Matrix effects in the analysis of polar organic water contaminants with HILIC-ESI-MS

Abstract

Matrix effects have been shown to be very pronounced and highly variable in the analysis of mobile chemicals, which may severely exacerbate accurate quantification. These matrix effects, however, are still scarcely studied in combination with hydrophilic interaction liquid chromatography (HILIC) and for very polar chemicals. In this study, the matrix effects of 26 polar model analytes were investigated in enriched drinking water, wastewater treatment plant effluent and solutions of inorganic salts, utilizing post-column infusion of the analytes into a HILIC-electrospray ionisation (ESI)-high-resolution mass spectrometry system. These experiments revealed the occurrence of structure-specific and unspecific matrix effects. The unspecific matrix effects were mainly observed in positive ESI polarity and predominantly coincided with a high ion count, resulting in ion suppression of all analytes. Thus, the excess charge is hypothesized to be the limiting factor in ion formation. Structurespecific matrix effects were more pronounced in negative ESI polarity and even structurally similar compounds were observed to react entirely differently: perfluoroalkyl carboxylic acids were suppressed, while perfluoroalkane sulfonic acids were simultaneously enhanced. These matrix effects were traced back to inorganic anions and cations, which eluted over a significant fraction of the chromatographic run time with this setup. Hence, it was concluded that inorganic ions are a main cause for matrix effects in the analysis of mobile chemicals utilizing HILIC.

Ultra-Short-Chain PFASs in the Sources of German Drinking Water: Prevalent, Overlooked, Difficult to Remove, and Unregulated

“…To compensate for the low trueness of some analytes (<70 and >130%), the concentration of substances was calculated considering recovery and matrix effects obtained from the validation. Since matrix effects in HILIC were shown to be highly sample and analyte specific, chemically similar IS cannot be used, and thus, matrix effects were determined for each analyte and sample individually. Therefore, all samples were split after reconstitution, and one part was spiked with a PFAS mix standard.…”

Correction of Matrix Effects for Reliable Non-target Screening LC–ESI–MS Analysis of Wastewater

“…Furthermore, a wide range of adduct formation of the oxides leads to many co-eluting compounds. Previous studies have referred to similarities of peaks in the ME PCI profile and the TIC , but were unable to show such a clear correlation. The close match between the TiChri scale representation of the matrix effect, and the TIC traces, provides strong evidence that the retention time-dependent matrix effect is associated with the competition between the co-eluting compounds; thus, the ion suppression can be defined as a competing matrix effect.…”

Occurrence, Distribution, and Environmental Behavior of Persistent, Mobile, and Toxic (PMT) and Very Persistent and Very Mobile (vPvM) Substances in the Sources of German Drinking Water

“…Some of the analytes exhibited recoveries <70% or >130% and thus, recovery and matrix effects (from validation) were included for concentration calculation/ correction. Since matrix effects for PMT/vPvM substances are highly structure-and sample-specific, 17 all samples enriched for HILIC measurements were split after reconstitution and one aliquot was spiked with the PMT standard mixture to calculate matrix effects for each sample individually.…”