Comparison of Isotope Abundance Analysis and Accurate Mass Analysis in their Ability to Provide Elemental Formula Information

Deriving elemental formulas from mass spectra used to be an exclusive feature provided only by expensive high-resolution mass spectrometry instruments. Nowadays this feature can be used on unit resolution quadrupole-based mass spectrometers (MS) combining isotope abundance analysis (IAA) and mass accuracy analysis (MAA) with surprising accuracy that is commonly lower than 1 ppm mass accuracy. In this Article, we assess the usefulness of both MAA and IAA in the elemental formula deriving process performed on unit resolution MS data with constant resolution across the m/z range. The methods' effective filtration power (EFP) are estimated along with their ability to provide useful elemental information under nonideal experimental conditions. The term effective mass accuracy (EMA) is introduced so that the identification power of IAA can be expressed in a familiar way and compared more readily to MAA. We found that IAA alone commonly has an EMA under 5 ppm. IAA and MAA work well together and provide improved results with median EMA < 1 ppm for calibrated MS or <3 ppm for uncalibrated MS. We have also found that even though these methods cannot be fully trusted to pinpoint the exact elemental formula under poor experimental conditions, IAA can still accurately provide the exact number of several heteroatoms such as sulfur, chlorine, and bromine, while MAA cannot. Under such conditions, a combination of both methods can also provide good insight into the amount of carbon, hydrogen, and other elements in the elemental formula.

Automated summary

This article evaluates the utility of MAA and IAA in deriving elemental formulas on unit resolution MS data, finding that using both methods together results in improved accuracy. Under nonideal conditions, IAA can accurately determine the count of certain heteroatoms, while MAA alone cannot pinpoint exact elemental formulas.