Battling Fuel Washing: Accurate Quantitation of ACCUTRACE™ Plus in Commercial Diesel and Full Characterization of Petroleum Samples

Importance of the Topic

Government-subsidized diesel dyes are frequently removed and resold illegally, leading to revenue loss and environmental pollution from chemical waste. Replacing the existing fiscal marker with a more robust, colorless alternative ensures regulatory compliance and protects ecosystems from improper disposal of dye solvents.

Aims and Study Overview

This work demonstrates a workflow for detecting and quantifying the new ACCUTRACE™ Plus marker (Butoxybenzene, BPE) in commercial diesel and kerosene. It also illustrates the broader capability of GC×GC-TOFMS for detailed characterization of light to medium petroleum fractions using a unified instrumental setup.

Methodology

Diesel B7 and kerosene samples were spiked with BPE at levels corresponding to 1%–125% dosage (0.095–11.875 mg/L). Six matrix-matched calibration standards were prepared. Spiked and blank samples underwent headspace injection (0.4 µL, split 200:1) into a dual-stage GC×GC system, with full mass range (40–600 m/z) acquisition. Quantitation employed deconvolution and target analyte search in ChromaTOF software. Recovery was assessed at two dosage levels (0.095 and 9.5 mg/L).

Instrumentation Used

• Gas chromatograph: Agilent 7890B with LECO Dual Stage QuadJet™ modulator
• Primary column: Stabilwax-MS 30 m × 0.25 mm × 0.25 µm
• Secondary column: Rxi-5SilMS 0.6 m × 0.15 mm × 0.15 µm
• Carrier gas: Helium at 1.4 mL/min
• Temperature program: 100 °C ramping to 260 °C over 30 min
• Modulation time: 3 s; secondary oven +5 °C; modulator +15 °C
• Mass spectrometer: LECO Pegasus BT 4D; source at 250 °C; acquisition rate 250 spectra/s

Main Results and Discussion

GC×GC separation alleviated coelution of BPE with paraffins and aromatics, producing narrow 2D peaks (~0.03 s FWHH). Fast acquisition (250 spectra/s) ensured sufficient data points for reliable quantitation. The calibration curve (R² = 0.99956) covered 0.095–11.875 mg/L, with accuracy within 0.1–10% and S/N >100 at the lowest level. Recoveries at 1% and 100% dosages were 97.9% and 99.6%, respectively. Additionally, 3D contour plots and classification tools enabled comprehensive bulk profiling of diesel hydrocarbons.

Benefits and Practical Applications

• High selectivity and sensitivity for BPE detection in complex matrices
• Single GC×GC configuration supports both regulatory testing and petroleum profiling
• Reduced downtime and cost savings by avoiding column changes

Future Trends and Applications

Advancements in modulation speed and data processing will further improve trace-level detection and peak deconvolution. Integration with AI-driven spectral libraries and automated classification may streamline routine analysis of fuel authenticity and petrochemical composition across regulatory and industrial laboratories.

Conclusion

The LECO Pegasus BT 4D GC×GC-TOFMS workflow provides robust quantitation of the ACCUTRACE™ Plus marker and detailed petroleum fraction characterization using a single instrumental setup, enhancing efficiency for fuel compliance and quality control laboratories.

References

1. LECO Application Note, Fuel Washing Diesel 203-821-522
2. Commission Implementing Decision (EU) 2022/197 of 17 January 2022