Effects-Driven Fractionation of Heavy Fuel Oil to Isolate Compounds Toxic to Trout Embryos

Abstract

Heavy Fuel Oil (HFO) is a petroleum product and emerging contaminant used as fuel by cargo ships, cruise liners, and oil tankers. As a high-frequency, low volume commodity shipped by pipeline, train, truck, and ship, it is at high risk for small-scale spills in terrestrial, aquatic, and marine environments. There are few reports characterizing HFOs and quantifying the contaminants therein, but previous studies have shown that the most toxic classes of compounds in petroleum products are polycyclic aromatic hydrocarbons (PAHs). This project seeks to address that by analyzing HFO 7102, the specific HFO spilled in Wabamun Lake, Alberta in August 2005. Through an Effects-Driven Fractionation and Analysis, HFO 7102 was successively fractionated by physical and chemical means. First, a low-temperature vacuum distillation separated the oil into three fractions by volatility. The most toxic of these (lowest median toxic concentration, or LC50), F3, underwent a series of solvent extractions to remove asphaltenes and waxes. The remaining PAH-rich extract (F3-1) was further separated using open column chromatography into non-polar, mid-polar, and polar fractions with groupings approximately by number of aromatic rings. At each stage, fractions and sub-fractions were characterized by GC-MS for compositional analysis and bioassays were conducted with rainbow trout embryos. In this fashion, toxicity thresholds were developed for all fractions and the components of HFO 7102 associated with toxicity were identified and quantified. The F3 fraction was six times more toxic than the whole oil. While the wax fraction (F3-2) was shown to be non-toxic, the remaining PAH-rich extract (F3-1) accounted for all of the toxicity in F3. Future work may be done to determine the relative toxicity of the last fractions generated and identify a range of PAH responsible for fish toxicity. It is expected that the F3-1-2 fraction will be most toxic, as it contains nearly all of the three-ring and most of the four-ring PAH. These size classes of PAH have been associated with chronic toxicity to fish embryos in studies of crude oil. Further separations may be attempted to identify a more specific range of toxic compounds, such as by degree of alkylation.