Investigation of interactions between surface water and petroleum-type pollutants

In oil spill investigations, one of the most important steps is a proper choice of approaches that imply an investigation of samples taken from different sedimentary environments, samples of oil contaminants taken in different periods of time and samples taken at different distances from the oil spill. In all these cases, conclusion on the influence of the environment, microorganisms or migration on the oil contaminants' composition can be drawn from the comparison of chemical compositions of the investigated contaminants. However, in case of water contaminants, it is very important to define which part of organic matter has been analyzed. Namely, previous investigations showed that there were some differences in chemical composition of the same oil contaminant depending on the intensity of its contact with ground water. The aim of this work is to define more precisely the interactions between oil contaminant and water, i.e. the influence of the intensity of interaction between the oil contaminant and water on its chemical composition. The study was based on a comparison of four fractionated extracts of an oil pollutant, after they had been analyzed in details.

Oil polluted surface water (wastewater canal, Pancevo, Serbia) was investigated. The study was based on a comparison of four extracts of an oil contaminant: extract 1 (decanted part), and extracts 2, 3 and 4 (extracted by shaking for 1 minute, 5 minutes and 24 hours, respectively). The fractionated extracts were saponified with a solution of KOH in methanol, and neutralized with 10% hydrochloric acid. The products were dissolved in a mixture of dichloromethane and hexane, and individually fractionated by column chromatography on alumina and silica gel (saturated hydrocarbon, aromatic, alcohol and fatty acid fractions). n-Alkanes and isoprenoid aliphatic alkanes, polycyclic alkanes of sterane and triterpane types, alcohols and fatty acids were analyzed using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). delta 13C(PDB) values of individual n-alkanes in the aliphatic fractions were determined using gas chromatography-isotope ratio monitoring-mass spectrometry (GC-irmMS).

Extracts 1 and 2 are characterized by uniform distribution of n-alkanes, whereas extract 3 is characterized by an even-numbered members dominating the odd-ones, and extract 4 showed a bimodal distribution. Extract 1 is characterized by the least negative delta 13C(PDB) values of C19-C26 n-alkanes. Sterane and triterpane analysis confirmed that all extracts originated from the same oil contaminant. n-Fatty acids, C19-C24, in all extracts are very low, being somewhat higher in extract 4. Even-numbered n-alcohols, C12-C16, were identified in the highest concentration in extract 3. It was assumed that algae were responsible for the composition of extract 3. Furthermore, a possible reason for higher concentrations of C19-C26 n-alkanes and C19-C24 fatty acids in extract 4 is the formation of inclusion compounds with colloidal micelles formed between the oil contaminant's NSO-compounds and water.

It was undoubtedly confirmed that there were specific differences in the compositions of the different extracts depending on the intensity of the interaction between the oil contaminant and the surface water.

When comparing the composition of oil contaminants from different water samples (regardless of the ultimate investigation goal) it is necessary to compare the extracts isolated under the same conditions, in other words, extracts that were in the same or very similar interaction with water.