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

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

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

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

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

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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.

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test matrix with proper standards.

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

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

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)

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

GC×GC The Molecular MarathonThe Molecular Marathon

© 2012 Chevron R. K. Nelson

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

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

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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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