FAME in AVTUR using GC Heart-Cut and refocusing – IP PM EL Piet Koppen – AC Analytical Controls EI Fame in Jet workshop March 1, 2012

Outline  Application approach  Current Status  Results & chromatograms  Ruggedness test AC  Scope extension  Feasibility test CME  Next steps

Draft Method Application is now approved as IP PM EL and method is available from the EI website

GC Heart-Cut Approach Multi-Dimensional GC Deans-switching and Cryo-focussing Cryo Trapping in 2nd Dimension Non Polar 1st Dimension column Polar 2nd Dimension column

System Overview

Current GC Heart-Cut Specifications Analysis Time → 55 min 1 st Dimension RT Repeatability → 0.10% RSD or better 2 nd Dimension RT Repeatability → 0.02% RSD or better Area Repeatability → 5.0% RSD or better Quant. Range Total FAME (Low Range) → 2.0 – 50 mg/kg Quant. Range Total FAME (High Range) → 10 – 150 mg/kg LOQ each FAME (Low Range) → 0.5 mg/kg or better LOQ each FAME (High Range) → 1.5 mg/kg or better

1 st Dimension Chromatogram Injection of Cal Mix with 100 mg/kg each FAME

1 st Dimension Chromatogram Determine cutting windows for C16:0 and C18:0/1/2/3 Typically Response Factors FAME’s are within 5% RSD → If not Replace Liner and/or 1 st Dimension Column

2 nd Dimension Chromatogram Injection of Cal Mix with 5 mg/kg each FAME

Points of Attention Matrix Induced Retention Time Shifts Refocus Trap Functionality 1 st Dimension Retention Repeatability 2 nd Dimension Peak Identification 2 nd Dimension Retention Repeatability Peak Integration

Matrix Induced Retention Time Shifts AVTUR spiked with ~ 100 ppm Wt FAME ( Red Chromatogram) Dodecane with ~ 100 ppm Wt FAME (Blue Chromatogram) C16:0 Retention Difference = min 0.1 ul Injection using GC Heart-Cut Method

Matrix Induced Retention Time Shifts AVTUR spiked with ~ 100 ppm Wt FAME ( Red Chromatogram) Dodecane with ~ 100 ppm Wt FAME (Blue Chromatogram) C16:0 Retention Difference = min 0.3 ul Injection using GC-Heart-Cut Method

Refocus Trap Functionality Confirm that at least part of C14:0 is trapped because then C16:0 is 100% trapped

1 st Dimension Retention Repeatability RSD Retention Times for All FAMES should be below 0.10% (plot above displays RSD of around 0.04%)

2 nd Dimension Peak Identification Make sure all FAME Components Elute within Retention Window at both High and Low FAME Content. Check Peak Symmetry (Typically between 0.5 and 2.0) Check Retention Window (Typically 0.2 min for all FAME peaks) Red = 100 mg/kg Green = 40 mg/kg Blue = 1 mg/kg

2 nd Dimension Retention Repeatability Real Life Sample RSD C16:0 = % RSD C18:0 = % RSD C18:1 = % RSD C18:2 = % RSD C18:3 = % RSD Retention Times for All FAMES should be below 0.02%

Peak Integration Integration Events can have Considerable Impact on Results AVTUR contaminated with 2 Wt% diesel 5 mg/kg Total FAME

Sensitivity Low Range Method C16:0 LOQ = 0.2 mg/kg C18:0 LOQ = 0.3 mg/kg C18:1 LOQ = 0.3 mg/kg C18:2 LOQ = 0.4 mg/kg C18:3 LOQ = 0.5 mg/kg Chromatogram shows 1 ppm Wt FAME in Real Life Sample Chromatogram shows 5 mg/kg FAME each peak in Dodecane

Sensitivity High Range Method C16:0 LOQ = 0.6 mg/kg C18:0 LOQ = 0.9 mg/kg C18:1 LOQ = 0.9 mg/kg C18:2 LOQ = 1.0 mg/kg C18:3 LOQ = 1.3 mg/kg Chromatogram shows 5 mg/kg FAME each peak in Dodecane

Linearity

Area Repeatability Real Life Sample Total FAME RSD: 1.7 % Mean Value: 4.2 mg/kg FAME

Area Repeatability Spiked AVTUR contaminated with 2 Wt% Diesel Total FAME RSD: 1.0 % Target Value: 5.3 mg/kg FAME Mean Value: 5.4 mg/kg FAME

Ruggedness Test 10 samples in total Materials used –2 Jet Fuels A-1 –2 B7 Diesels –2 FAME free Diesels

Ruggedness Test Sample NameEstimated FAME Content (mg/kg) Diesel Content (Wt%) RR RR RR RR RR RR RR RR RR RR

Ruggedness Test

Extended scope FAME Method adaptations required to cover CME : More heart-cuts Higher matrix background Longer analysis time Refocus-trap needs to be colder in temperature and/or trapping needs to be shorter in time For other FAME types in the range of C16 to C18 no influence is expected

Higher specification levels  Matrix background lower  Improved precision  Improved CME determination Effect of a higher specification limit such as 100 mg/kg in scope:

Additives No effects anticipated  Additives vented by backflushing  Additives separated in 2nd dimension  Use of FID detector Influence of additives:

Feasibility CME Determination  Use of separate oven for 1st dimension column  Optimize column dimensions of both 1st and 2nd dimension column  Increase film thickness of 2nd dimension column (loadability)  Re-focus and inject all heart-cuts separately Expected modifications towards current system configuration:

Feasibility CME Determination Preliminary Results Using Columns with Medium Bore ID Red Chromatogram = 100 mg/kg Spiked Contaminated AVTUR Blue Chromatogram = 100 mg/kg Calibration Standard

Feasibility CME Determination Preliminary Results Using Columns with Medium Bore ID Red Chromatogram = 100 mg/kg Spiked Contaminated AVTUR Blue Chromatogram = 100 mg/kg Calibration Standard

Feasibility CME Determination Preliminary Results Using Columns with Medium Bore ID Red Chromatogram = 100 mg/kg Spiked Contaminated AVTUR Blue Chromatogram = 100 mg/kg Calibration Standard

Feasibility CME Determination Preliminary Results Using Columns with Medium Bore ID Red Chromatogram = 100 mg/kg Spiked Contaminated AVTUR Blue Chromatogram = 100 mg/kg Calibration Standard

Next Steps Complete Ruggedness Test Participate in EI Round Robin Get precision statement Finalize tests on CME analysis Implement System and Method modifications for CME

Questions