Microbially Mediated Rubber Recycling to Facilitate the Valorization of Scrap Tires.

The recycling of scrap tire rubber requires high levels of energy, which poses challenges to its proper valorization. The application of rubber in construction requires significant mechanical and/or chemical treatment of scrap rubber to compatiblize it with the surrounding matrix. These methods are energy-consuming and costly and may lead to environmental concerns associated with chemical leachates. Furthermore, recent methods usually call for single-size rubber particles or a narrow rubber particle size distribution; this, in turn, adds to the pre-processing cost. Here, we used microbial etching (e.g., microbial metabolism) to modify the surface of rubber particles of varying sizes. Specifically, we subjected rubber particles with diameters of 1.18 mm and 0.6 mm to incubation in flask bioreactors containing a mineral medium with thiosulfate and acetate and inoculated them with a microbial culture from waste-activated sludge. The near-stoichiometric oxidation of thiosulfate to sulfate was observed in the bioreactors. Most notably, two of the most potent rubber-degrading bacteria (Gordonia and Nocardia) were found to be significantly enriched in the medium. In the absence of added thiosulfate in the medium, sulfate production, likely from the desulfurization of the rubber, was also observed. Microbial etching increased the surface polarity of rubber particles, enhancing their interactions with bitumen. This was evidenced by an 82% reduction in rubber-bitumen separation when 1.18 mm microbially etched rubber was used. The study outcomes provide supporting evidence for a rubber recycling method that is environmentally friendly and has a low cost, promoting pavement sustainability and resource conservation.

Pyrolysis of biomass harvested from heavy-metal contaminated area: Characteristics of bio-oils and biochars from batch-wise one-stage and continuous two-stage pyrolysis.

This study evaluates pyrolysis products obtained from biomasses (silver grass, pine, and acacia) harvested from heavy-metal-contaminated soil. To do so, we utilized two methods: a batch one-stage pyrolysis, and a continuous two-stage pyrolysis. The study results show that the yields and characteristics of bio-oils and biochars varied depending on the pyrolysis process and the type of biomass. The two-stage pyrolysis having two reactors (auger and fluidized bed reactors) appeared to be very suitable for specific chemicals production such as acetic acid, acetol, catechol, and levoglucosan. The biochar obtained from the fluidized-bed reactor of two-stage pyrolysis had high thermal stability, high crystallinity, high inorganic content, and a small number of functional groups. In contrast, the biochar obtained from the one-stage pyrolysis had low thermal stability, low crystallinity, a high carbon content, and a large number of functional groups. The biochar obtained from the two-stage pyrolysis appeared to be suitable as a material for catalyst support and as an adsorbent. The biochar obtained from one-stage pyrolysis appeared to be a suitable as a soil amendment, as an adsorbent, and as a precursor of activated carbon. All biochars showed a negative carbon footprint. In the end, this study, which was conducted using two different processes, was able to obtain the fact that products of pyrolysis biomass contaminated with heavy metals have different characteristics depending on the process characteristics and that their utilization plans are different accordingly. If the optimal utilization method proposed through this study is found, pyrolysis will be able to gain importance as an effective treatment method for biomass contaminated with heavy metals.

Soil amended with Algal Biochar Reduces Mobility of deicing salt contaminants in the environment: An atomistic insight.

Soil-based filter media in green infrastructure buffers only a minor portion of deicing salt in surface water, allowing most of that to infiltrate into groundwater, thus negatively impacting drinking water and the aquatic ecosystem. The capacity of the filter medium to adsorb and fixate sodium (Na+) and chloride (Cl-) ions has been shown to improve by biochar amendment. The extent of improvement, however, depends on the type and density of functional groups on the biochar surface. Here, we use density functional theory (DFT) and molecular dynamics (MD) simulations to show the merits of biochar grafted by nitrogenous functional groups to adsorb Cl-. Our group has shown that such functional groups are abundant in biochar made from protein-rich algae feedstock. DFT is used to model algal biochar surface and its possible interactions with Cl- through two possible mechanisms: direct adsorption and cation (Na+)-bridging. Our DFT calculations reveal strong adsorption of Cl- to the biochar surface through hydrogen bonding and electrostatic attractions between the ions and active sites on biochar. MD results indicate the efficacy of algal biochar in delaying chloride diffusion. This study demonstrates the potential of amending soils with algal biochar as a dual-targeting strategy to sequestrate carbon and prevent deicing salt contaminants from leaching into water bodies.

Distinguishing nanoparticle drug release mechanisms by asymmetric flow field-flow fractionation.

This research demonstrates the development, application, and mechanistic value of a multi-detector asymmetric flow field-flow fractionation (AF4) approach to acquire size-resolved drug loading and release profiles from polymeric nanoparticles (NPs). AF4 was hyphenated with multiple online detectors, including dynamic and multi-angle light scattering for NP size and shape factor analysis, fluorescence for drug detection, and total organic carbon (TOC) to quantify the NPs and dissolved polymer in nanoformulations. The method was demonstrated on poly(lactic-co-glycolic acid) (PLGA) NPs loaded with coumarin 6 (C6) as a lipophilic drug surrogate. The bulk C6 release profile using AF4 was validated against conventional analysis of drug extracted from the NPs and complemented with high performance liquid chromatography - quadrupole time-of-flight (HPLC-QTOF) mass spectrometry analysis of oligomeric PLGA species. Interpretation of the bulk drug release profile was ambiguous, with several release models yielding reasonable fits. In contrast, the size-resolved release profiles from AF4 provided critical information to confidently establish the release mechanism. Specifically, the C6-loaded NPs exhibited size-independent release rate constants and no significant NP size or shape transformations, suggesting surface desorption rather than diffusion through the PLGA matrix or erosion. This conclusion was supported through comparative experimental evaluation of PLGA NPs carrying a fully entrapped drug, enrofloxacin, which showed size-dependent diffusive release, along with density functional theory (DFT) calculations indicating a higher adsorption affinity of C6 onto PLGA. In summary, the development of the size-resolved AF4 method and data analysis framework fulfills salient analytical gaps to determine drug localization and release mechanisms from nanomedicines.

Bio-grafted silica to make an asphalt road a sink for reactive environmental pollutants.

Asphalt-surfaced areas such as roads have been reported as major non-combustion sources of reactive organic compounds in urban areas. Emission of latter compounds from asphalt is exacerbated due to exposure to sunlight and high temperature, contributing to negative human and environmental health outcomes. Furthermore, loss of asphalt components over time is linked to bitumen's aging that reduces service life of roads. Here, we introduce a designed bio-grafted-silica nano-filler derived from wood pellet as a sink for latter volatile compounds in an asphalt mixture. Molecular modeling calculations showed the remarkable adsorptive activity of the bio-grafted silica for trapping select asphalt volatiles, especially for the sulfur-containing aromatics and the oxygen-containing aromatics. Laboratory experiment revealed that the bitumen modified with bio-grafted silica exhibited up to 23% lower signs of aging. Thermogravimetric analysis proved that the modified bitumen exhibited a 16% reduction in mass loss compared to neat bitumen. Dynamic vapor sorption analysis also showed bio-grafted silica adsorbed higher amounts of a candidate volatile than pristine silica. The study outcomes highlights the advantages of a bio-derived modifier in asphalt to address concerns associated with the loss of hazardous compounds.

Interaction mechanisms of polyphosphoric acid and nano clay in bituminous composites.

It has been reported that adding polyphosphoric acid (PPA) to bitumen modified with Montmorillonite clay (MMT) makes the bituminous composite less prone to swelling and more resistant to moisture damage, thus improving two major causes of pavement distress. There has been no in-depth study on the underlying mechanism for such a synergistic effect between MMT and PPA. Here, we used laboratory experiments and computational modeling to study how PPA moderates the intermolecular interactions in bitumen modified with MMT. The results showed that PPA had notable interactions with both MMT and bitumen components (BCs); however, PPA's preferential adsorption to MMT was verified by a significantly higher binding energy (-127.3 kcal/mol) for PPA-sealed MMT than for PPA-BCs (-85.9 kcal/mol). The higher binding energy for PPA-sealed MMT caused PPA to be strongly adsorbed on the MMT surface in the first stage, causing partial intercalation into the clay gallery and blocking subsequent entry of water. PPA's affinity to interact with BCs then allowed PPA to be a bridge between MMT and BCs, leading to more intermolecular interactions and better sealing for MMT. The calculated binding energies for interactions of BC with pre-adsorbed PPA on MMT were higher than those for interactions of BC with PPA alone. In both dry and wet laboratory conditions, bitumen modified with PPA-sealed MMT had higher values of shear thinning and G*/sin(δ) than bitumen modified with MMT.

Interactions of SARS-CoV-2 with inanimate surfaces in built and transportation environments.

Understanding the interactions and transmission of pathogens with/via inanimate surfaces common in the built environment and public transport vehicles is critical to promoting sustainable and resilient urban development. Here, molecular dynamics (MD) simulations are used to study the adhesion of SARS-CoV-2 (the causative agent of COVID-19) to some of these surfaces at different temperatures (same for surfaces and ambiance) ranging from -23 to 60 °C. Surfaces simulated are aluminum, copper, copper oxide, polyethylene (PE), and silicon dioxide (SiO2). Steered MD (SMD) simulations are also used to investigate the transfer of the virus from PE and SiO2 when a contaminated surface is touched. The virus shows the lowest and highest adhesions to PE and SiO2, respectively (20 vs 534 eV). Influence of temperature is not found to be noticeable. Using simulated water molecules to represent moisture on the skin, SMD simulations show that water molecules can lift the virus from the PE surface but damage the virus when lifting it from the the SiO2 surface. The results suggest that the PE surface is a more favorable surface to transmit the virus than the other surfaces simulated in this study. The results are compared with those reported in a few experimental studies.

Inherently Functionalized Carbon from Lipid and Protein-Rich Biomass to Reduce Ultraviolet-Induced Damages in Bituminous Materials.

This paper examines the merits of using an inherently functionalized carbon, referred to as biochar as a free radical scavenger. The biochar was made from thermochemical liquefaction of a blend of algae (rich in protein and nucleic acids) and manure (rich in lipid). Here, we studied biochar's efficacy as a free-radical scavenger and ultraviolet blocker to qualify it as an anti-aging additive in construction, including roofing shingles made from the bituminous composite. The study's results show that the addition of biochar to bitumen significantly reduced the aging of bitumen. All tested biochars made from various relative proportions of algae and swine manure were found to be effective at reducing the extent of aging; however, the biochar made from algae alone was the most effective. The algal biochar was found to be an effective antiaging additive delaying aging up to 36%, as evidenced by lower rheology and the chemistry-based aging index compared to those of control bitumen after being exposed to the same aging protocol. Algal biochar was found to be more effective than other studied biochar scenarios owing to its inherently functionalized nature. The latter result could be attributed to the high surface area and rich phenol functional groups in algal biochar, turning it into an effective free-radical scavenger. The study outcome highlights the applicability of this inherently functionalized carbon referred to as biochar in construction to enhance sustainability while promoting the circular economy and the biomass value chain.

Non-Covalent π-Stacking Interactions between Asphaltene and Porphyrin in Bitumen.

In recent years, the dominant organizing role of non-covalent π-stacking interactions in the association of asphaltenes and porphyrins was criticized and replaced with cooperative forces that are mostly covalent in nature. Here, we show the significant contribution of non-covalent forces in stabilizing the π-stacking of asphaltenes and porphyrins. To understand the binding chemistry of metalloporphyrin-asphaltene, the interaction of nickel octaethylporphyrin with a series of model fragments for asphaltene was studied in two different pathways: axial coordination and π-stacking. Nickel octaethylporphyrin was specifically studied because a main fraction of vanadium and nickel metals in petroleum residues are chelated with porphyrins, and the refining processes in petroleum industries are affected by the significant detrimental impact of these metal compounds. The results of the extended transition state-natural orbital of chemical valence (ETS-NOCV) technique provide strong evidence that the bonding interaction in the π-stacking configuration is much preferred to the axial coordination. Energy decomposition analysis verifies the significant contribution of non-covalent forces in stabilizing the π-stacking of asphaltene-porphyrin, showing that there are other forces driving the formation of asphaltene-porphyrin stacks. Indeed, a non-negligible portion of these stabilizing forces is contributed by strong orbital mixing interactions through charge transfer between active centers; this contribution is mostly overlooked in π-stacking interactions. This matter includes the π-stacking interactions of asphaltene-asphaltene. Isosurfaces of deformation density (Δρ) provide better insights into the π-stacking preference. NOCV deformation densities are delocalized over the entire complex in the π-stacking conformer, leading to the multi-centric charge transfer zone; Δρ isosurfaces of axial coordination are mostly localized on the limited centers involved in chemical bonding.

Using Fundamental Material Properties to Predict the Moisture Susceptibility of the Asphalt Binder: Polarizability and a Moisture-Induced Shear-Thinning Index.

Many biomodifiers have recently been introduced to the asphalt industry to improve the performance of asphalt mixtures, rejuvenate aged asphalt, and/or partially replace asphalt binder. It is critical to screen these biomodifiers for their susceptibility to moisture damage before they are used in construction. This study develops a computational approach and a laboratory technique to predict the moisture susceptibility of modifiers used in asphalt binder mixtures. The computational approach uses the "polarizability" factor, which is one of the conceptual descriptors in density functional theory. Polarizability is indicative of the formation of instantaneous dipoles that are oriented in the applied field. A lower polarizability indicates a lower propensity of the chemical species to interact with other species in their chemical environment. The laboratory method defines a moisture-induced shear-thinning index. Moisture-induced shear-thinning measures the loss of interfacial bonds between the asphalt binder and siliceous surfaces due to water exposure. Both proposed indicators are used to evaluate and compare biomodifiers from four sources: waste vegetable oil, swine manure, algae, and a co-liquefied blend of swine manure and algae. In a comparative study, waste vegetable oil with a high content of long-chain alkanes and fatty acids showed the highest polarizability and the highest moisture-induced shear-thinning index, indicating the highest susceptibility to moisture damage. In contrast, the chemical composition of the biomodifier produced from the co-liquefaction of swine manure and algae showed the lowest polarizability and the lowest moisture-induced shear-thinning index, indicating the highest resistance to moisture damage.

Multiscale Characterization of a Wood-Based Biocrude as a Green Compatibilizing Agent for High-Impact Polystyrene/Halloysite Nanotube Nanocomposites.

This paper investigates merits of using a wood-based biocrude (WB) from aspen wood to improve the compatibility of halloysite nanotubes (HNTs) with high-impact polystyrene to develop nanocomposites with desirable thermomechanical properties. Morphological, thermal, and rheological properties of the resulting nanocomposite are used as indicators of the compatibility and dispersion of the modified HNT within the polymer matrix. Computational modeling using density functional theory is used along with laboratory experiments to provide a multiscale characterization of the above biocrude and nanocomposites. Studies performed through dispersion-corrected density functional theory calculations show that the active functional groups of WB molecules including carbonyl, hydroxyl, and carboxylic interact with the HNT surface, while their aromatic tails interact with the phenyl groups of the polystyrene. Furthermore, the studies reveal how WB molecules act as bridges between the hydrophobic polymer and the hydrophilic clay improving the compatibility. The latter was confirmed by Hansen solubility parameters and was evidenced in improved dispersion of clay within the polystyrene matrix observed by microscopy. Rheological and thermal analyses of the modified HNT and nanocomposites showed physical interactions of WB with HNT surface as well as interactions between the WB-modified HNT and the high-impact polystyrene. The WB was found to be a strong candidate as a green compatibilizing agent for HNT in high-impact polystyrene. The study results can provide insights for formulators and manufacturers looking for green compatibilizing agents in conventional nanocomposites for construction and manufacturing applications.

Multiscale Evaluation of Moisture Susceptibility of Biomodified Bitumen.

This paper studies the selective adsorption and dewetting processes of various biomodifiers with respect to siliceous surfaces to determine dominant moisture damage mechanisms in bitumen doped with biomodifiers. Accordingly, it introduces four different biomodifiers made from various biomasses while explaining their differential effects on moisture susceptibility of bitumen when they are introduced to bitumen as a modifier to make commonly used biomodified binders. The biomodified binders studied here are made from extracts of biomass: wood pellets, miscanthus, corn stover, and animal waste. The moisture effect on biomodified bitumen was evaluated through contact angle measurement followed by molecular-level binding energy based on density functional theory (DFT). The change of contact angle between each biomodified bitumen and a silica surface when exposed to water was used as an indicator of the propensity for dewetting. The biomodifiers from animal waste showed the least change, followed by corn stover, wood pellet, and miscanthus. This aligns with our results of in situ Fourier transform infrared analysis, which showed that the biomodifier from miscanthus has the lowest adsorption affinity, while the one from animal waste has the highest adsorption onto siliceous stones. The higher adsorption efficiency of animal-based biomodifier is also verified by DFT-based molecular modeling, showing that the lipid and protein contents of animal waste, containing highly polar small compounds, exhibit a better adsorption to silica nanoparticles compared to carbohydrate of terrestrial plants.

Compositional mapping of bitumen using local electrostatic force interactions in atomic force microscopy.

In recent years, many researchers have investigated bitumen surface morphology, especially the so-called bee-like structures, in an attempt to relate the chemical composition and molecular conformation to bitumen micromechanics and ultimately performance properties. Even though recent studies related surface morphology and its evolution to stiffness and stress localization, the complex chemical nature of bitumen and its time- and temperature-dependent properties still engender significant questions about the nature and origin of the observed morphological features and how they evolve due to exposure to various environmental and loading conditions. One such question is whether the observed surface features are formed from wax or from the coprecipitation of wax and asphaltene. Our prior work was mainly theoretical; it used density functional theory and showed that the coprecipitation theory may not stand, mainly because wax-asphaltene interactions are not thermodynamically favourable compared to wax-wax interactions. This paper presents a comprehensive approach based on experiments to study surface morphology of bitumen and conduct compositional mapping to shed light on the origin of the bee-like surface morphological features. We used Atomic Force Microscopy (AFM), with the main focus being on single-pass detection and mapping of local electric properties, as a novel approach to enhance existing compositional mapping techniques. This method was found to be highly effective in differentiating various domains with respect to their polarity. The results of our study favour the hypothesis that the bee-like features are mainly composed of wax, including a variety of alkanes.