Experimental application of a zero-point charge based on pH as a simple indicator of microplastic particle aggregation.

Micro/nanoplastics - a useful but threatening material - continuously require fundamental research on its behaviors and properties for aggregation. Zeta potential (ζ) has been using as an indicator to determine the optimal aggregation for particle removal in water treatment processes. In the field work, however, an alternative method for streamlining these tasks and reducing the variability in processing efficiency is necessary. To improve practical utility in the field work, this study aimed at investigating applicability of the zero-point charge (ZPC) of the isoelectric point (IEP; ψpI) as an alternative indicator for aggregation in place of ζ. For the purpose, this study conducted laboratory experiments and model simulations. The experiments measured ψpI of microplastics in a trivalent-electrolyte aqueous solution using various concentrations of polyaluminum chloride (PAC) for reproducing the behavior of microplastics in natural water environments. As a result, ψpI for polyethylene (PE) and polyvinylchloride (PVC) were found to be pH 6.59 and 6.43, respectively. The removal rates (r) depended on the aggregation at the initial pH and optimal PAC concentration. The experimental attachment efficiency (αE), 0.14 to 0.4, showed a good correlation of over 95% with r, 0.04 to 0.84, both based on the pH change and PAC concentration and differing slightly with the type and size of the plastic. The highest αE was achieved with the highest r when ψpI was close to zero in the pH range of 6-8 using the optimized PAC concentration. Based on the experimental results, the model confirmed the applicability of ψpI instead of ζ as an indicator of the aggregation by simulating αE based on ψpI and ionic strength, which are themselves based on the change in pH. Therefore, this study provides some insights into behaviors of microplastics by using the isoelectric point (IEP, ψpI) as an indicator of aggregation of microplastics in place of ζ. The IEP method is limited by initial pH, optimal dosage of coagulant, and type and size of microplastics, but it will increase practical utility in the field.

Modeling study on fate of micro/nano-plastics in micro/nano-hydrodynamic flow of freshwater.

As the risk of micro/nano-plastics (MPs/NPs) on marine ecosystems is reported, there is a growing interest in behaviors of MPs/NPs in freshwater. Thus, this study aims at developing a plastics fate model linked with a flocculation kinetics model, PsFM/FKM, to understand the vertical behaviors of MPs/NPs in freshwater. Based on the Population Balance approach, the model numerically predicts vertical transport (sedimentation, resuspension, and burial) and transformation (degradation and aggregation) in water and sediments. This study performed model simulations to validate model accuracy and precision as estimating temporal changes in MPs/NPs concentration in water and sediments, based on the aggregation process to form homo-aggregates between plastics and hetero-aggregates between plastics and SS in water. It confirmed that a significant parameter of the aggregation was collision frequency in water and that attachment efficiency influenced the aggregation rate occurring in the collision. The model emphasized the importance of attachment efficiency with the size-dependence and confirmed that the formed hetero-aggregates promoted the sedimentation process to settle down to the sediments. The model validity was demonstrated by comparing experiments and simulations for attachment efficiency. A further study improves the model and extends its applicability to various types of MPs/NPs, SS, microalgae, and metal hydrate salts.

Modeling behaviors of permeable non-spherical micro-plastic aggregates by aggregation/sedimentation in turbulent freshwater flow.

This study developed and evaluated a behavior model for permeable non-spherical micro-plastic aggregates in a turbulent flow of freshwater based on fractal theory, as conducting experimental and modeling studies. Laboratory-scale experiments evaluated attachment efficiency α to aggregation kinetics in an aquatic environment (pH 6, 20 â„ƒ) of the electrolyte (Al3+). The experimental α was dependent on characteristics of plastics (type, size, and density) and ranged from 0.062 to 0.2772 (averaging 0.1) with a high correlation with the modeled α (R2 > 0.92). Model validation was conducted under two simulation conditions: one drawn from a previously published study of impermeable spherical aggregates and the other based on fractal theory. The simulations verified the limited primary particle size with the lowest retention rate based on the previous study but it was difficult to determine the specific particle size with the lowest retention rate as a limiting factor. The sum of residual errors for aggregation/sedimentation between the two types of structures showed an overestimation of spherical structures. Such overestimation influenced the aggregate number concentration and distribution pattern. Therefore, the model needs to more detailed express the aggregation mechanism of permeable non-spherical aggregate structures in terms of surface growth.

Biogenic Hematite from Bacteria: Facile Synthesis of Secondary Nanoclusters for Lithium Storage Capacity.

Ferrihydrite, or iron(III) (oxyhydr)oxide (Fe(OH)3), a representative scavenger of environmentally relevant toxic elements, has been repurposed as a low-cost and scalable precursor of well-developed hematite (α-Fe2O3) secondary nanoclusters with a hierarchically structured morphology for lithium-ion anode materials. Here, we report that the bacteria Clostridium sp. C8, isolated from a methane-gas-producing consortium, can synthesize self-assembled secondary hematite nanoclusters (∼150 nm) composed of small nanoparticles (∼15 nm) through the molecular structural rearrangement of amorphous ferrihydrite under mild conditions. The biogenic hematite particles, wrapped with graphene oxide reduced in situ by the reducing bacteria Shewanella sp. HN-41 via one-pot synthesis, deliver an excellent reversible capacity of ∼1000 mA h g-1 after 100 cycles at a current density of 1 A g-1. Furthermore, the heat-treated hematite/rGO exhibits a capacity of 820 mA h g-1 at a high current density of 5 A g-1 and a reversible capacity of up to 1635 mA h g-1 at a current density of 100 mA g-1. This study provides an easy, eco-efficient, and scalable microbiological synthetic route to produce hierarchical hematite/rGO secondary nanoclusters with potential as high-performance Li-ion anode materials.

Estimation and evaluation of auto-flocculated algae harvesting efficiency using the population balance in turbulence model in flotation process.

Algae are considered water pollutants because they form algal blooms in stagnant water. Algae harvesting technology, however, can help convert them into a useful industrial material like biomass. The core technique (flocculation) separates microalgae from other flocculants, allowing for the harvest of clean and pure algal biomass. This study aims to estimate and evaluate algal separation (removal or harvesting) efficiency (X) to concurrently obtain the objectives of algal bloom management and algal particle collection. To simulate algal separation by auto-flocculation (no flocculants) related flotation, the population balance in turbulence (PBT) model is used. Model simulations are conducted under optimal conditions provided by previous studies about the biological impact factors of algae, operating parameters of the flotation process, and so on. This modeling study determines the efficiency (X) of separating algae from the water body in the separation zone after forming auto-flocculated bubble-floc agglomerates by making them collide and attach to each other in the contact zone of the flotation tank. The X is examined as a function of size distribution of agglomerates and bubbles and of the number of initially injected bubbles. Optimal conditions for forming and harvesting the agglomerates may be found through further modeling studies.

Flotation of algae for water reuse and biomass production: role of zeta potential and surfactant to separate algal particles.

The effect of chemical coagulation and biological auto-flocculation relative to zeta potential was examined to compare flotation and sedimentation separation processes for algae harvesting. Experiments revealed that microalgae separation is related to auto-flocculation of Anabaena spp. and requires chemical coagulation for the whole period of microalgae cultivation. In addition, microalgae separation characteristics which are associated with surfactants demonstrated optimal microalgae cultivation time and separation efficiency of dissolved CO2 flotation (DCF) as an alternative to dissolved air flotation (DAF). Microalgae were significantly separated in response to anionic surfactant rather than cationic surfactant as a function of bubble size and zeta potential. DAF and DCF both showed slightly efficient flotation; however, application of anionic surfactant was required when using DCF.

Evaluation of initial collision-attachment efficiency between carbon dioxide bubbles and algae particles for separation and harvesting.

Microalgae have been regarded as a pollutant causing algal blooms in lakes or reservoirs but have recently been considered as a useful source of biomass to produce biofuel or feed for livestock. For the algae particle separation process, carbon dioxide (CO2), one of the main greenhouse gases, is dissolved into a body of water rather than being emitted into atmosphere. This study aims at determining the feasibility of CO2 bubbles as an algae particle separation collector in a flotation process and providing useful information for effective algae harvesting by describing optimal operating conditions of dissolved carbon dioxide flotation or dissolved air flotation. The first step is to develop a flotation model for bi-functional activity, algae control and algae harvesting at the same time. A series of model simulations is run to investigate algae particle separation possibilities such as an initial collision-attachment efficiency that depends upon separation characteristics due to an algae life cycle, including: pH, size distribution, zeta potential, cell surface charge, density, electric double layer, alkalinity, and so on. Based on the separation characteristics, conditions required to form flocculation are predicted in order to obtain the optimal flotation efficiency.