Samples of motor oil and creosote are subjected to three-dimensional fluorescence spectroscopy to document the shifting of excitation/emission maxima as the solutions undergo serial dilutions. Effects such as self-quenching of individual polycyclic aromatic hydrocarbons (PAHs) and energy transfer between PAHs combine to produce large red-shifts in the resulting fluorescence emission spectra. The concentration-imposed complications are also demonstrated for several synthetic ternary PAH mixtures and a diesel residue mimic.

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Polycyclic aromatic hydrocarbons (PAHs) are a challenge for fluorescence analysis. Inner-filter quenching effects and energy transfers of PAHs in petroleum differ with concentration, leading to characteristically different fluorescence. At high concentrations of single PAH molecules and petroleum mixtures the classic rectangular quartz cell presents a particular challenge due to inner filter effects from right-angle illumination. While quite a few instrumental and mathematical corrections for these effects are reported throughout the literature, for researchers with standard instrumental sample compartments a triangular fluorometer cell can be used to emulate front-surface fluorescence analysis. This work presents concentration study results from the single PAH molecules fluoranthene and azulene dissolved in spectral-grade cyclohexane and also seeks to correct an aspect of our past work on the fluorescence of petroleum mixtures.

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