Activated carbon is employed for the adsorption of organic micropollutants (OMPs) from water, typically present in concentrations ranging from ng L⁻¹ to μg L⁻¹. However, the efficacy of OMP removal is considerably deteriorated due to competitive adsorption from background dissolved organic matter (DOM), present at substantially higher concentrations in mg L⁻¹. Interpreting the characteristics of competitive DOM is crucial in predicting OMP adsorption efficiencies across diverse natural waters. Molecular weight (MW), aromaticity, and polarity influence DOM competitiveness. Although the aromaticity-related metrics, such as UV₂₅₄, of low MW DOM were proposed to correlate with DOM competitiveness, the method suffers from limitations in understanding the interplay of polarity and aromaticity in determining DOM competitiveness. Here, we elucidate the intricate influence of aromaticity and polarity in low MW DOM competition, spanning from a fraction level to a compound level, by employing direct sample injection liquid chromatography coupled with ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry. Anion exchange resin pre-treatment eliminated 93% of UV₂₅₄-active DOM, predominantly aromatic and polar DOM, and only minimally alleviated DOM competition. Molecular characterization revealed that nonpolar molecular formulas (constituting 26% PAC-adsorbable DOM) with medium aromaticity contributed more to the DOM competitiveness. Isomer-level analysis indicated that the competitiveness of highly aromatic LMW DOM compounds was strongly counterbalanced by increased polarity. Strong aromaticity-derived π-π interaction cannot facilitate the competitive adsorption of hydrophilic DOM compounds. Our results underscore the constraints of depending solely on aromaticity-based approaches as the exclusive interpretive measure for DOM competitiveness. In a broader context, this study demonstrates an effect-oriented DOM analysis, elucidating counterbalancing interactions of DOM molecular properties from fraction to compound level.

It was widely acknowledged that dissolved organic matter (DOM) in natural water has ubiquitous competitiveness against organic micropollutants (OMPs) during adsorption onto activated carbon. However, some (model) low molecular weight organics have been reported to adsorb onto activated carbon, but were not competitive against co-adsorbates. The objective of this study is to identify which adsorbable DOM fractions in natural water contribute to the DOM competitiveness, and what is the impact of the OMP adsorbability and initial OMP concentration on this competitiveness. We, therefore, disassociated the adsorption of DOM fractions and OMPs (carbamazepine, caffeine and sulfamethoxazole) using a two-stage adsorption procedure, removing various adsorbable DOM fractions with powdered activated carbon pretreatment and then unraveling the competitiveness against OMPs of the remaining DOM. Our results demonstrated that DOM competition was not ubiquitous for all adsorbable fractions in natural water, and ∼ 25% of the adsorbable DOM was not competitive. The poorly adsorbable DOM was shown to be a non-competitive co-adsorbate, and its complexation even elevated the adsorption capacity of one of the OMPs (carbamazepine). The amount of DOM competitors increased for weaker adsorbable OMPs, and at higher initial OMP concentrations. The variability in DOM competition, differentiated by DOM adsorbability, has advanced the understanding of DOM competition, from ubiquitous competition to variable roles (varying competitiveness/complementary adsorption) of differently adsorbable DOM fractions during OMP adsorption.