TITLE: Quantitative Spectroscopic Analysis of Water Populations in the Hydrated Nanopore Environments of a Natural Montmorillonite
–ABSTRACT: Smectite clays are implicated in solute trapping in natural and engineered processes. Here we evaluated 23Na solid-state nuclear magnetic resonance (NMR) and thermogravimetric analysis-coupled mass spectrometry (TGA-MS) for quantitative analysis of a hydrated natural Na-montmorillonite equilibrated at different relative humidity (RH). Using X-ray diffraction, we determined predominantly large-sized (~1.55 nm) interlayers at 93% and 75% RH, 2:1 ratio of medium-sized (~1.23 nm) to large-sized interlayers at 55% RH, and 2:1 ratio of small-sized (<0.96 nm) to medium-sized interlayers at 11% RH. The 23Na NMR data revealed 100% of the Na+ populations were fully-hydrated at 93% RH, and loss of fully hydrated Na+ resonance accompanied by a 2:1 ratio of partially-hydrated (outer-sphere) to mineral-bound (inner-sphere) Na+ populations at 55% RH and, remarkably, a near-equal proportion of these latter two Na+ populations at 11% RH. Between 93% and 11% RH, the TGA-MS data captured a 57% increase in tightly-bound waters (water loss at 100-300 ˚C) but only a 22% decrease in freely-exchangeable waters (water loss below 40 ˚C). The addition of exogenous NaCl altered the aforementioned hydration behaviors, particularly at low RH. Our findings of persisting hydrated environments despite interlayer nanopore collapse implied water populations incongruent with smectite interlayer nanopore size distributions. [Link to Article]