Detecting and Characterizing Heteroatom-Containing Compounds in Fuels

A researcher at the US Naval Research Laboratory created new analytical techniques using high-resolution mass spectrometry to analyze fuels and complex petroleum products quickly. The study has been published in the scientific journal Fuel.

Mark Romanczyk's methods enable detailed minute-by-minute qualitative analysis of complex mixtures, significantly aiding the study of chemical changes in weathered crude oil in terrestrial environments.

Despite the accidental rise of oil spilled onto landmasses, less research has been dedicated to evaluating the compositional changes/fate of oil prior to its introduction into bodies of water. The lack of information affords an opportunity to investigate and qualitatively characterize oil as a function of weathering time in the absence of an aqueous environment. These studies may provide highly useful information for oil spill cleanup and exposure concerns.

Mark Romanczyk, Ph.D., Researcher, US Naval Research Laboratory

The lightest aromatic hydrocarbons in crude oil, such as alkylbenzenes and alkyltetralins with a carbon content of around twelve, began to evolve within the first 24 hours of weathering when exposed to direct sunlight. After 24 hours, these light hydrocarbons were trapped in a thin surface layer, but the overall composition of the oil remained largely unchanged.

Despite film formation, the heaviest aromatic hydrocarbons, such as naphthalenes and anthracenes, exhibited signs of photooxidation. Since wave action is likely to stir the oil and prevent film formation, the results show that the compositional changes of oil in a terrestrial environment may differ from those in an aquatic environment.

Different techniques have been used to find and characterize heteroatom-containing compounds (HCCs) in fuels. These compounds are of concern for fuel stability due to their potential to trigger unfavorable chemical reactions. The innovative techniques help establish a connection between fuel composition, performance, and properties. They also found new classes of HCCs that had not been previously reported.

The approaches Mark and his colleagues are developing enable highly detailed analysis of fuel composition in minutes. I think this is going to lead to significant advancements in the near future in how we formulate and handle fuels in the Navy and Department of Defense.

Kevin J. Johnson, Ph.D., Head, Navy Technology Center for Safety and Survivability, US Naval Research Laboratory

At the IASH 2024 International Symposium in September in Louisville, Kentucky, Romanczyk received the Chevron Research Award of Excellence from the International Association for Fuel Stability and Handling (IASH) in honor of John Bacha.

Bacha worked as a consultant scientist for Chevron Products Company. He was a fervent advocate of IASH and is well-known worldwide for his research on the chemistry of residual fuel and diesel fuel. He was committed to inspiring the next generation to enter and contribute to the industry.

Romanczyk is recognized as a leading expert in the analysis of complex mixtures, including crude oils, alternative fuels, and petroleum-derived fuels. His current research focuses on developing connections between fuel compositions and stability characteristics, as well as creating analytical methods for detecting PFAS (per- and polyfluoroalkyl substances) at part-per-billion levels. Additionally, he conducts research on the weathering of crude oil.

Romanczyk has been cited hundreds of times and has 16 publications in prestigious journals. He is a member of the American Society for Mass Spectrometry, IASH, and the American Chemical Society.

The Chemical Sensing and Fuel Technology Section, where Romanczyk works, conducts research to expand the Navy's understanding of chemical processes, leading to the development of innovative sensing techniques and analytical data analysis methods. The section's projects include developing analytical techniques, applying chemometrics to sensor systems, enhancing intelligent data fusion, and improving the detection of hazardous chemicals and biological agents.

This research program encompasses advanced techniques for detecting hazardous chemicals, understanding Navy mobility fuel properties, conducting trace chemical analyses, and managing damage control events like flooding and fire. The work requires expertise in organic chemistry, chemical analysis, instrument design, high-resolution mass spectrometry, analytical method development, computational modeling, chemometrics, and system verification.

Research areas also include using area monitoring, personal dosimetry, and chemical sensors to meet workplace and environmental detection needs. Another significant research focus is applying artificial intelligence to interpret data for improved fuel situational awareness and hazardous material detection, as well as developing novel chemometric algorithms to advance sensing technologies for automated fuel quality diagnostics and prognostics.

Journal Reference:

Romanczyk, M., et al. (2024) Compositional analysis and fate of aromatic hydrocarbons in weathered crude oil in a non-aqueous environment by using a high-resolution orbitrap mass spectrometer. Fuel. doi.org/10.1016/j.fuel.2024.132379