Natural dissolved organic matter affects electrospray ionization during analysis of emerging contaminants by mass spectrometry

Dissolved organic matter (DOM), present in many forms in water, can interfere with analysis of organic contaminants by atmospheric pressure ionization–mass spectrometry. A quantitative analysis of this interference, or matrix effect, on organic contaminant target analyte measurements was carried out using un-fractionated and fractionated dissolved natural organic matter from the Suwannee River, GA (SROM), a standard reference material, that was directly infused into the tandem mass spectrometer during multiple reaction monitoring (MRM) of a suite of endocrine disrupting compounds–pharmaceuticals and personal care products (EDC/PPCPs). Most target analytes suffered signal suppression in the presence of both fractionated and un-fractionated SROM, however greater interferences were measured with fractionated relative to bulk SROM. This finding is consistent with the view of organic matter as a supramolecular association of low molecular mass components having separate charged and structural features revealed only after dissociation.

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► Matrix effects on EDC/PPCPs analysis were quantified by post column DOM infusion.
► Matrix effects were distinguished between Suwannee River DOM and its fractions.
► A supramolecular association of DOM is interpreted with matrix effects measurements.
► The greatest interferences were produced by fractionated DOM.