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Improved Performance of the Analysis of Aromatics in Gasoline by ASTM Method D5769 Using the Agilent 5977B GC/MS with the InertPlus Source
Agilent technologies, Inc.
June 2016
Fred Feyerherm
Reformulated Gasoline from epa.gov website
Reformulated Gasoline - background:
US Congress Clean Air Act of 1973
Amended 1990
Directed EPA to clean up urban air
EPA method 80.46 (f) (from 40 CFR)
ASTM subsequently developed D5769
High accuracy and precision using GCMS
Impacted 180 refineries in US and anyone
shipping gasoline to US
Reformulated Gasoline - background:
Parameters Regulated:
Total Aromatics (GCMS) limited to <25 vol%
Benzene (GC)
Oxygenates (GC-OFID)
Olefins (D1319 FIA)
Sulphur (X-ray)
Reid Vapor Pressure
Why GCMS for Aromatics?
EPA wanted to identify unknowns from possible dumping
EPA has a lab in Ann Arbor Michigan
What is Gasoline…chemically?
Saturates
Olefins
Napthenes (e.g. cyclohexane)
Aromatics
Oxygenates
Traces of other compounds
GCMS Chromatogram of Gasoline
Use Mass Spec to identify peaks
ASTM Method D5769 for Total Aromatics in Gasoline
Use Extracted ion to find targeted compoundsExtracted Ion Chromatogram EIC m/z 78
Quantitation by GCMS
Get a standard for each compound
Use extracted ion chromatogram to get peak and integrate
Use an Internal Standard (e.g. Benzene-d6)
But you can’t readily get standards for every possible aromatic
Get standards for all C6 – C9 and selected C10 Aromatics
Create Uncalibrated Compound Groups as directed in D5769
D5769 Uncalibrated C10-benzenes
C7 (Toluene m/z 91) and C8 Aromatics
C9 Aromatics m/z 120
C10 Aromatics m/z 134
C11 Aromatics m/z 148
C12 Aromatics m/z 162
Additional Aromatics: Indane and alkylated Indanes m/z 117
Additional Aromatics: Naphthalenes
Quantitation Compound List for D5769
D5769 differences from normal GCMS type analysisSpecial Software
Gravimetric calibration
• Raw weights
• Multiple gravimetric ISTDs
• Update from disc (Accustandard)
Quantitate Uncalibrated aromatics using RF from
calibrated cpnd
Report both Wt % and Vol %
Keys for SuccessExcellent Linearity for all analytes on 5977B GCMS
Regulatory Compliance
EPA has contracted Southwest Research Institute (SWRI) for
compliance monitoring
SWRI Lab in San Antonio does most monitoring samples
EPA Ann Arbor also does some
Regulatory Compliance
My Opinion: Everyone needs to get the same answer, not necessarily the best answer for total aromatics in gasoline.
As SWRI
Same STDs
Same column
Same method
Thank you Let’s Continue the Conversation