
Petroleum Biomarkers: Hopanes and Steranes
Bacteriohopanetetrol
(hopanoid in prokaryotes) Hopanes
A B
C D
E
1
2
3
4 5
6
7
8
9
10
11
12
13
14 15
16
17
18
19 20
21
22
23 24
25 26
27
28
30
29
31
32
33
34
35
C35H62O4
Cholesterol steroid in eukaryotes
Steranes
A B
C D 1
2
3
4 5
6
7
8
9
10
11
12
13
14 15
16
17
18
19
20 21 22
23
24 25 26
27
28
C27H46O
============================================================ 29
M+•
4% of TIC
C27H46
EI mass spectrum of 17α (H)-22,29,30-tris-norhopane
Petroleum Biomarkers
Steranes Hopanes
Multiple reaction monitoring mode
MRM
m/z 191
m/z 217
M+• → m/z 191 M+• → m/z 217
Waters Xevo TQ-S
Ion Source Diagram of APCI-GC/MS-MS
Corona Pin
Capillary
GC Column
Ionization
Chamber
Adapted from Waters Corporation
Ion source
Housing
Mass Spec
Heated Transfer Line
N2+• + M M+• + N2
(Atmospheric
Pressure)
Charge Transfer
Protonation
======================================================
Ionization mechanisms:
Charge Transfer vs. Protonation
By courtesy of Waters Corporation
Phenanthrene 100 pg
100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185
%
0
100
100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185
%
0
100
100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185
%
0
100 179
178
178
179
178
179
m/z
Ionization mechanisms: Charge Transfer vs. Protonation
“wet” source
“wet” source
“dry” source
M+•
[M+H]+
MW 178
Phenanthrene
M+•
[M+H]+
M+•
APCI-GC Mass Spectrum of 17α(H)-22,29,30-trisnorhopane
50 100 150 200 250 300 350 400
Rela
tive A
bu
nd
an
ce,
%
0
100 370
191
121 95 149 355
m/z
44% of TIC
M+•
APCI-GC/MS-MS of 17α(H)-22,29,30-trisnorhopane
Product (daughter) scan from M+• (m/z 370)
M+•
Collision energy: 15 eV
Collision gas: Ar
C27H46
m/z 50 70 90 110 130 150 170 190 210 230 250 270 290 310 330 350 370
%
0
100 191
95
81 69
149
109
135
121
163
177 355 370
MRM transition: m/z 370 → 191
MS/MS spectrum of 17α(H)-22,29,30-trisnorhopane
MS/MS spectrum from m/z 370
NIST library EI mass spectrum 17β(H)-22,29,30-trisnorhopane
The first match
Sum of 7 MRM transitions
17α(H)-22,29,30-trisnorhopane C27H46 M+•→ 191
17α(H),21β(H)-30-norhopane C29H50 M+•→ 191
17α(H),21β(H)-30-hopane C30H52 M+•→ 191
ααα 20R-cholestane C27H48 M+•→ 217
αββ 20R-cholestane C27H48 M+•→ 217
αββ 20R 24S-methylcholestane C28H50 M+•→ 217
ααα 20R 24R-ethylsholestane C29H52 M+•→ 217
17α(H),21β(H)-22R-homohopane C31H54 M+•→ 191
17α(H),21β(H)-22S-homohopane C31H54 M+•→ 191
αββ 20R 24R- ethylcholestane C29H52 M+•→ 217
pg
Calibration curve
17α(H),21β(H)-30-hopane
5E5
1E6
2E6
1.5E6
APCI-GC/MS-MS of NIST2266
(hopanes & steranes standard)
0 100 200 300 400 500 600
R² = 0.999
17α(H)-22,29,30-trisnorhopane
17α(H),21β(H)-hopane
17α(H),21β(H)-22S-homohopane 17α(H),21β(H)-22R-homohopane
17α(H),21β(H)-30-norhopane
APCI-GC/MS-MS of NIST2266. Hopanes.
m/z 370 → 191
m/z 398 → 191
m/z 412 → 191
m/z 426 → 191
αββ 20R-cholestane ααα 20R-cholestane
αββ 20R 24S-methylcholestane
αββ 20R 24R- ethylcholestane
ααα 20R 24R-ethylsholestane
APCI-GC/MS-MS of NIST2266. Steranes.
m/z 372 → 217
m/z 386 → 217
m/z 400 → 217
NIST2779 (Macondo crude oil)
Pricey samples from BP oil spill being sold to scientists
http://www.nola.com/news/gulf-oil-spill/index.ssf/2012/03/federal_government_sells_price.html
By Mark Schleifstein, NOLA.com | The Times-Picayune. March 08, 2012
It's likely to be one of the oddest ironies to emerge from the BP oil spill: the federal
government is selling tiny containers of oil siphoned from the Macondo well at a price
equal to $76.3 million a barrel. By comparison, a barrel of crude oil was selling for
$106 on Wednesday.
Of course, the BP oil is not being sold by the
barrel.
The National Institute of Standards and
Technology, an agency of the U.S. Department of
Commerce, is selling 1.2 milliliter bottles of the oil
to scientists who need it for comparison with
materials collected as part of the federal Natural
Resources Damage Assessment process. The
price: $480 for a set of five.
MS/MS conditions for acquisition of MRM transitions
Compound class MRM transition Dwell time, ms Collision
energy, eV
C27-Hopanes 370.30 > 191.10 50 15
C27-Steranes 372.30 > 217.10 50 20
C27-Steranes 372.30 > 218.10 50 20
C27-Steranes 372.30 > 259.20 50 20
C28-Hopanes 384.30 > 191.10 50 15
C28-Steranes 386.30 > 217.10 50 20
C28-Steranes 386.30 > 218.10 50 20
C28-Steranes 386.30 > 259.20 50 20
C29-Hopanes 398.30 > 191.10 50 15
C29-Steranes 400.30 > 217.10 50 20
C29-Steranes 400.30 > 218.10 50 20
C29-Steranes 400.30 > 259.10 50 20
C30-Hopanes 412.30 > 191.10 50 20
C30-Steranes 414.30 > 217.10 50 20
C31-Hopanes 426.30 > 191.10 50 20
C32-Hopanes 440.40 > 191.10 50 20
C33-Hopanes 454.40 > 191.10 50 20
C34-Hopanes 468.40 > 191.10 50 20
C35-Hopanes 482.40 > 191.10 50 20
APCI/GC-MS/MS of NIST2779 (Macondo crude oil)
Time, min
50.00 60.00 70.00 80.00 90.00 100.00 110.00 120.00
RA
, %
0
100
Time 80.00 82.00 84.00 86.00 88.00 90.00 92.00 94.00
Hopanes: Summed Signals for C27-C35 (M+• → m/z 191)
C35
C34 C33
C32
C31
H30
H29
Ts
Tm
H31S
H31R
H32S
H32R H33S
H33R H34S
H34R H35R
H35S
A B
C D
E
1 2
3 4
5 6
7 8
9
10
11 12
13
14 15
16
17
18
19 20
21
22
23 24
25 26
27
28 29
30
31
32
33
34
35
C29Ts
DH30
M30
m/z 372 → 217
m/z 386 → 217
m/z 372 → 217
βα
βα
αβ αβ
βα
βα
αβ αβ
αααS
βα
βα
αβ αααS
αααR
αβ
Time 50.00 55.00 60.00 65.00 70.00 75.00 80.00
50.00 55.00 60.00 65.00 70.00 75.00 80.00
%
100
50.00 55.00 60.00 65.00 70.00 75.00 80.00
50.00 55.00 60.00 65.00 70.00 75.00 80.00
0
%
100
0
%
100
%
100
0
0
APCI/GC-MS/MS of NIST2779 (Macondo crude oil)
C27 -Diasteranes C27-Steranes
C28 -Diasteranes
C28-Steranes
C29 -Diasteranes C29-Steranes
Sum of C27-C29 Steranes/Diasteranes
A B
C D 1 2
3
4 5
6
7
8
9
10
11 12
13
14 15
16
17
18
19
20 21 22
23
24 25 26
27
28 29
αααS
αββR
αααR αββS
αββR αββS
αααR
αββR αββS
Oil Spill Source Identification
NIST 2779 (Macondo crude oil) Environmental sample
ASTM D3328
ASTM D5739
Direct Visual Comparison of TIC
(and selected ion) chromatograms.
Reporting results:
Similar
Inconclusive
Dissimilar
C28
C29
C29
C27
C29
C27
C29
C30
C27
C28
C27
C29
C29
NIST 2779 (Macondo crude oil)
C30
C31
C32 C33
C29
C34
m/z 191
m/z 217
C28
C29
C29
C27
C29
C27
C29
C30
C27
C28
C27 C29
C29
Natural Oil Seep
m/z 217 Steranes/Diasteranes
Hopanes
C30
C31
C32
C33
C29
C34
C27
m/z 191
0
0,4
0,8
1,2
1,6
2
βαC27/βαC29
Diasteranes
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R
αββC27/αββC29
Steranes
H30/H31+H32+H33+H34+H35
NIST 2779 (Macondo crude oil)
0
0,4
0,8
1,2
1,6
2
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R H30/(H31+H32+H33+H34
+H35)
αββC27/αββC29
βαC27/βαC29
NIST2779 (Macondo crude oil)
Steranes
Diasteranes
SAM 1-18 collected
1-45 months after
the oil spill
"Megaplume" in the GC600 lease block:
Lat: 27° 22.466' N
Long: 90° 30.689'W
water depth: 1382m
Natural Oil Seeps (GC600, Megaplume)
Natural oils seeps in the Gulf of Mexico - 140,000 tonnes per year (range of
80,000 to 200,000 tonnes.
Natural Oil Seeps. The Gulf of Mexico.
from www.sarsea.org
0
0,4
0,8
1,2
1,6
2
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R H30/(H31+H32+H33+H34+H3
5)
αββC27/αββC29
βαC27/βαC29
Steranes
Diasteranes
Megaplume Oil Seep (GC600)
0
0,4
0,8
1,2
1,6
2
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R H30/(H31+H32+H33+H34+H35)
αββC27/αββC29
βαC27/βαC29
Steranes
Diasteranes
Blue crude (Anadarko Independence Hub)
Energy Fuels, 2011, 25 (1), pp 172–182
0
0,5
1
1,5
2
0
0,5
1
1,5
2
0
0,5
1
1,5
2
0
0,5
1
1,5
2
SAM-1 SAM-2 SAM-3
SAM-4 SAM-6
0
0,5
1
1,5
2
SAM-7
0
0,5
1
1,5
2
SAM-8
0
0,5
1
1,5
2
0
0,5
1
1,5
2
SAM-5
βαC27/βαC29
Diasteranes
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27βα/C29βα
Diasteranes
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27βα/C29βα
Diasteranes
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
Ts/Tm
βαC27/βαC29
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes C27αββ/C29αββ
Steranes
0
0,5
1
1,5
2
SAM-9
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
C27αββ/C29αββ
Steranes
0
0,5
1
1,5
2
SAM-10
0
0,5
1
1,5
2
SAM-11
0
0,5
1
1,5
2
SAM-12
0
0,5
1
1,5
2
SAM-13
0
0,5
1
1,5
2
SAM-14
0
0,5
1
1,5
2
SAM-15
SAM-16
0
0,5
1
1,5
2
0
0,5
1
1,5
2
SAM-17
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm Ts/Tm
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
C27αββ/C29αββ
Steranes C27αββ/C29αββ
Steranes C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes
C27αββ/C29αββ
Steranes C27αββ/C29αββ
Steranes
0
0,5
1
1,5
2
SAM-18
C27βα/C29βα
Diasteranes H29/H30
H32S/H32R
H33S/H33R H30/ΣH31‒H35
Ts/Tm
C27αββ/C29αββ
Steranes
0
0,4
0,8
1,2
1,6
2
βαC27/βαC29
Diasteranes
Ts/Tm
H29/H30
H32S/H32R
H33S/H33R
αββC27/αββC29
Steranes
H30/H31+H32+H33+H34+H35
NIST2779 (Macondo crude oil)
Blue crude (Independence Hub)
Megaplume oil seep (GC600)
SAM-10 (Pensacola Beach)
Overlaid spider diagrams
Correlation coefficients
Other case studies: Exxon Valdez oil spill
from www.uaf.edu
Prince William Sound, Alaska
March 24, 1989. 258,000 barrels
25,500 peaks
150 < m/z < 850
850 750 650 550 450 350 250 150
m/z
(+) APPI FT-ICR MS of Macondo crude oil
Relative Abundance (% total) Carbon Number
10
15
5
0
20
DB
E
10 20 30 40
S class (M+•)
50 60
DBE=12
S
DBE=9
R
10 20 30 40 50 60
25
30 HC class (M+•)
DBE=10
S
R
R
(+) APPI FT-ICR MS of Macondo crude oil
Mass Spec
UV-lamp
(Atmospheric
Pressure)
Heated Transfer Line
Capillary
GC Column
Ionization
Chamber
Ion source
Housing
APPI-GC/MS Ion Source Diagram
Kr UV-lamp
Atmospheric Pressure PhotoIonization (APPI)
Spectral distribution of a Krypton lamp
E=10.6 eV, λ= 117 nm
E=10.0 eV, λ= 124 nm
M+• M hν
hν > IE(M)
Ionization energies, IE (eV)
IE(N2) = 15.6 eV
IE(H2O)= 12.6 eV
IE(O2) = 12.1 eV
IE(C6H6) = 9.2 eV
IE(Toluene)= 8.8 eV
IE(Naphthalene) = 8.1 eV
IE (Phenanthrene) = 7.9 eV
IE (Thiophene) = 8.9 eV
IE (DBT) = 8.0 eV
IE(Alkanes) ~ 10 eV
- ē
100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190
%
0
100 178
m/z
APPI-GC/MS. Mass Spectrum of Phenanthrene
M+•
MW 178
IE = 7.9 eV
Phenanthrene (20 pg injected)
M+• M hν
time
5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00
%
0
100 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00
%
0
100
APPI-GC/MS vs APCI-GC/MS of Phenanthrene
APCI-GC/MS
m/z 178 →m/z 152
APPI-GC/MS
m/z 178 → m/z 152
S/N 4160
S/N 32830
APPI-GC/MS of Aromatic compounds
M+•
M+•
M+•
MW 168
IE = 8.1 eV
MW 167
IE = 7.6 eV
MW 184
IE = 7.9 eV
Time 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
%
0
100
Acenaphthylene
Naphthalene
Acenaphthene
Fluorene Anthracene
Benz[a]anthracene
Fluoranthene
Pyrene
Phenanthrene
Chrysene
Benzo[b]fluoranthene
Benzo[k]fluoranthene
Dibenz[a,h]anthracene
Benzo[g,h,i]perylene
Benzo[a]pyrene
Indeno[1,2,3-cd]pyrene
Boiling T 500 °C
APPI-GC/MS of 610 PAH Calibration Mix A
610 PAH Calibration Std (x 1000 dilution)
Final concentration: 500-1000 ng/mL
APPI/GC-MS/MS of NIST2779 (Macondo crude oil)
S
Me
Me
S
APPI with Argon lamp
Ar UV-lamp
E=11.6 eV, λ= 106.7 nm
E=11.8 eV, λ= 104.8 nm
Spectral distribution
of Ar lamp
0.105 ‒ 9 µm
LiF wavelength transmission range
17α(H),21β(H)-30-hopane
as internal standard Environ. Sci. Technol. 1994, 28, 142-145
APPI(Ar)-GC/MS-MS. PAHs and PASHs ratios.
Depletion of PAHs and PASHs in Environmental
samples from AL-MS shore line.
Phen DBT C2-Phen C2-DBT C3-Phen C3-DBT Chrys
≈
100
NIST 2779
(DWH) Jul, 2011 Feb, 2012 Jan, 2014
Depletion is relative to 17α(H),21β(H)-30-hopane (C30-Hopane)
We first utilized AP-GC/MS for a trace analysis of petroleum
biomarkers from the Macondo crude oil and environmental
samples.
We describe an Atmospheric Pressure PhotoIonization
(APPI) source that in combination with GC separation and
MS/MS analysis is an efficient method for characterization of
aromatic compounds in wellhead and spilled oil.
Analysis of petroleum compounds with APGC/MS-MS
provides a sensitive analytical tool for targeted analysis,
source identification of the oil spill, and tracking a fate of oil
spill residues.
SUMMARY
FT-ICR Group, NHMFL
Thank you!