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In a system where protons and hydroxide ions are the only aqueous species, the point of zero net proton charge (pHPZNPC) of a mineral defines the pH at which the positively and negatively charged functional groups on its surface are equal (Drever, 1997). Ascertaining the pHPZNPC of clay minerals, a ubiquitous component in soils, sediment and rivers, is useful in predicting its electrostatic interactions with charged aqueous species, colloids, and bacteria. While the pHPZNPC values of most clays have been reported, the variation of pHPZNPC with changing solution ionic strength (IS) and the mathematic relationship between them are not well-understood but critical in assessing the surface reactivity of clays in aqueous solutions ranging from freshwater to brines. To address this gap, we studied the relationship of the pHPZNPC of three clay minerals (kaolinite, illite, and montmorillonite) at seven ionic strengths (from 0.001 to 0.1 M). Titration data for each clay were used to calculate the pHPZNPC by two methods previously documented in literature: (1) using the difference between the blank titration and clay titrations, and (2) by the difference between the number of protons added during titration and the number of protons remaining in solution. The results show that: (1) unlike simple metal oxides (e.g., hematite, gibbsite, quartz), titration curves of clay minerals at different IS do not intersect at a common pHPZNPC value; (2) the pHPZNPC for kaolinite is around 5.6 to 6.6 while the pHPZNPC for illite and montmorillonite is in the range of 9 to10; (3) the pHPZNPC value decreases systematically with increasing IS for all three clay minerals studied; and (4) the change of pHPZNPC is linear with log(IS). A third method using surface complexation modeling (SCM) approach was applied to calculate the pHPZNPC of the clay minerals, and the results match well with Method 2. Our results allow for a more accurate estimation of clay surface charge property in aqueous environment, which, in turn, will improve model predictions of the adsorption of charged species in systems in which ionic strength changes.

Given the high surface reactivity of clay minerals, it is assumed that flocculation will lead to metal accumulation in marginal marine settings. However, the degree of metal sorption to clays is impacted by solution pH and ionic strength, and it remains unknown whether riverine clays indeed serve as a metal sink once they encounter seawater where pH and ionic strength markedly increase. Here, we conducted cadmium (Cd) adsorption experiments to three types of common clay minerals – kaolinite, illite and montmorillonite. We found that 20–30% of Cd from illite and montmorillonite surfaces were desorbed when transitioning from freshwater to seawater pH and ionic strength conditions, while kaolinite showed no discernible differences. Synchrotron X-ray adsorption spectroscopy confirmed that Cd release corresponded to a change in bonding from outer- to inner-sphere complexes when clays encountered seawater pH and ionic strength conditions. If other trace nutrients (such as Cu, Zn, Co) adsorbed onto riverine clay minerals behave in a similar manner to Cd, we speculate that their desorption in marginal marine settings should exert a significant impact on the productivity of the biosphere.