Bruker Daltonics Technical Note # TN-34 Rapid Analysis of Complex Mixtures Using the solariX-CM, FTMS Platform Abstract The solariX-CM FTMS represents the ultimate MS solution for addressing complex mixtures that are not easily amenable to chromatographic separation techniques. These application areas include, but are not limited to, petroleomics (e.g. crude oil analysis), environmental analysis (e.g. humic acid analysis in river waters), and metabolomics. The resolving power required for dealing with the inherent and extreme complexity of these applications is typically greater than 400,000. Mass accuracies in the sub-ppm range are also essential to help ensure reliable molecular formulae assignments. The solariX-CM routinely delivers ultimate selectivity and specificity with “benchtop” ease-of-use. Introduction Mass spectrometry, in combination with chromatographic separation methods, has been widely used to address the challenges associated with complex mixtures. However, the development and optimization of chromatographic separation methods for complex mixtures can be laborious and increases the overall analysis time. Moreover, some compound classes and mixtures are simply not amenable to standard separation techniques such as high pressure liquid chromatography (HPLC) or capillary electrophoresis (CE). The unparalleled resolving power of the solariX-CM Fourier transform mass spectrometer (FTMS) reduces the demands on chromatographic separation methods thereby making complex mixture analysis much more efficient. The classification of the components in crude oil including the speciation of heteroatomic compounds like sulfur or nitrogen compounds with specific double bond equivalents are necessary for crude oil analysis on the molecular level. Leveraging the resolution and mass accuracy of the FTMS, the elemental composition of individual compounds of crude oil has been analyzed [1] – [5]. Since the compound classes in oil represent a range of polarity and gas-phase basicity it is essential to analyze each sample under both positive and negative modes and with different atmospheric pressure ionization (API) techniques. An advantage of the solariX is quick change-over (in less than 5 minutes!) between API sources, such as electrospray (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photo ionization (APPI). Complex, rich datasets are quickly analyzed using Composer™ from Sierra Analytics. Composer is a comprehensive software package that is specific to petroleomics data. It quickly and accurately provides classification and DBE

diluted 1:100 with a solution of 50% MeOH/50% toluene. This sample was infused at a flow rate of 120 μL/h for ESI and @ 6 ml/h for APPI, respectively. information through a range of data representations that include Kendrick mapping and Van Krevelen plots. Facilitated by Composer (Sierra Analytics, Modesto, CA, USA), data was internally calibrated using identified and known series of compound classes: ESI positive (N series), ESI negative (O2 series), APPI positive (CH series). All other data analysis was carried out using Composer. Analyses were carried out using a solariX-CM 12T (Bruker Daltonics,...

Figure 3: Enhancement of dynamic range using CASI for the analysis of crude oil. Broadband resolving power of 950,000 with 100 ppb average mass measurement error. Figure 4: DBE vs. carbon number plots for different compound classes of crude oil (APPI Positive, radical ions), average error for all assigned compounds is 85 ppb Results Perhaps the most challenging and complex samples to analyze by mass spectrometry are crude oils. Therefore, the analysis of these samples requires extreme resolving powers to discern each elemental component within a dense matrix. Figure 1 illustrates this complexity...

The DBE plots in Figure 6 show different distributions, demonstrating the need for different ionization sources to achieve complete analysis of the heteroatom fraction of crude oil samples. Composer is used to comprehensively analyze the data from oil samples. Loading peak lists into Composer is straightforward and facile. From the main user interface one can easily generate different plots ranging from DBE vs. carbon number, Kendrick- and van Krevelen-plots. For example, Figure 4 displays DBE vs. carbon number-plots for different compound classes. Another example of the output from the data...