Vlad Lobodin, National High Magnetic Field Laboratory & Future Fuels Institute, Florida State University, Tallahassee, Florida - discusses advanced mass spectrometry techniques for the characterization of crude oil.
APCI and APPI GC/MSMS for Characterization of the Macondo Wellhead Crude Oil and the Oil Spill
1. APCI- and APPI-GC/MS-MS for
Characterization of the Macondo Wellhead
Crude Oil and the Oil Spill
Vlad Lobodin
1
National High Magnetic Field Laboratory, Tallahassee, FL
Future Fuels Institute, Florida State University, Tallahassee, FL
17. 462.1345
m/z
464463462
m/z 462.13489
[ C27 H24 N4
58Ni ]+•
(+80ppb)
m/z 462.13432
[ C30 H24 N1 S2 ]+•
(+300ppb)
570 µDa
Theoretical Abundance 2.6%
Experimental Abundance 1.9%
N
N
N
N
OV
DBE = 18
58Ni
Mass e- 548 µDa
Direct Speciation of Metalloporphyrins in Crude Oil
18. 1H = 1.007825
12C= 12.00000
Mass Defect
1
H
2
H
13
C
14
N 15
N12
C
16
O
19
F
17
O
18
O
31
P 32
S
33
S 34
S 36
S
35
Cl 37
Cl
79
Br
81
Br
127
I
Nuclide
Massdefect,mDa
14N = 14.003074
16O= 15.994915
19. 1. Carbon Number
2. Heteroatom Composition
3. Aromaticity
m/z 704.53510
[C50H72S1]+•
800700600500400
*
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
DBE
S1 Class
Relative Abundance (% total)
40
30
20
10
0
20 40 60 80
Workflow for High Resolution “Petroleomics”
20. S
CH3
Isomeric structure for S-compounds
S
CH3
C1-dibenzothiophenes (4 isomers)
S
CH3
S
CH3
1-methyl-dibenzothiophene 4-methyl-dibenzothiophene3-methyl-dibenzothiophene2-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
SCH3
6-methyl-
benzothiophene
S
CH3
7-methyl-
benzothiophene
Benzonaphthotiophenes
S
S S
Benzo[b]naphtho[1,2-d]thiopheneBenzo[b]naphtho[2,3-d]thiopheneBenzo[b]naphtho[2,1-d]thiophene
21. 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 D1
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
25. 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)
29. 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
33. 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.
39. "Megaplume" in the GC600 lease block:
Lat: 27° 22.466' N
Long: 90° 30.689'W
water depth: 1382m
Natural Oil Seeps (GC600, Megaplume)
40. 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
47. Other case studies: Exxon Valdez oil spill
from www.uaf.edu
Prince William Sound, Alaska
March 24, 1989. 258,000 barrels
48. 25,500 peaks
150 < m/z < 850
850750650550450350250150
m/z
(+) APPI FT-ICR MS of Macondo crude oil
49. Relative Abundance (% total) Carbon Number
10
15
5
0
20
DBE
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
57. 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
59. 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)
60. 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
66. APCI-GC/MS conditions
Mass spectrometer – Waters Xevo TQ-S
Tsource 150ºC
Corona 2.5 μA
Cone voltage 30V
Source offset 50V
Auxilliary gas (N2) 200 L/hr
Cone gas (N2) 250 L/hr
Collision gas Ar
Gas chromatograph –7890
Tinj=300ºC
Column: MXT-5 (or MXT-1), 60m × 0.25mm × 0.25 µm
Carrier gas: He
Flow rate: 1.2 mL/min
Split ratio: 1:10
Oven: 50ºC - 20ºC/min -150ºC- 2ºC/min - 350ºC (25 min)
Transfer Line: 380ºC
Injected volume: 1 μL
67. APPI-GC/MS conditions
Mass spectrometer – Waters Xevo TQ-S
Tsource 150ºC
Kr UV lamp 10 eV (or Ar UV lamp 11.7 eV)
Cone voltage 30V
Source offset 50V
Auxiliary gas (N2) 200 L/hr
Cone gas (N2) 150 L/hr
Collision gas Ar
Gas chromatograph –7890
Tinj=300ºC
Column: MXT-5 (or MXT-1), 60m × 0.25mm × 0.25 µm
Carrier gas: He
Flow rate: 1.2 mL/min
Split ratio: 1:10
Oven: 50ºC - 20ºC/min -150ºC- 2ºC/min - 350ºC (25 min)
Transfer Line: 380ºC
Injected volume: 1 μL
68. APPI(Ar)-GC/MS-MS. PAHs and PASHs ratios.
NIST2279 (DWH) Jul 17, 2011 Feb 8, 2012 Jan 27, 2014
С2-Phen/C2-DBT 2.9 2.8 2.3 2.8
С3-Phen/C3-DBT 1.9 1.4 1.4 1.5
С2-Phen/C2-DBT and С3-Phen/C3-DBT ratios
69. SAM-1 (30°17'15.0”N, 87°28'44.6”W))on 04.05.2011,
SAM-2 (30°17'14.6”N, 87°28'50.2”W) on 04.06.2011,
SAM-3 (30°14'25.6”N, 87°44'14.8”W) on 07.17.2011
SAM-4 (29°10'29.3”N, 90°04'33.2”W) on 07.17.2011,
SAM-5 (30°17'18.4”N, 87°28'37.8”W) on 07.19.2011,
SAM-6 (30°14'48.4”N, 87°41'35.2”W) on 11.27.2011
SAM-7 (30°14'25.4”N, 87°44'15.2”W) on 11.28.2011,
SAM-8 (29°56'41.0”N, 88°49'27.0”W) on 11.28.2011,
SAM-9 (29°17'35.5”N, 90°29'17.5”W) on 05.31.2010,
SAM-10 (30°19'32.1”N, 87°10'30.5”W) on 06.23.1010,
SAM-11 (30°14'60.6”N, 88°53'21.1”W) on 02.09.2012,
SAM-12 (30°18'16.4”N, 87°23'20.9”W) on 02.07.2102,
SAM-13 (30°14'34.8”N, 88°42'59.1”W) on 02.08.2012,
SAM-14 (30°14'26.3”N, 87°44'16.9”W) on 08.31.2012,
SAM-15 (30°13'54.4”N, 88°53'47.0”W) on 02.09.21012,
SAM-16 (30°18'30.8”N, 87°22'16.3”W) on 02.07.2012,
SAM-17 (29°10'30.0”N, 90°04'33.6”W) on 07.31.2011,
SAM-18 (30°15'16”N, 88°7'50”W) on 01.27.2014,
Megaplume (27°22'27.96”N, 90°30'41.34”W) - depth – 1200 m, GC600.
Blue crude oil (28°05'89.0”N, 87°59'27.0”W).
Samples’ collection sites and time
70. Petroleum Biomarkers. Hopanes.
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
29
30
31
32
33
34
35
Over 150 distinct, naturally-occurring hopanoids have been identified in soils, sediments, and other
organic matter. Hopanoids have a fixed stereochemistry and differ in the orientation about Carbon-
17 and Carbon-21 (α or β) and Carbon-22 (R or S).
17β, 21β(H) is biological configuration
The order of thermodynamic stability of the 17-21 hopane isomers is
17α(H),21β(H) > 17β(H),21α(H) > 17α(H),21α(H) > 17β(H),21β(H)
22R is biological configuration.
17α(H),21β(H) –hopanes are the most stable. 17β(H),21α(H) are called moretanes.
22S/(22S+22R) ~ 0.58-0.62 for C31-hopane
C35H62O4
71. Cholesterol
Petroleum Biomarkers. Steranes.
steroid in eukaryotes Steranes
A B
C D1
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
C27H46O
5α,14α,17α(H)–cholestane-20R
biological configuration
5α,14β,17β(H)
stable configuration
14β,17β(H)/[14α,17α(H) + 14β,17β(H)] ~ 0.7 – Endpoint configuration
Diasteranes (rearranged steranes) - rearrangement product from sterol precursors through
diasterenes. The rearrangement involves migration of C-10 and C-13 methyl groups to C-5 and
C-14 and is favored by acidic conditions, clay catalysis, and/or high temperatures. Diasteranes
increase relative to steranes with thermal maturation and they are low in clay-poor carbonate
source rocks and related oils.
13β(H),17α – diasteranes 20S or 20R
89. Relative Abundance (% total)
Carbon Number
10
15
5
0
20
DBE
10 20 30 40
S class (M+•)
50 60
C#=19
DBE=12
DBE=6
S
R
25
30
S
C3
S
R
(+) APPI FT-ICR MS of Macondo crude oil
DBE=12
DBE=9
S
R
C2-dibenzothiophenes (26 isomers):
22 dimethyl-dibenzotiophene isomers and
4 ethyl-dibenzotiophene isomers
90. S
CH3
Isomeric structure for S-compounds
S
CH3
C1-dibenzothiophenes (4 isomers)
S
CH3
S
CH3
1-methyl-dibenzothiophene 4-methyl-dibenzothiophene3-methyl-dibenzothiophene2-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
SCH3
6-methyl-
benzothiophene
S
CH3
7-methyl-
benzothiophene
Benzonaphthotiophenes
S
S S
Benzo[b]naphtho[1,2-d]thiopheneBenzo[b]naphtho[2,3-d]thiopheneBenzo[b]naphtho[2,1-d]thiophene
93. APCI. Mechanism of Ionization (I)
Charge Transfer
• The nitrogen in the source is ionized by corona discharge by the
following series of reactions:
N2 + e ¯ → N2
+• + 2e ¯
N2
+• + 2N2 → N4
+• + N2
• If the nitrogen is dry the N2
+• and N4
+• act as reagent ions with charge
transfer being the most likely pathway for ionization.
N2
+•/ N4
+• + A → A+• + xN2 charge transfer
Where A represents an analyte molecule
• Charge transfer results in the formation of radical cations and is
particularly useful for the ionization of non-polars.
94. APCI. Mechanism of Ionization (II)
Proton Transfer
• In the presence of water vapour the following reactions then occur to
generate ionized water clusters:
N4
+• + H2O → H2O+• + 2 N2
H2O+• + H2O → H3O+ + OH•
H3O+ + H2O + N2 → H+(H2O)2 + N2
H2O + H+(H2O)2 → H+(H2O)3 + N2
• The last reaction can then proceed further with successive additions
of water
• Ionization of the analyte then occurs by proton transfer
H3O+ + A → AH+ + H2O proton transfer
• Proton transfer is the main ionization pathway associated with APCI
in LC/MS.
95. 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170
%
0
100
152
128
178
APPI-GC/MS-MS of Phenanthrene (m/z 178)
m/z
M+•
[M-C2H2]+•
[C10H8]+•
C14H10
-C2H2
Collision energy (Ekin) = 27 eV
Collision gas - Ar
Eint =Ekin
Mgas
Mion + Mgas
Product (daughter) scan from M+• (m/z 178)
96. MS/MS spectrum of Phenanthrene (m/z 178)
MS/MS spectrum
from m/z 178
NIST library EI mass spectrum
of Phenanthrene
The first match
97. Wavelength Transmission/Absorption Range
0.11 ‒ 7.5 µm
N2 < 0.1 O3 0.17-0.35 0.45-0.75
O2 < 0.245 H2O < 0.21 0.6-0.72
Gas Absorption wavelengths (μm)
MgF2 (window) wavelength transmission range