Are Geotextiles Silent Contributors of Ultrashort Chain PFASs to the Environment?

We investigated the presence of per- and poly fluoroalkyl substances (PFASs) in woven and nonwoven polypropylene geotextiles and four nonwoven polyester geotextiles commonly used in modern geosynthetic composite lining systems for waste containment facilities such as landfills. Targeted analysis for 23 environmentally significant PFAS molecules and methods for examining "PFAS total" concentrations were utilized to assess their occurrence in geotextiles. This analysis showed that most geotextile specimens evaluated in the current investigation contained the ultrashort chain PFAS compound pentafluoropropionic acid (PFPrA). While the concentrations ranged from nondetectable to 10.84 µg/g, the average measured concentrations of PFPrA were higher in polypropylene than in polyester geotextiles. "PFAS total" parameters comprising total fluorine (TF) and total oxidizable precursors (TOPs) indicate that no significant precursor mass nor untargeted intermediates were present in geotextiles. Therefore, this study identified geotextiles as a possible source of ultrashort PFASs in engineered lined waste containment facilities, which may contribute to the overall PFAS total concentrations in leachates or liquors they are in contact with. The findings reported for the first time herein may lead to further implications on the fate and migration of PFASs in geosynthetic composite liners, as previously unidentified concentrations, particularly of ultrashort-chain PFASs, may impact the extent of PFAS migration through and attenuation by constituents of geosynthetic composite liner systems. Given the widespread use of geotextiles in various engineering activities, these findings may have other unknown impacts. The significance of these findings needs to be further elucidated by more extensive studies with larger geotextile sample sizes to allow broader, generalized conclusions to be drawn.

Tunable Colloidal Properties of Lauramidopropyl Betaine and Li Co-modified Montmorillonite in Ethanol/Water.

Montmorillonite (Mt) is a hydrophilic clay mineral with a generally high cationic exchange capacity and a remarkable swellability in water. Yet the application of Mt in cosmetics, paints, polymer nanocomposites, drug delivery systems, and tissue engineering are limited due to its unfavorable swelling and dispersion in alcohol/water mixtures. Improving the swellability and dispersibility of Mt in mixtures of ethanol and water remains challenging. Here, we showed that the swellability and dispersibility of Mt in ethanol/water could be significantly enhanced when lithium-Mt (Li-Mt) was intercalated by zwitterionic surfactant lauramidopropyl betaine (LPB). The binding mechanism of the LPB intercalate to Li-Mt originated from a combination of van der Waals forces, ion-dipole interaction, and electrostatic attraction. Due to the synergistic effect of Li+ and LPB, the comodified Mt (LPB-Li-Mt) exhibited excellent swellability, dispersibility, and rheological properties. The structure, morphology, zeta potential, dispersibility, and gel-forming performance of LPB-Li-Mt can be modulated by the concentrations of ethanol in ethanol/water mixtures. When the ethanol concentration increased to 75% v/v ethanol solution, the free swelling of LPB-Li-Mt remained above 80%. The results from X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoemission spectrometry, and small-angle X-ray scattering confirmed the full exfoliation of LPB-Li-Mt at 75% (v/v) ethanol solution. The formation of a stable colloidal LPB-Li-Mt dispersion in a mixture of ethanol/water might be derived from the association between water molecules and the Li+, the hydrophobic interaction, and the ion-dipole of ethanol with the LPB molecules. The findings provide a guide for improving dispersion and swelling of Mt and modified ones in water-miscible organic solvents.

Role of Exchange Cations and Layer Charge on the Dynamics of Confined Water.

Describing the dynamic behavior of water confined in clay minerals is a fascinating challenge and crucial in many research areas, ranging from materials science and geotechnical engineering to environmental sustainability. Water is the most abundant resource on Earth, and the high reactivity of naturally occurring hydrous clay minerals used since prehistoric times for a variety of applications means that water-clay interaction is a ubiquitous phenomenon in nature. We have attempted to experimentally distinguish the rotational dynamics and translational diffusion of two distinct populations of interlayer water, confined and ultraconfined, in the sodium (Na) forms of two smectite clay minerals, montmorillonite (Mt) and hectorite (Ht). Samples hydrated at a pseudo one-layer hydration (1LH) state under ambient conditions were studied with quasi-elastic neutron scattering (QENS) between 150 and 300 K. Using a simplified revised jump-diffusion and rotation-diffusion model (srJRM), we observed that while interlayer water near the ditrigonal cavity in Ht forms strong H-bonds to both adjacent surface O and structural OH, H-bonding of other more prevalent interlayer water with the surface O is weaker compared to Mt, inducing a higher temperature for dynamical changes of confined water. Given the lower layer charge and faster dynamics observed for Ht compared to Mt, we consider this strong evidence confirming the influence of the interlayer cation and surfaces on confined water dynamics.

Suitability of remediated heat-treated soil in concrete applications.

Significant quantities of soil are adversely impacted by organic contaminants, including per- and poly-fluoroalkyl substances (PFAS). One proven technology for remediating PFAS affected soils is excavation and heat-treatment which destroys the PFAS, but renders the soil as an industrial waste that is normally diverted to landfill. This study investigated alternative uses for heat-treated industrial waste (HIW) soils as components in concrete, as aggregate replacement and as partial substitution of cement binder. At a replacement rate of 100% fine aggregate and ≈15% coarse aggregate, concretes made with HIW soil exhibited a strength of 47.2-48.3 MPa after 28 days' curing, compared with a reference concrete of 49.7-53.1 MPa, making the HIW ideal for aggregate replacement. Overall, the study demonstrated a novel, holistic approach to (1) remediating PFAS-affected soils, (2) diverting contaminated soil away from landfill, (3) reducing the use of high quality quarried concrete aggregates and (4) producing normal-strength concretes with a lower embodied carbon footprint than existing approaches. This study reveals that in Australia, up to 93% of all contaminated soil currently sent to landfill annually could instead be used a resource for mid-strength concretes, suitable for many applications.

Frequency Dependent Silica Dissolution Rate Enhancement under Oscillating Pressure via an Electrochemical Pressure Solution-like, Surface Resonance Mechanism.

From atomic force microscopy (AFM) experiments, we report a new phenomenon in which the dissolution rate of fused silica is enhanced by more than 5 orders of magnitude by simply pressing a second, dissimilar surface against it and oscillating the contact pressure at low kHz frequencies in deionized water. The silica dissolution rate enhancement was found to exhibit a strong dependence on the pressure oscillation frequency consistent with a resonance effect. This harmonic enhancement of the silica dissolution rate was only observed at asymmetric material interfaces (e.g., diamond on silica) with no evidence of dissolution rate enhancement observed at symmetric material interfaces (i.e., silica on silica) within the experimental time scales. The apparent requirement for interface dissimilarity, the results of analogous experiments performed in anhydrous dodecane, and the observation that the silica "dissolution pits" continue to grow in size under contact stresses well below the silica yield stress refute a mechanical deformation or chemo-mechanical origin to the observed phenomenon. Instead, the silica dissolution rate enhancement exhibits characteristics consistent with a previously described 'electrochemical pressure solution' mechanism, albeit, with greatly amplified kinetics. Using a framework of electrochemical pressure solution, an electrochemical model of mineral dissolution, and a recently proposed "surface resonance" theory, we present an electro-chemo-mechanical mechanism that explains how oscillating the contact pressure between dissimilar surfaces in water can amplify surface dissolution rates by many orders of magnitude. This reaction rate enhancement mechanism has implications not only for dissolution but also for potentially other reactions occurring at the solid-liquid interface, e.g. catalysis.

Durability Characterisation of Portland Cement-Carbon Nanotube Nanocomposites.

Multiwalled carbon nanotubes have outstanding mechanical properties that, when combined with Portland cement, can provide cementitious composites that could lead to the innovative construction of stronger, lighter, and thinner built infrastructure. This paper addresses a knowledge gap that relates to the durability of CNT-cement composites. The durability to corrosive chloride, uptake of water by sorption, and flow of the permeability of water acting under high water pressure are addressed. Flow simulations were undertaken through segmented 3D pore networks, based on X-ray computed microtomography measurements, the creation of a virtual microstructure, and fluid simulations that were compared with larger-scale samples. The investigation showed decreased water sorptivity of CNT-cement mixtures, indicating improved durability for the cover zone of concrete that is prone to the uptake of water and water-borne corrosives. Chloride diffusion of CNT-cement composites provided up to 63% improvement compared with control samples. The favourable durability bodes well for the construction of long-life CNT-reinforced concrete infrastructure.

Miniature Resistance Measurement Device for Structural Health Monitoring of Reinforced Concrete Infrastructure.

A vast amount of civil infrastructure is constructed using reinforced concrete, which can be susceptible to corrosion, posing significant risks. Corrosion of reinforced concrete has various causes, with chloride ingress known to be a major contributor. Monitoring this chloride ingress would allow for preventative maintenance to be less intrusive at a lower cost. Currently, chloride sensing methods are bulky and expensive, leaving the majority of concrete infrastructures unmonitored. This paper presents the design and fabrication of a miniature, low-cost device that can be embedded into concrete at various locations and depths. The device measures localized concrete resistance, correlating to the chloride ingress in the concrete using equations listed in this paper, and calculated results from two experiments are presented. The device benefits from a four-probe architecture, injecting a fixed frequency AC waveform across its outer electrodes within the cement block. Voltage across the internal electrodes is measured with a microcontroller and converted to a resistance value, communicated serially to an external computer. A final test showcases the ability of the device for three-dimensional mass deployment.

Insights into the Rheological Behavior of Aqueous Dispersions of Synthetic Saponite: Effects of Saponite Composition and Sodium Polyacrylate.

Synthetic saponite (Sap) easily delaminates in water to form a transparent sol and hydrogel with excellent rheological performance and is thus widely used in paints, cosmetics, and nanomaterials. The thixotropic property of Sap hydrogels is heavily dependent on the nature of Sap and the external electrolyte and polyelectrolyte; yet, details on the relationship between rheological behaviors of saponite hydrogels and Sap composition and polyelectrolyte remain unclear. In this work, thixotropic rheological behaviors of a series of synthetic Sap hydrogels, with and without added sodium polyacrylate polyelectrolyte (NaPA), were investigated. The Sap samples, with a Si/Al molar ratio from 5 to 25, were successfully synthesized using hydrothermal methods and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The rheological performances of aqueous Sap dispersions and particle sizes and ζ-potentials of Sap were measured. The results showed that the crystallinity of the Sap increased with an increasing Si/Al molar ratio. All Sap samples, with the exception of the Sap with a Si/Al molar ratio of 5, dispersed well in water (3 wt %) to form hydrogels. The rheological behaviors of the hydrogels were related to the chemical composition and the layer charge of the Sap. The Sap with a Si/Al molar ratio of 25 had higher viscosity due to improved delamination. The addition of the NaPA, an anionic polyelectrolyte, into the hydrogels decreased the viscosity and altered the thixotropic properties such that the hydrogel becomes a sol. The addition of NaPA facilitated the dispersion and delamination of Sap, because under the electric field of negatively charged Sap particles in the hydrogel, the anionic NaPA was instantaneously polarized and thereby entered the hydration layer of the Sap particles.

Partial exchange of Fe(III) montmorillonite with hexadecyltrimethylammonium cation increases catalytic activity for hydrophobic substrates.

Fe(III) montmorillonite clay that was partially exchanged with hexadecyltrimethylammonium (HDTMA(+)) cations achieved increased catalytic activity for the oxidative coupling of hydrophobic organic substrates. A series of mixed-cation organoclays were produced, where the organic cation content ranged from 6 to 50% relative to the cation-exchange capacity (CEC) of the clay, and were tested for catalytic activity using different Fe(III)-mediated oxidative coupling reactions. Enhanced catalytic activity by Fe(3+)/HDTMA(+) montmorillonite for coupling hydrophobic substrates was observed, with maximum catalytic activity in the oxidative coupling of 2-naphthol observed at 6% HDTMA(+) coverage. However, maximum catalytic activity with a more hydrophobic substrate, anthrone, was achieved with 50% HDTMA(+) coverage, indicating that matching levels of organic modification to substrate hydrophobicity improves catalytic activity. The organization of the organic cations at the clay surfaces proved to be heterogeneous, as determined by scanning transmission X-ray microscopy (STXM) and powder X-ray diffraction. Results from molecular dynamics simulations supported the heterogeneous nature of the catalysts but also pointed toward large regions within the interlayers that may be filled with nonreactive hydrated Fe oxides resulting from the organic cation treatment. The exchangeable Fe content of the organic treated clays, as determined by AAS and ICP measurements, was observed to be higher than expected relative to that of Fe-saturated clay, substantiating this hypothesis. These findings have implications for the development of substrate-specific clay catalysts, where the composition and configuration of exchangeable cations can be matched to a particular substrate or reaction.