Adsorption to solid-water interfaces is a major process governing the fate of waterborne viruses in natural and engineered systems. The relative contributions of different interaction forces to adsorption and their dependence on the physicochemical properties of the viruses remain, however, only poorly understood. Herein, we systematically studied the adsorption of four bacteriophages (MS2, fr, GA, and Qβ) to five model surfaces with varying surface chemistries and to three dissolved organic matter adlayers, as a function of solution pH and ionic strength, using quartz crystal microbalance with dissipation monitoring. The viruses were selected to have similar sizes and shapes but different surface charges, polarities, and topographies, as identified by modeling the distributions of amino acids in the virus capsids. Virus-sorbent interactions were governed by long-ranged electrostatics and favorable contributions from the hydrophobic effect, and shorter-ranged van der Waals interactions were of secondary importance. Steric effects depended on the topographic irregularities on both the virus and sorbent surfaces. Differences in the adsorption characteristics of the tested viruses were successfully linked to differences in their capsid surface properties. Besides identifying the major interaction forces, this work highlights the potential of computable virus surface charge and polarity descriptors to predict virus adsorption to solid-water interfaces.

Adlayers of dissolved organic matter (DOM) form on many surfaces in natural and engineered systems and affect a number of important processes in these systems. Yet, the nanoscalar properties and dynamics of DOM adlayers remain poorly investigated. This work provides a systematic analysis of the properties and dynamics of adlayers formed from a diverse set of eight humic and fulvic acids, used as DOM models, on surfaces of self-assembled monolayers (SAMs) of different alkylthiols covalently bound to gold supports. DOM adsorption to positively charged amine-terminated SAMs resulted in the formation of water-rich adlayers with nanometer thicknesses that were relatively rigid, irreversibly adsorbed, and collapsed upon air drying, as demonstrated by combined quartz crystal microbalance and ellipsometry measurements. DOM adlayer thicknesses varied only slightly with solution pH from 5 to 8 but increased markedly with increasing ionic strength. Contact angle measurements revealed that the DOM adlayers were relatively polar, likely due to the high water contents of the adlayers. Comparing DOM adsorption to SAM-coated sensors that systematically differed in surface charge and polarity characteristics showed that electrostatics dominated DOM-surface interactions. Laccase adsorption to DOM adlayers on amine-terminated SAMs served to demonstrate the applicability of the presented experimental approach to study the interactions of (bio)macromolecules and (nano)particles with DOM.

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Adsorption onto solid-water interfaces is a key process governing the fate and transport of waterborne viruses. Although negatively charged viruses are known to extensively adsorb onto positively charged adsorbent surfaces, virus adsorption in such systems in the presence of negatively charged dissolved organic matter (DOM) as coadsorbate remains poorly studied and understood. This work provides a systematic assessment of the adsorption dynamics of negatively charged viruses (i.e., bacteriophages MS2, fr, GA, and Qβ) and polystyrene nanospheres onto a positively charged model sorbent surface in the presence of varying DOM concentrations. In all systems studied, DOM competitively suppressed the adsorption of the viruses and nanospheres onto the model surface. Electrostatic repulsion of the highly negatively charged MS2, fr, and the nanospheres impaired their adsorption onto DOM adlayers that formed during the coadsorption process. In contrast, the effect of competition on overall adsorption was attenuated for less-negatively charged GA and Qβ because these viruses also adsorbed onto DOM adlayer surfaces. Competition in MS2-DOM coadsorbate systems were accurately described by a random sequential adsorption model that explicitly accounts for the unfolding of adsorbed DOM. Consistent findings for viruses and nanospheres suggest that the coadsorbate effects described herein generally apply to systems containing negatively charged nanoparticles and DOM.