Resolution and identification of elemental compositions for more than 3000 crude acids in heavy petroleum by negative-ion microelectrospray high-field Fourier transform ion cyclotron resonance mass spectrometry

Although crude acids are minor constituents in petroleum, they have significant implications for crude oil geochemistry, corrosion, and commerce. We have previously demonstrated that a single positive-ion electrospray ionization (ESI) high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) experiment can resolve and identify 3000 chemically different elemental compositions of bases (basic nitrogen compounds) in a crude oil. Here, we show that negative-ion ESI high-field FT-ICR MS can selectively ionize and identify naphthenic acids without interference from the hydrocarbon background. When combined with prechromatographic separation, ESI FT-ICR MS reveals an even more detailed acid composition. An average mass resolving power, m/Deltam(50%) greater than or equal to 80 000 (Deltam(50%) is mass spectral peak full width at half-maximum peak height) across a wide mass range (200 < m/z < 1000), distinguishes as many as 15 distinct chemical formulas within a 0.26 Da mass window. Collectively, more than 3000 chemically different elemental compositions containing O-2, O-3, O-4, and O2S, O3S, and O4S were determined in a South American heavy crude. Our data indicates that the crude acids consist of a mixture of structures ranging from C-15-C-55 with cyclic (1-6 rings) and aromatic (1-3 ring) structures. The acid composition appears to be simpler than that of the corresponding hydrocarbon analogues.