On
December 9, 2014, ∼94 000 gallons of furnace oil
spilled into the Shela River in Bangladesh, a designated World Heritage
Site by the United Nations Educational, Scientific and Cultural Organization.
It was the largest recorded oil spill in the Sundarbans region. Visually,
furnace oil appears similar to heavy fuel oil, but little is known
about its composition even though it is heavily utilized worldwide.
A shift in global oil production to heavier, less well-known feeds
(i.e., heavy oil and bitumen) requires molecular-level knowledge for
efficient response, damage assessment, and restoration in the event
of any oil spill. However, little is known about the chemical composition
of furnace oil in chronic and acute releases. For the first time,
we catalog the molecular-level composition of a relatively unknown
furnace oil collected immediately after the 2014 Bangladesh spill
and compare it to a well-characterized intermediate fuel oil (IFO)
spilled in Texas City, Texas (U.S.A.) in March 2014. Through a combined
technique approach, we apply comprehensive two-dimensional gas chromatography
(GC×GC) analysis and Fourier transform ion cyclotron resonance
mass spectrometry (FT-ICR MS) to contrast the unknown furnace oil
to IFO. Combined, these techniques capture the continuum of oil components
and access the less volatile, highly complex non-GC amenable compounds.
GC×GC analysis provides biomarker signatures that suggest the
furnace oil likely originated in the Middle East and is a refined
product. We further compared the furnace oil with the Arabian light
crude from Middle East origin (WP681) and revealed remarkable similarities
between the two oils. Simulated distillation for the furnace oil showed
that 42% of the oil mass is not volatile below 478 °C (equivalent
to C40; the upper limit for GC-based techniques), whereas
the IFO contained 38% of the total mass >C40. Furthermore,
FT-ICR MS extends the carbon number range and unlocks the molecular
composition of non-GC amenable compounds. Atmospheric pressure photoionization
(APPI) and electrospray ionization (ESI) FT-ICR MS resolve and identify
tens of thousands of molecular formulas in each oil and report furnace
oil composition similar to whole heavy crudes. To the best of our
knowledge, this is the first report of the detailed compositional
characterization of any furnace oil.