Application of Bicyclic Sesquiterpanes · Total saturated hydrocarbons 13.3 26.8 41.2 18.8 Total...
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Transcript of Application of Bicyclic Sesquiterpanes · Total saturated hydrocarbons 13.3 26.8 41.2 18.8 Total...
Application of Bicyclic Sesquiterpanes Application of Bicyclic Sesquiterpanes in Forensic Identification of Light in Forensic Identification of Light Petroleum Products Spilled on WaterPetroleum Products Spilled on Water
Chun Yang, Zhendi Wang, Bruce Hollebone, Carl E. BrownChun Yang, Zhendi Wang, Bruce Hollebone, Carl E. BrownMike Landriault, Zeyu YangMike Landriault, Zeyu Yang
Emergencies Science and Technology SectionEmergencies Science and Technology SectionScience and Technology Branch, Environment CanadaScience and Technology Branch, Environment Canada335 River Road, Ottawa, Ontario, Canada K1A 0H3335 River Road, Ottawa, Ontario, Canada K1A 0H3EE--mail: mail: [email protected]@ec.gc.ca
PolymethylPolymethyl--substituted decalinssubstituted decalins
Containing three isoprene subunitsContaining three isoprene subunits
Containing two hexylContaining two hexyl--ring (or cyclohexylring (or cyclohexyl--).).
What is Bicyclic What is Bicyclic SesquiterpanesSesquiterpanes??SesquiterpanesSesquiterpanes
head
tail
The bicyclic biomarker sesquiterpanes with theThe bicyclic biomarker sesquiterpanes with thedrimane skeleton (Cdrimane skeleton (C1414--CC1616) are ubiquitous components ) are ubiquitous components of crude oils and ancient sediments. of crude oils and ancient sediments.
Most sesquiterpanes probably originate not only from Most sesquiterpanes probably originate not only from high plantshigh plants but also from but also from algae or bacteriaalgae or bacteria
The concentration of CThe concentration of C1414 sesquiterpanes is higher sesquiterpanes is higher at at the immature stagethe immature stage, while those of C, while those of C1515 drimane and drimane and CC1616 homodrimane are homodrimane are relatively lowerrelatively lower..
What is Bicyclic What is Bicyclic SesquiterpanesSesquiterpanes??
Early studies mainly focused on geological application Early studies mainly focused on geological application of sesquiterpane compounds. of sesquiterpane compounds.
The abundance of major compounds in the The abundance of major compounds in the m/z m/z 123 123 chromatograms has been employed to differentiate the chromatograms has been employed to differentiate the organic matter input from various sedimentary organic matter input from various sedimentary environments. environments.
TThe naturally occurring bicyclic sesquiterpanes are he naturally occurring bicyclic sesquiterpanes are stable in biodegradation, therefore, have stable in biodegradation, therefore, have potential potential applications in oilapplications in oil--source correlation and source correlation and differentiation.differentiation.
What is Bicyclic What is Bicyclic SesquiterpanesSesquiterpanes??
Biomarkers play a very important role in Biomarkers play a very important role in characterization, correlation, differentiation, and characterization, correlation, differentiation, and source identification in environmental forensic source identification in environmental forensic investigations of oil spills. investigations of oil spills.
The commonly used biomarkers include pentacyclic The commonly used biomarkers include pentacyclic triterpanes (e.g., hopanes), regular and rearranged triterpanes (e.g., hopanes), regular and rearranged steranes, and monosteranes, and mono-- and triand tri--aromatic steranes.aromatic steranes.
WhyWhy SesquiterpanesSesquiterpanes??
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Bicyclic sesquiterpane
n-C
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n-C
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n-C
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n-C
24
n-C
27
n-C
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n-C
33
n-C
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Diterpanes
Tri- & tetra- cyclic terpanes
Pentacyclic terpanes
C21 to C22 steranes C27 to C29 steranes
n-C
13
Gasoline (~n-C3 to n-C13)
Jet fuels/kerosenes (~n-C5 to n-C18)
Diesel fuels (~n-C9 to n-C24)
Heavy fuels (HFO)/lube oils, etc. (~n-C18 +)
Crude oils (~n-C5 to n-C44+)
n-C
21
n-C
9
The The high MW high MW biomarkers biomarkers occur within the residual occur within the residual rangerange.. For lighter petroleum products like jet fuels and For lighter petroleum products like jet fuels and diesel, the refining processes diesel, the refining processes remove remove most most of these of these compoundscompounds from the original oil feedstock. from the original oil feedstock.
The smaller The smaller bicyclic sesquiterpanes bicyclic sesquiterpanes are are concentratedconcentrated in in these products.these products.
WhyWhy SesquiterpanesSesquiterpanes??
C16
(MW: 222)
C15
(MW: 208)
C14
(MW: 194)
Bp: 235ºC
Bp: 287ºC
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1238β(H)-drimane
GC/MS GC/MS Determination of Determination of bicyclic bicyclic sesquiterpanessesquiterpanes
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Bicyclic terpane
Sesquiterpanes in Sesquiterpanes in Crude Crude Oils Oils and and PPetroleum Productsetroleum Products
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Sesquiterpanes in Crude Oils
Sesquiterpanes in Crude Oils
Oil samples Total (µg/g oil)
Mississippi Canyon 917Maya 969Mars TLP 976West Delta Canyon 1,010Platform Elly 1,129
Arabian Heavy 1,904
Alaska North Slope 2,179Cook Inlet 2,211Prudhoe Bay 2,551
Orinoco bitumen 1,302
Cold Lake bitumen 2,124
Federated 3,670Troll 5,119South Louisiana 5,155
Sesquiterpanes in Petroleum Products
Col 1 vs Col 2 Col 1 vs Col 2
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Sesquiterpanes (m/z 123)
Biomarker terpanes(m/z 191)
Sesquiterpanes in Petroleum ProductsOil samples Total (µg/g oil)Winter gasoline NDKerosene 0.7Aviation gasoline 30.6Jet-A 6,770Diesel-Pioneer 7,628Diesel-Shell 8,703Diesel-Stinson 8,447Diesel-Ottawa 6,028Korea diesel #1 7,658Korea diesel #2 5,819Korea diesel #3 6,129Fuel #4 4,221IFO-180 2,033Fuel No. 5 1,449Bunker C 255Valvoline-10W-30 10.1Pennzoil synthetic-10W-30 15.3Extreme pressure gear 15.6
Summaries:Summaries: Sesquiterpanes in OilsSesquiterpanes in Oils
The presence of bicyclic sesquiterpanes in crudes and The presence of bicyclic sesquiterpanes in crudes and petroleum products are apparent.petroleum products are apparent.The oils from different sources demonstrate The oils from different sources demonstrate differences in both the absolute concentrations and differences in both the absolute concentrations and relative distribution patterns of sesquiterpanes. relative distribution patterns of sesquiterpanes. The pentacyclic triterpanes and steranes are The pentacyclic triterpanes and steranes are generally generally absentabsent in lighter petroleum products, but in lighter petroleum products, but bicyclic bicyclic sesquiterpanes are present in diesels and certain jet sesquiterpanes are present in diesels and certain jet fuels with significant abundances.fuels with significant abundances.
Sesquiterpanes in Distillation FractionSesquiterpanes in Distillation Fractionss
Alaska Alaska nnorth orth sslopelope crude oilcrude oil F1 F2 F3 F4
Mass (%) 20.6 15.5 31.3 29.5Boiling point range (ºC) IBP-180 180-287 287-481 >481Main carbon range <C12 C9 – C18 C14 – C34 >C34
Hydrocarbon groups (%)Total petroleum hydrocarbons 11.1 22.5 43.4 23.0Total saturated hydrocarbons 13.3 26.8 41.2 18.8Total aromatic hydrocarbons 4.0 9.3 50.4 36.2n-Alkanes 20.2 34.8 41.8 3.2Biomarker terpanes 0.0 0.3 53.4 46.3Biomarker steranes 0.0 0.2 90.4 9.5C30 bb-Hopane 0.0 0.1 51.3 48.6
100%100%
0%0%
0.3%0.3%
53.4%53.4%
46.3%46.3%
Sesquiterpanes Biomarker Terpanes
0%0%
100%100%
0.7%0.7%
46.7%46.7%
52.6%52.6%
SesquiterpanesSesquiterpanes (%)(%) F1 F2 F3 F4BS1 1.0 89.4 9.6 0.0
BS2 1.3 86.6 12.1 0.0
BS3 0.8 71.3 28.0 0.0
BS4 0.6 62.5 36.9 0.0
BS5 0.4 56.1 43.4 0.0
BS6 0.4 52.6 47.0 0.0
BS7 0.3 48.4 51.3 0.0
BS8 0.2 43.5 56.3 0.0
BS9 0.3 40.4 59.3 0.0
BS10 0.4 37.5 62.1 0.0
Sesquiterpanes in Distillation FractionSesquiterpanes in Distillation Fractionss
Biomarker terpanes and steranesBiomarker terpanes and steranes were found almost were found almost entirely in heavier entirely in heavier fractions 3 and 4fractions 3 and 4 due to their high due to their high boiling pointsboiling pointsSesquiterpanesSesquiterpanes were largely found in were largely found in fractions 2 and 3fractions 2 and 3. . For fraction 2, all ten target sesquiterpanes were For fraction 2, all ten target sesquiterpanes were concentrated up to approximately fiveconcentrated up to approximately five--fold compared fold compared to the native crude oilsto the native crude oilsSesquiterpanes were in low concentration in the Sesquiterpanes were in low concentration in the lightest fraction 1 and rarely found in the heaviest lightest fraction 1 and rarely found in the heaviest fraction 4.fraction 4.
Summaries:Summaries: Sesquiterpanes in Sesquiterpanes in Distillation FractionDistillation Fractionss
Weathering Weathering EEffects on ffects on SSesquiterpane esquiterpane DistributionsDistributions
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Prudhoe Bay (13.1% w eathered)
Prudhoe Bay (6.3% w eathered)
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Diesel [2002] (22.0% w eathered)
Diesel [2002] (14.2% w eathered)
Diesel [2002] (7.2% w eathered)
Diesel [2002] (fresh)
Summaries:Summaries: Weathering Weathering EEffects on ffects on SSesquiterpane Distributionsesquiterpane DistributionsIn general, In general, light to mediumlight to medium weathering has little weathering has little effects on distribution pattern and diagnostic ratio effects on distribution pattern and diagnostic ratio values of sesquiterpanes. values of sesquiterpanes. SSmaller Cmaller C1414 sesquiterpanes (BS1 and BS2) start to be sesquiterpanes (BS1 and BS2) start to be lost as oil subjected to high percentages of weathering lost as oil subjected to high percentages of weathering ..MMost of sesquiterpane ratios are robust for correlation ost of sesquiterpane ratios are robust for correlation and differentiation of oil samples in that have only and differentiation of oil samples in that have only lightly to moderately weatheredlightly to moderately weatheredTThe he most heavily weatheredmost heavily weathered might result in certain might result in certain changes for such ratios as BS1/BS5, BS3/BS10 and changes for such ratios as BS1/BS5, BS3/BS10 and BS5/BS10.BS5/BS10.
Application of Bicyclic Application of Bicyclic Sesquiterpanes in Forensic Sesquiterpanes in Forensic Identification of Oil SpillIdentification of Oil Spill
Case Study:Case Study:Oil Spill in Northbay, OntarioOil Spill in Northbay, Ontario
Oil Spill in Northbay, OntarioOil Spill in Northbay, OntarioIn 2008, WaggIn 2008, Wagg’’s Petroleum Equipment Ltd. was s Petroleum Equipment Ltd. was hired by the Department of National hired by the Department of National DefenceDefence(DND) and Canadian Forces Exchange System (DND) and Canadian Forces Exchange System ((CanexCanex) at Canadian Force Base (CFB) at North ) at Canadian Force Base (CFB) at North Bay to clean up a hydrocarbon spill at one of the Bay to clean up a hydrocarbon spill at one of the sites.sites.The site is a fueling site for gasoline only and this The site is a fueling site for gasoline only and this site has had 3 spills; one in 1998, one in 2002 and site has had 3 spills; one in 1998, one in 2002 and one in 2008one in 2008Preliminary laboratory test indicates the spilled oil Preliminary laboratory test indicates the spilled oil is not pure gasoline, could be a mixture with other is not pure gasoline, could be a mixture with other type of fuel.type of fuel.
Oil Spill in Northbay, OntarioOil Spill in Northbay, Ontario
Spill site: Northbay, OntarioSpill site: Northbay, OntarioTwo water samples: Two water samples:
2008/04/22/2008/04/22/--1290, 1290, 2008/04/22/2008/04/22/--12911291Oil layer on water surface was Oil layer on water surface was clearly observed. clearly observed.
Oil Fingerprinting AnalysisOil Fingerprinting Analysis
The water samples were separated into two parts: The water samples were separated into two parts: oil phase and water phaseoil phase and water phase respectively;respectively;Oil layerOil layer:: Approximately 0.5 Approximately 0.5 mLmL of oil was of oil was
removed from the top oil layer of two water removed from the top oil layer of two water samples. About 16.0 mg of oil was used for samples. About 16.0 mg of oil was used for fingerprinting analysis.fingerprinting analysis.Water layerWater layer: The water samples were weighed : The water samples were weighed and then transferred to and then transferred to separatoryseparatory funnels and funnels and extracted (liquid/liquid extraction) with extracted (liquid/liquid extraction) with dichloromethane (DCM) three times (50/50/50 dichloromethane (DCM) three times (50/50/50 mLmL).).
Oil Fingerprinting AnalysisOil Fingerprinting Analysis~
16 mg of oil
3-g silica gelcolumn cleanup and fractionation
Surrogates
Saturated fraction (F1) Aromatic fraction (F2)
GC/MS-SIM(biomarker, sesquiterpanes, diamondoids, n-alkanes, etc.)
GC/MS-SIM(BTEX, EPA priority PAHs, alkylated PAHs,
mono-/tri-aromatic steranes, etc.)
Internal Standards(d18-decalin, ßß-hopnae,etc.)
Internal Standard (d14-terphenyl)
Sample 1290
ESTD code2008/04/22-
1290Oil2008/04/22-
1290L2008/04/22-
1291Oil2008/04/22-
1291L Diesel
Customer sample info. Oil Layer Water Oil Layer Water Shell [2003]
TPH (mg/g) 768 803 805 705 957
TSH/TPH (%) 75.8 80.2 84.4 77.9 89.8
TAH/TPH (%) 24.2 19.8 15.6 22.1 13.6
Resolved/TPH (%) 57.0 53.5 53.9 52.0 22.3
∑n-Alkanes (mg/g) 72.4 77.4 76.5 67.9 128
∑EPA PAHs (mg/g) 0.24 0.30 0.25 0.27 0.61
∑APAHs (mg/g) 13.4 16.6 13.6 14.9 19.9
∑Biomarkers (mg/g) 0.052 0.067 0.060 0.060 0.014
Hydrocarbon Group Analysis ResultsHydrocarbon Group Analysis Results
Sample 1290
N-Alkane Distribution
Sample 1290
2008/04/22-1290Oil
0.02.04.06.08.0
10.0
n-C
8n-
C9
n-C
10n-
C11
n-C
12n-
C13
n-C
14n-
C15
n-C
16n-
C17
Pris
tane
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18Ph
ytan
en-
C19
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20n-
C21
n-C
22n-
C23
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24n-
C25
n-C
26n-
C27
n-C
28n-
C29
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30n-
C31
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C33
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2008/04/22-1291Oil
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n-C
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tane
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18Ph
ytan
en-
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C21
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22n-
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26n-
C27
n-C
28n-
C29
n-C
30n-
C31
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C33
n-C
34
Con
c. (m
g/g
sam
ple)
BTEX and PAHs Analysis
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TIC: 0402014.D
BTEX and substituted benzenes
Sample 1290
2008/04/22-1290Oil
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aph
C1-
N
C2-
N
C3-
N
C4-
N
Phen
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P
C3-
P
C4-
P
Dib
en
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Fluo
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Other EPA Priority PAHs
0100200
Bph
Acl
Ace An Fl Py
BaA
BbF
BkF
BeP
BaP Pe IP DA
DgP
2008/04/22-1291Oil
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h
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C2-
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C3-
N
C4-
N
Phen
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C3-
P
C4-
P
Dib
en
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C2-
D
C3-
D
Fluo
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Chr
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0100200
Bph
Acl
Ace An Fl Py
BaA
BbF
BkF
BeP
BaP Pe IP DA
DgP
BTEX and PAHs Analysis
Biomarkers Analysis
26.0028.0030.0032.0034.0036.0038.0040.0042.0044.0046.0048.0050.0052.0054.000
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Ion 191.00 (190.70 to 191.70): 1202038.D
30.0031.0032.0033.0034.0035.0036.0037.0038.0039.0040.0041.0042.0043.0044.000
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Ion 218.00 (217.70 to 218.70): 1202038.D
Sample 1290
Biomarker terpanes(m/z 191)
IS
Biomarker steranes(m/z 218)
C27 α
ββ
C28 α
ββ
C29 α
ββ
AnswerAnswerThe spilled oil is a mixture of a The spilled oil is a mixture of a GasolineGasoline and aand a DieselDiesel !!!!!!
Questions Questions How much How much GasolineGasoline ??How much How much DieselDiesel ??
Bicyclic Sesquiterpanes Analysis
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Ion 123.00 (122.70 to 123.70): 1202038.D
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Ion 123.00 (122.70 to 123.70): 1302042.D
Sample 1290 BS10
BS3
BS5
BS1 B
S2
BS4
BS6 B
S7
BS8
Sample 1291
Sesquiterpanes AnalysisOil samples Total (µg/g)2008/04/22-1290 Oil 3,4762008/04/22-1290 Water 3,9732008/04/22-1291 Oil 4,0222008/04/22-1291 Water 3,772Mean 3811
Diesel-Ottawa 6,028
Gasoline NDKerosene 0.7Diesel-Pioneer 7,628Diesel-Shell 8,703Diesel-Stinson 8,447
Mean 7702
AnswerAnswerThe spilled oil is a mixture of a The spilled oil is a mixture of a GasolineGasoline and aand a DieselDiesel
GasolineGasoline :: DieselDiesel = ~50:50= ~50:50 !!!!!!
Simulation of Spilled Oils
Gasoline: from Petro Canada gas station, Ottawa
Diesel: from Shell gas station, Ottawa
Gasoline : Diesel = 100:0, 90:10, …, 0:100 (v:v).
Simulation of Spilled Oils
Bicyclic Bicyclic sesquiterpanes are widely present in sesquiterpanes are widely present in crude oils and diesel range petroleum products crude oils and diesel range petroleum products with significant abundances. with significant abundances. Sesquiterpanes offer potential criteria for both Sesquiterpanes offer potential criteria for both oil identification and oiloil identification and oil--source correlation in source correlation in cases where the traditional biomarkers are cases where the traditional biomarkers are absent due to refining of petroleum product or absent due to refining of petroleum product or environmental weathering. environmental weathering.
ConclusionsConclusions
ConclusionsConclusions
The oil samples are gasoline/diesel type fuel. The oil samples are gasoline/diesel type fuel.
The oil samples are probably mixtures of The oil samples are probably mixtures of gasoline and diesel (No. 2) at an approximate gasoline and diesel (No. 2) at an approximate ratio of 50:50 (v:v).ratio of 50:50 (v:v).
Thank You!Thank You!
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