Petroleomics by EASI(±) FT-ICR MS

An ambient ionization/desorption technique, namely, easy ambient sonic-spray ionization mass spectrometry (EASI), has been applied to crude oil samples. From a single droplet of the sample placed on an inert surface, EASI(±) is shown to promote efficient desorption and ionization of a myriad of polar components via the action of its cloud of very minute supersonic bipolar charged droplets. The gaseous [M + H]+ and [M − H]− ions concurrently formed by EASI(±) were analyzed by Fourier transform mass spectrometry (FT-ICR MS), and a total of ∼6000 acidic and basic components have been attributed. EASI(±) FT-ICR MS of crude oils is show to be almost as fast as ESI(+)/ESI(−) FT-ICR MS, providing similar compositional information of polar components and spectral quality comparable to that of a commercial nonochip-based robotic ESI device. EASI(±) requires no sample workup thus eliminating risks of contamination during sample manipulation and memory effects because of carry over in pumping ESI lines. More importantly, EASI(±) is a voltage-free ionization technique therefore eliminating risks of redox processes or duality of ionization mechanisms that can be observed in voltage-assisted processes. Data visualization via typical petroleomic plots confirms the similarity of the compositional information provided by EASI(±) compared to ESI(+)/ESI(−). The ambient EASI(±) FT-ICR MS method requires no voltage switching in changing the ion polarity mode, offering a workup, heating and voltage-free protocol for petroleomic studies performed at open atmosphere directly on the undisturbed crude oil sample.