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Oil Spill Source Identification with Advanced and Tiered Analytical Tools
Deyuan(Kitty) Kong, Mike Moir
Chevron Energy Technology Company
Robert Nelson, Chris Reddy
Woods Hole Oceanography InstitutionWoods Hole Oceanography Institution
August 6th, 2012
© 2012 Chevron
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Goal of Analysis – Data Quality Objective
What is it?How much is there?
Is it toxic?How old is it?
Who is responsible?H d ll t t ?How do we allocate costs?
Increasing cost, time, interpretive skill, fuzziness, and …
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Source Identification
You would like :
– Clarification ownership
You usually get:
Most Likely– Most Likely
– Multiple contributions
– Relative description – hypothesis
– Inconclusive or paradoxical results
You need to use:
M lti l li f id– Multiple lines of evidence
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Petroleum Product – Specifications
Specifications are designed to meet customer’s performance requirements
C ifi i i l d Customer specifications include:– Engine performance
– Environmental performanceEnvironmental performance
Performance is related to the complex mixture of hydrocarbons
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Gasoline Specifications- ASTM D4814
Prior to Federal RFG and CARB, gasoline was typically blended to meet octane RVP and distillation specificationsoctane, RVP and distillation specifications
– Reformulated (RFG) gasoline reduced RVP and added oxygenate, benzene and aromatics specifications for targeted air basins
– CARB gasoline went further by added specifications for sulfur, olefins, and more stringent distillation requirements for California
Emerging requirements – EPA Tier II and CARB Phase 3 g g q(Pharmaceutical Grade Gasoline!)
– Further reduction in sulfur and benzene specifications– Ethanol addition driven by renewable legislationEthanol addition driven by renewable legislation
Chemistry: Desire streams with iso-paraffins, naphthenes, toluene (non-b ti ) d l fi l l ithi li it h ll f
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benzene aromatic), and olefin molecules within limits, manage challenge of ethanol addition, minimize low octane normal paraffins
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Source Identification of Gasoline-Gasoline Blending ComponentsComponents
Distillation - light straight rung g Cracking Thermal - Coker light naphthag p Catalytic - FCC light naphtha Hydro - Isomaxatey
Alkylation - Alkylate Reforming - reformate Reforming reformate
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Approximate Carbon and Boiling Ranges of Petroleum ProductsProducts
Gasoline
Stoddard Solvent
Naphthas
JP-4
Jet Fuel/Kerosene
Diesel Fuel/ Middle Distillates
Lube Oil, Motor Oil, Grease
Fuel Oils
C CC CC C CC CC CC CC
69°C 126°C 216°C 343°C 402°C
750°F
449°C
840°F156°F 258°F 421°F 649°F
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40+C
C2 CC4 C C24C C10C C14C12 C18C16 C22C20 C30C28C266 8
7
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Diesel Fuel Oils by ASTM D975
Diesel Fuel Class SpecificationNo. 1-D S15 Special Purpose, Light middle Distillate UL
Diesel S< 15ppmNo. 1-D S500 Special Purpose, Light middle Distillate UL
Diesel S< 500 ppm
No. 1-D S5000 Special Purpose, Light middle Distillate UL Diesel S< 5000 ppmpp
No. 2-D S15 General Purpose, Light middle Distillate UL Diesel S< 15ppm
No. 2-D S500 General Purpose, Light middle Distillate ULNo. 2 D S500 General Purpose, Light middle Distillate UL Diesel S< 500 ppm
No. 2-D S5000 General Purpose, Light middle Distillate UL Diesel S< 5000 ppm
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No. 4-D A heavy distillate/Blend distillate/Residual Oil
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What are in Our Tool Boxes for source identification?
Refining Technology/Composition Changes
Star-gram- Pattern Recognition based on composition analysis
PAH distribution double ratio plot PAH distribution-double ratio plot
Biomarker Analysis for Diesel/Crude Oil
Bulk Stable Isotope Ratio Mass Spectrometry and CSIA-MS p p y(Compound Specific Isotope Analysis Mass Spectrometry)
Multidimensional GCxGC
M lti i t t ti ti l l i Multivariate statistical analysis
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Tiered Approach to Fingerprint oils in Environmental Forensic
D3328D6729D67298015
D57398260/8270
© 2012 Chevron
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Comparison of the Fingerprinting Methods
Both ASTM D3328-Standard Test Methods for comparison of waterborne Petroleum Oils by GC and D5739-Oil spill identification by GC and positive ion electron impact low resolution Mass spectrometry was introduced in 1995 are not suitable for Gasolines.
Both ASTM D3288 and D5739 are Semi-quantification though D5739 will provide the normalized histogram for the distribution of class of components.
D6729 Gasoline composition analysis with High Resolution GC only suitable for gasoline. EPA 8260 also could be used as the PIANO analysis. y
8015m and 8270C modification came from ASTM 3328 in 1974. Polyaromatic hydrocarbon and Biomarker could be added into 8270 test matrix with proper standards.
© 2012 Chevron
test matrix with proper standards.
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Qualitative Assessment by GC-FID-depends on DQO (Data Quality Objective)(Data Quality Objective)
8channel 38Las Vegas non carb oxygenated gasoline 00410/5/99 10:54:28 PM
channel 38Summer Diesel 00310/5/99 8:47:40 PM
Channel AEFT 1998-2 JET-A BATCH 1093
6
Crude OilC5
C10 C15 C20 C25C30 C35 C40
ts
6
IBF 380
Vol 4
Diesel #2
2Jet A
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0Gasoline
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Modified 8015 vs. Detailed Hydrocarbon Analysis D6729 (DHA method for gasoline composition analysis)(DHA method for gasoline composition analysis)
C3
nC
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Biomarkers in Petroleum Hydrocarbons
SESQUITERPANES (C13-C17)
OTP
OS
TAN
E ACYCLIC ISOPRENOIDS (C12-C19)LOW BOILING BIOMARKERS
AN
DR
DITERPENOIDS (C19-C22)
SESTERTERPENOIDS (C23-C26)
STEROIDS (C27-C31)TRITERPENOIDS
(C29-C40)
HIGH BOILING BIOMARKERS
GASOLINE/HEAVY NAPHTHA KEROSENE-JET A-DIESEL #1 DIESEL FUEL #2/FUEL OIL #2
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S U # / U O # BUNKER C/FUEL OIL#6
ENGINE/LUBE OILS
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Biomarkers provide additional evidence when dealing with biodegraded products m/z 191 tricyclic terpaneswith biodegraded products-m/z 191 tricyclic terpanes
180000
15000
17500
20000
22500
140000
160000
1400
Minutes0 10 20 30 40 50 60 70 80 90 100 110
uV
0
2500
5000
7500
10000
12500
80000
100000
120000
Res
pons
e uV
400
600
800
1000
1200
40000
60000
80000R
Minutes
0 10 20 30 40 50 60 70 80 90 100 110
0
200
0
20000
40000
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45 47 49 51 53 55 57 59
Retention Time (mints)
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Diagnostic Ratio originated from different classes of component to correlate the sourcecomponent to correlate the source
1Probable different mid-distillate oil inupriver mudflat sediments than Site oils
0.6
0.8
hena
nthr
enes
p
Probably two different mid-distillate oils at Site
0.4
0.6
open
es/C
3-Ph
Also have a heavyoil present
0
0.2
C3-
Dib
enzo
thi
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00 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
C
C2-Dibenzothiophenes/C2-Phenanthrenes
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GC×GC The Molecular MarathonThe Molecular Marathon
© 2012 Chevron R. K. Nelson
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Multidimensional Biomarker Separation
bicyclic biphytanes monocyclic biphytanes25-norhopanes
10374 isoprenoidalalkaneshopanes
8374
1st DimensionRetention Time
( d )
diasteranes&
steranes
6374
(seconds)
triaromaticsteranes
monoaromatic(C-ring) steranes
normalalkanes
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05102nd Dimension Retention Time (seconds)
4374
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uniqueisoprenoid
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Difference Chromatogram
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Interpretation of fingerprinting data is not always easy
Broad range of fuel specifications• no product is sold as molecules, specifications are based on
performance -octane number, V/L (vapor/liquid) and regulations -RVP (Reid vapor pressure), Benzene( p p )
• Limits on total olefins, aromatics, Lead, Sulfur, and MTBE are recent regulation
W th i Weathering– Evaporation
– BiodegradationBiodegradation
– Oxidation
– sorption
© 2012 Chevron
Mixtures of products and sources
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Acknowledgement
Al Verstuyft- Chevron Retireey
Liz Harvey-Chevron Retiree
Chevron EMC
Q&AQ&A
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