Analysis of Trace Fatty IP Method PM-DY/09 -

Acid Methyl Esters GC/MS with Selected Ion

(FAME) in Jet Fuel Monitoring

Chemical Analysis Group

James D. McCurry, Ph.D.

Senior Scientist
Agilent Restricted
January, 14, 2010

Agilent Restricted
1 January 14, 2010
Introduction

• Increasing quantities of biodiesel and jet are being co-transported in multi-

product pipelines (MPP)
• In MPP transportation trace amounts of FAME can be found in jet parcels
following biodiesel parcels due to FAME ‘trail back’.
• Following pipeline trials to establish the amount and profile of FAME ‘trail
back’ into jet fuel
• JIG PQ committee work on the effect of various FAMEs (up to 400 ppm) on
the specification properties of jet fuel the main engine
• Commercial aircraft OEMs gave approval of limit of 5 mg/kg total FAME in
jet fuel
• New method developed using single column GC/MS to detect individual
FAMEs from 0.5 mg/kg to 50 mg/kg
– IP PM-DY/09 Method for Determination of FAME in Jet Fuel – GC/MS
with Selected Ion Monitoring

Agilent Restricted
2 January 14, 2010
FAMEs from Vegetable Derived Biodiesel
Data courtesy of Tom Lynch, BP

Acid (% wt) Castor Coconut Corn Linseed Olive Palm Peanut Rape Soya Sunflower Jatropha

Saturated acids
Caproic C6:0 0.8
Caprylic C8:0 5.4
Capric C10:0 8.4
Lauric C12:0 45.4
Myristic C14:0 18.0 1.0 1..5 0.06
Palmitic C16:0 10.5 7..5 9.0 48 5.0 4.2 6.5 3.5 14.6
Stearic C18:0 0.3 2..3 3.5 3.5 2..3 4.0 5.0 1.5 4.2 2.9 7.15
Arachidic C20:0 0.4 0.5 0.2 4.0 0.7 0.6 0.2
Behenic C22:0 0..5 0.1

Lignoceric C24:0 0.2 3.0 2.4 0.4

Mono-unsaturated acids
Palmitoleic
0.4 0.85
C16:1
Oleic C18:1 8.0 7..5 46.3 5.0 82.5 38 60.0 60.0 33.6 33.4 46.3
Ricinoleic C18:1 87.8 0.2
Erucic C22:1
Bi-unsaturated acids
9
Linoleic C18:2 3.6 42.0 61.5 6.0 21.0 21.0 52.6 57.5 30.8

Poly-unsaturated acids
Linolenic C18:3 25.0 10 2.3
 Major FAMEs Found in Most Biodiesel Feedstocks

Fatty Acids (% wt) Castor Corn Linseed Olive Palm Peanut Rape Soya Sunflower Jatropha
Saturated Palmitic C16:0 0.9 13 6 14 48 14 5 6.5 4 14.6
Stearic C18:0 0.3 4 4 2 4 4 2 4.2 3 7.2
Mono-unsaturated Oleic C18:1 3.3 29 22 66 38 48 61 33.6 34 46.3
Ricinoleic C18:1 89
Bi-unsaturated Linoleic C18:2 3.7 54 16 16 9 30 19 52.6 58 30.8
Poly-unsaturated Linolenic C18:3 52 10 2.3
Total C18 96 87 94 84 51 82 92 93 95 84
Total C18 + C16:0 97 100 100 98 99 96 97 99 99 99

• Data taken from Bailey’s Industrial Oil and Fat Products Vol 1, 4th Ed,
Wiley ISBN 0-471-839574

•Total C18 recovers between 80 and 95% of most feeds listed except Palm

•Total C18 +C16:0 recovers >95% of all feeds listed.

Data courtesy of Tom Lynch, BP

IP PM-DY/09 Method for Determination of FAME in
Jet Fuel – GC/MS with Selected Ion Monitoring

7890A GC Conditions: 5975C MSD Settings:

Inlet: • Electron ionization (EI) at 70 eV
• Temperature: 260 oC • Source Temperature: 230 oC
• Mode: splitless • Quad Temperature: 150 oC
• Sample size: 1 uL • Scan Range: m/z 33 to m/z 320
• SIM Groups: see next slide
Column:
• HP-Innowax, 50m x 0.20 mm ID x 0.4 um
• Flow: 0.6 mL/min helium constant flow mode

GC Oven:
• Initial temperature: 150 oC for 5 min.
• Ramp 1: 20 oC/min to 200 oC for 17 min.
• Ramp 2: 3 oC to 252 oC for 2 min.
Mass Spec SIM Ions Used for FAME Quantification

FAME Species SIM Ions SIM Group Start Time

Methyl Palmitate
270 (mol. ion), 271, 239, 227 20 min.
(C16:0)
Methyl Heptadecanoate
284 (mol. ion) , 253, 241 28 min.
(C17:0)*

Methyl Stearate (C18:0) 298 (mol. Ion), 267, 255 32 min.

Methyl Oleate
296 (mol. ion), 265, 264 35.5 min.
(C18:1)
Methyl Linoleate
294 (mol. ion), 295, 264, 263, 262 36.5 min.
(C18:2)
Methyl Linolenate
292 (mol. ion) 293, 263, 236 39 min.
(C18:3)
*C17:0 added to accommodate biodiesel made from animal fats
SIM/SCAN of Calibration Standard
0.5 mg/kg Each FAME in Dodecane

Scan TIC
C18:3
C18:2
C18:0 C18:1
C17:0
C16:0

SIM TIC
FAME Calibration – 0 to 50 mg/kg

Confidentiality Label
8 January 14, 2010
FAME Calibration – 0 to 5 mg/kg

Confidentiality Label
9 January 14, 2010
Matrix Induced Retention Time Shifts of FAME
Peaks
50 mg/kg FAME Calibration Standard
50 mg/kg Each FAME Spiked in Jet Fuel
C18:0
+0.083 min.
C16:0
+0.138 min. C17:0
+0.098 min.

C18:1
+0.076 min.
C18:2
+0.067 min.
C18:3
+0.054 min.

26 28 30 32 34 36 38 40
5 mg/kg and 1 mg/kg Total FAME Spiked in Jet
Fuel Sample 1
Abundance
22000 Jet Fuel Blank

18000

1 mg/kg Total
14000 FAME Spike

10000 C18:0
C16:0 C17:0

6000 C18:1
5 mg/kg Total C18:2
FAME Spike
C18:3
2000
0
20 22 24 26 28 30 32 34 36 38 40 42 44 Min.
Qunatitative Results for 5 mg/kg and 1 mg/kg Total
FAME Spiked in Jet Fuel Sample 1
5 mg/kg Total FAME Spike 1 mg/kg Total FAME Spike

FAME Run 1 Run 2 Run 3 Std Dev FAME Run 1 Run 2 Run 3 Std Dev

C16:0 0.8 0.8 0.8 0.02 C16:0 0.3 0.5 0.5 0.09

C17:0 0.9 0.8 0.8 0.01 C17:0 0.1 0.1 0.1 0.02

C18:0 0.9 0.9 0.9 0.01 C18:0 0.1 0.1 0.1 0.02

C18:1 0.8 0.8 0.8 0.01 C18:1 0.2 0.1 0.1 0.02

C18:2 0.9 0.9 0.9 0.04 C18:2 0.2 0.2 0.2 0.01

C18:3 0.9 0.9 0.9 0.02 C18:3 0.2 0.2 0.1 0.03

Total 5.2 5.0 5.0 0.10 Total 1.0 1.2 1.2 0.12
Matrix Interference in Jet Fuel Sample 2

0.9 mg/kg Each FAME Spiked Second Jet Fuel Sample

0.5 mg/kg Std

of Each FAME

20 22 24 26 28 30 32 34 36 38 40 42 44 Min.
Known Matrix Effects Raised C16:0 Detection Limit
Data courtesy of Tom Lynch, BP

Abundance Abundance

11000
38000

36000
C16:0 C18:1
10000

34000

9000
32000
5 mg/kg 5 mg/kg
30000

8000
28000
2 mg/kg 2 mg/kg
26000
7000

24000
1 mg/kg 1 mg/kg
22000 6000

20000
0.5 mg/kg 5000
0.5 mg/kg
18000

16000
0.1 mg/kg 4000 0.1 mg/kg
14000

12000
3000

10000

8000 2000

6000
Reference fuel 1000
4000

2000
0
35.10 35.20 35.30 35.40 35.50 35.60 35.70 35.80 35.90 36.00 36.10 36.20 36.30 36.40 36.50
22.90 23.00 23.10 23.20 23.30 23.40 23.50 23.60 23.70

Time--> Time-->
Reference fuel
 Questions

For questions, at break

please dial *1 on your
phone, or type onto the
Q&A box at any time during
the presentation.

Pesticide Analysis with New Agilent

Page 15
Jet Stream Technology
December 12, 2008
Ongoing Research to Improve Method
Lowering the Detection Limit to 0.1 mg/kg of Each FAME in
Jet Fuel

• Reduce matrix co-elution with C16:0 FAME

– Use Heart-Cutting Multidimensional GC (MDGC)
– Second, non-polar column may be able to separate FAME from aromatic
hydrocarbons
– Must also heart-cut all other FAMEs even though no significant matrix
interference in standard method

• Improved detection of lower concentration FAMEs

– Industry would like detection limit of 0.1 mg/kg
– Heart-cutting MDGC may reduce background
– Look for higher abundance SIM ions to improve mass spec signal
Heart-Cutting 2-Dimensional GC Overview

FID

Column1 Column 2

7890 GC
5975C MSD
Deans
Switch

Confidentiality Label
17 January 14, 2010
Capillary Flow Technology Deans Switch
Combined with Mass Spec Detection

FID

Restrictor

S/S Inlet Aux EPC

HP-Innowax

MSD

Capillary Flow Technology

HP-5ms Deans Switch
MDGC Method:
GC/MS Instrument Conditions
Inlet: CC Oven:
• Temperature: 260 oC • Initial temperature: 150 oC for 5 min.
• Mode: splitless • Ramp 1: 20 oC/min to 200 oC for 17 min.
• Sample size: 1 uL • Ramp 2: 3 oC to 252 oC for 2 min.
Column 1:
MSD Settings:
• HP-Innowax, 30m x 0.25 mm ID x 0.5 um
• Electron ionization (EI) at 70 eV
• Flow: 1.0 mL/min He constant P (225 oC)
• Source Temperature: 230 oC
Column 2: • Quad Temperature: 150 oC
• HP-5ms, 30m x 0.25mm ID x 0.25 um • Scan Range: m/z 33 to m/z 320
• Flow: 2.0 mL/min He constant P (225 oC) • SIM Groups: see next slide

Restrictor:
0.7m x 0.1 um ID deactivated fused silica
 FID Signal Used to Set Heart-Cut Times
Primary Column
Heart-Cut
Primary Column: HP-Innowax FAME Retention Time
Time (min.)
(min.)
AVTUR C16:0 24.080 23.7 – 24.6
Blank C17:0 29.151 28.9 – 29.5
C18:0 33.798 33.5 – 34.1
C18:1 34.841 34.5 – 35.1
C18:2 36.825 36.6 – 37.2
C18:3 39.570 39.3 – 39.9
AVTUR
Wider cut windows used to account for
100 mg/kg Total
matrix induced retention time shifts
FAME Spike

50 mg/kg
Total FAME Std
22 24 26 28 30 32 34 36 38 40
Improve SIM Ion Groups for FAME Peaks
Hydrocarbon mass peaks (mostly aromatics) in co-eluting jet fuel have
little overlap with most FAME mass peaks
167
Prototype Software recommends SIM
ions to reduce background interference
Jet Fuel Blank
and improve S/N in the target peak
Average Spectra
elution time
25.5 – 25.8 min.
115 190
77 141
51
210 230 258 304

40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
74

5 ppm C16:0 Standard

Average Spectra
25.5 – 25.8 min.
43
143
185 227 270
239

40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
Expand SIM Ions Groups to Include FAME Base
Peaks
FAME Species SIM Ions SIM Group Start Time

Methyl Palmitate
270(mol. ion), 271, 239, 227, 74(base) 20 min.
(C16:0)
Methyl Heptadecanoate
284(mol. ion) , 253, 241, 74(base) 28 min.
(C17:0)

Methyl Stearate (C18:0) 298(mol. Ion), 267, 255, 74(base) 32 min.

Methyl Oleate
296(mol. ion), 265, 264, 55(base) 35.5 min.
(C18:1)
Methyl Linoleate
294(mol. ion), 295, 264, 263, 262, 67(base) 36.5 min.
(C18:2)

Methyl Linolenate
292(mol. ion) 293, 263, 236, 79(base) 39 min.
(C18:3)
HP-5ms Secondary Column Elution of FAMES After
Heart-Cut
C16:0 C17:0 C18:0 C18:1 C18:2 C18:3

HP-5ms Column
MS Scan Data

HP-5ms Column
MS SIM Data

Innowax Column
FID Data C18:2 C18:3
C17:0
C16:0 C18:0 C18:1
Combination of Heart-Cutting MDGC and Base
Peak SIM Ions
1 mg/kg total FAME Spiked in Jet Fuel Sample 2
(< 0.2 mg/kg each FAME)

• Improved detection of C16:0 FAME

• Better(?) detection of C17:0 C18:0, C18:2 and C18:3
• Added matrix interference with C18:1 FAME

C18:0
36.545

C16:0 C18:1
27.399 C17:0 37.336
32.133 C18:2 C18:3
39.110 41.558

26 28 30 32 34 36 38 40 Min.
Research Summary

• Application of MDGC reduces matrix interference with most FAMEs in Jet Fuel
• Addition of higher intensity SIM ions improved detection of FAMEs
• Increase background for C18:0 and C18:1 FAMEs

• Future work still needed before proposing these changes

– Better accounting for primary column retention time shifts due to matrix
• Narrow heart-cut time windows for samples to eliminate additional matrix on secondary
column
• Will need two methods: one for calibration standards and one for samples
– Improve separation in secondary column
• Different Wax column dimensions to lower elution temperature
– Reverse columns: C18 FAMES elute as a single peak
• Fewer hear cuts needed
– Use more jet fuel matrix samples
– Chemical Ionization
This information is subject to change without notice.
© Agilent Technologies, Inc. 2010