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  1. Free, publicly-accessible full text available December 1, 2024
  2. Free, publicly-accessible full text available November 1, 2024
  3. Per- and polyfluoroalkyl substances (PFAS) are a group of synthetic organofluorine surfactants that are resistant to typical methods of degradation. Thermal techniques along with other novel, less energy-intensive techniques are currently being investigated for the treatment of PFAS-contaminated matrices. Non-equilibrium plasma is one technique that has shown promise for the treatment of PFAS-contaminated water. To better tailor non-equilibrium plasma systems for this application, knowledge of the energy required for mineralization, and in turn the roles that plasma reactive species and heat can play in this process, would be useful. In this study, fundamental thermodynamic equations were used to estimate the enthalpies of reaction (480 kJ/mol) and formation (−4640 kJ/mol) of perfluorooctanoic acid (PFOA, a long-chain legacy PFAS) in water. This enthalpy of reaction estimate indicates that plasma reactive species alone cannot catalyze the reaction; because the reaction is endothermic, energy input (e.g., heat) is required. The estimated enthalpies were used with HSC Chemistry software to produce a model of PFOA defluorination in a 100 mg/L aqueous solution as a function of enthalpy. The model indicated that as enthalpy of the reaction system increased, higher PFOA defluorination, and thus a higher extent of mineralization, was achieved. The model results were validated using experimental results from the gliding arc plasmatron (GAP) treatment of PFOA or PFOS-contaminated water using argon and air, separately, as the plasma gas. It was demonstrated that PFOA and PFOS mineralization in both types of plasma required more energy than predicted by thermodynamics, which was anticipated as the model did not take kinetics into account. However, the observed trends were similar to that of the model, especially when argon was used as the plasma gas. Overall, it was demonstrated that while energy input (e.g., heat) was required for the non-equilibrium plasma degradation of PFOA in water, a lower energy barrier was present with plasma treatment compared to conventional thermal treatments, and therefore mineralization was improved. Plasma reactive species, such as hydroxyl radicals (⋅OH) and/or hydrated electrons (e−(aq)), though unable to accelerate an endothermic reaction alone, likely served as catalysts for PFOA mineralization, helping to lower the energy barrier. In this study, the activation energies (Ea) for these species to react with the alpha C–F bond in PFOA were estimated to be roughly 1 eV for hydroxyl radicals and 2 eV for hydrated electrons.

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    Free, publicly-accessible full text available September 1, 2024
  4. Per- and polyfluoroalkyl substances (PFAS) are a large group of man-made fluorinated organic chemicals that can accumulate in the environment. In water resource recovery facilities (WRRFs), some commonly detected PFAS tend to partition to and concentrate in biosolids where they can act as a source to ecological receptors and may leach to groundwater when land-applied. Although biosolids undergo some stabilization to reduce pathogens before land application, they still contain many microorganisms, contributing to the eventual decomposition of different components of the biosolids. This work demonstrates ways in which microbial weathering can influence biosolids decomposition, degrade PFAS, and impact PFAS partitioning in small-scale, controlled laboratory experiments. In the microbial weathering experiments, compound-specific PFAS biosolids–water partitioning coefficients ( K d ) were demonstrated to decrease, on average, 0.4 logs over the course of the 91 day study, with the most rapid changes occurring during the first 10 days. Additionally, the highest rates of lipid, protein, and organic matter removal occurred during the same time. Among the evaluated independent variables, statistical analyses demonstrated that the most significant solids characteristics that impacted PFAS partitioning were organic matter, proteins, lipids, and molecular weight of organics. A multiple linear regression model was built to predict PFAS partitioning behavior in biosolids based on solid characteristics of the biosolids and PFAS characteristics with a R 2 value of 0.7391 when plotting predicted and measured log  K d . The findings from this work reveal that microbial weathering can play a significant role in the eventual fate and transport of PFAS and their precursors from biosolids. 
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  5. Van Mullem, T. ; De Belie, N. ; Ferrara, L. ; Gruyaert, E. ; Van Tittelboom, K. (Ed.)

    The goal of this research is to develop innovative damage-responsive bacterial-based self-healing fibers (hereafter called BioFiber) that can be incorporated into concrete to enable two functionalities simultaneously: (1) crack bridging functionality to control crack growth and (2) crack healing functionality when a crack occurs. The BioFiber is comprised of a load-bearing core fiber, a sheath of bacteria-laden hydrogel, and an outer impermeable strain-responsive shell coating. An instant soaking manufacturing process was used with multiple reservoirs containing bacteria-laden, hydrophilic prepolymer and crosslinking reagents to develop BioFiber. Sodium-alginate was used as a prepolymer to produce calcium-alginate hydrogel via ionic crosslinking on the core fiber. The dormant bacteria (spore) ofLysinibacillus sphaericuswas incorporated in hydrogel as a self-healing agent. Then, an impermeable polymeric coating was applied to the hydrogel-coated core fibers. The impermeable strain-responsive shell coating material was manufactured using the polymer blend of polystyrene and polylactic acid. The high swelling capacity of calcium-alginate provides the water required for the microbially induced calcium carbonate precipitation (MICP) chemical pathway, i.e., ureolysis in this study. The strain-responsive impermeable coating provides adequate flexibility during concrete casting to protect the spores and alginate before cracking and sufficient stress-strain behavior to grant damage-responsiveness upon crack occurrence to activate MICP. To evaluate the behavior of developed BioFiber, the swelling capacity of the hydrogel, the impermeability of shell coating, the spore casting survivability, and MICP activities were investigated.

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  6. Van Mullem, T. ; De Belie, N. ; Ferrara, L. ; Gruyaert, E. ; Van Tittelboom, K. (Ed.)

    Vegetative cells used for the concrete bio self-healing process often face threatening environmental conditions such as extreme temperature, pH, salinity, shear stress, and starvation during the hardening process and the service life of the concrete. These conditions can eventually lead to cell death. Since endospores are likely to remain dormant for prolonged periods and can survive, germinate, and grow under inhospitable conditions, they are a suitable bacterial phenotype to introduce into concrete for microbial-inducing calcite precipitation. This study investigated how different endosporulation methods affect the endosporulation ratio (i.e., the fraction of vegetative cells that are converted to endospores during endosporulation), as well as the germination ratio (i.e., the fraction of endospores that are converted to vegetative cells following germination) and the microbial-induced calcite precipitation (MICP) performance of germinated endospores after facing harsh conditions of concrete, specifically, freeze and that cycling. Results from this study show that thermal shock followed by cell incubation in alkaline conditions leads to increased sporulation and germination ratios. It was also observed that freeze and thaw cycling had negligible effects on calcite production by endospores, while exposure of vegetative cells to these harsh conditions led to not only less biomass and calcite production but also to a lower mass of calcite produced per mass of cells, as determined by thermogravimetric analysis (TGA). The results from this study provide key insights into improving methods for endosporulation and germination to effectively use them for bio self-healing applications in concrete.

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