Derjaguin-Landau-Verwey-Overbeek Research Articles

Perfluorobutanoic acid weakens the heterogeneous aggregation of microplastics and microalgae: Perspective from physicochemical properties, extracellular polymeric substances secretion and DLVO theory

Microplastics (MPs) and per- and poly-fluoroalkyl substances extensively coexist in aquatic environments and potentially endanger organisms. Microalgae may decrease the effective concentration of pollutants via hetero-aggregation with MPs and adsorption of emerging contaminants. However, the potential influence of coexistent pollutants on hetero-aggregation of MPs and microalgae remains unknown. This study investigated the hetero-aggregation process involving different sizes of polystyrene (PS, 3.0 and 50.0 μm) with Chlorella sorokiniana (C. sorokiniana) in the presence or absence of perfluorobutanoic acid (PFBA) along settling experiments, scanning electron microscope, and Derjaguin-Landau-Verwey-Overbeek (DLVO) model. We found that the hetero-aggregation between C. sorokiniana and 3 μm PS was more pronounced than with 50 μm PS, while PFBA inhibited this process. ΔOD1 values (reflected hetero-aggregation level) for 3PS-cells and 50PS-cells were 0.189 and 0.087, respectively, and PFBA decreased these values to 0.134 and 0.033. Furthermore, extracellular polymeric substances, known as inducer of hetero-aggregation, increased by 14.33% when exposed to 3 μm PS alone, whereas the co-exposure group showed a decrease of 4.52% compared to 3PS-cells group. PFBA also significantly decreased the protein/polysaccharide ratios in both MPs sizes, reducing hetero-aggregation. DLVO theory revealed that microalgae lowered the energy barrier significantly, while PFBA elevated it, indicating that hetero-aggregation was inhibited by PFBA. This study provides new perspectives for pollutant removal and toxicity variation in aquatic environments.

Influence of Particle Size on Flotation Separation of Ilmenite and Forsterite

In addition to bubble–particle interaction, particle–particle interaction also has a significant influence on mineral flotation. Fine particles that coat the mineral surface prevent direct contact with collectors and/or air bubbles, thereby lowering flotation recovery. Calculating the particle interaction energy can help in evaluating the interaction behavior of particles. In this study, the floatability of coarse ilmenite (−151 + 74 μm) and different particle sizes (−45 + 25, −25 + 19, −19 μm) of forsterite with NaOL as a collector was investigated. The results showed that forsterite sizes of −45 + 25 and −25 + 19 μm had no effect on the ilmenite floatability, whereas −19 μm forsterite significantly reduced ilmenite floatability. A particle size analysis of artificially mixed minerals and a scanning electron microscopy (SEM) analysis of the flotation products showed that heterogeneous aggregation occurred between ilmenite and −19 μm forsterite particles. The extended DLVO (Derjaguin–Landau–Verwey–Overbeek) theory was applied to calculate the interaction energy between mineral particles using data from zeta potential and contact angle measurements. The results showed that the interaction barriers between ilmenite (−151 + 74 μm) and forsterite (−45 + 25, −25 + 19, and −19 μm) were 11.94 × 103 kT, 8.23 × 103 kT and 4.09 × 103 kT, respectively. Additionally, the interaction barrier between forsterite particles smaller than 19 μm was 0.51 × 103 kT. The strength of the barrier decreased as the size of the forsterite decreased. Therefore, fine forsterite particles and aggregated forsterite can easily overcome the energy barrier, coating the ilmenite particle surface. This explains the effect of different forsterite sizes on the floatability of ilmenite and the underlying mechanism of particle interaction.

Effect of droplet charge density on stabilization of oil‐in‐dispersion emulsions co‐stabilized by binary mixed surfactants and nanoparticles

AbstractIonic surfactant and similarly charged nanoparticles can co‐stabilize oil‐in‐dispersion (OID) emulsions at extremely low concentrations (0.001 cmc/0.001 wt%), in which particles do not adsorb at the oil/water interface but distribute in the aqueous phase forming a dispersion. In this paper, the effect of droplet charge density on stabilization of the n‐decane‐in‐water OID emulsion was examined by using a cetyl trimethyl ammonium bromide (CTAB)/C12B (dodecyl dimethyl carboxyl betaine) binary mixture at a low fixed total concentration (0.01 mM) with varying molar fractions of CTAB. A model based on the Derjaguin‐Landau‐Verwey‐Overbeek (DLVO) theory is proposed to calculate interaction energies between droplets and between droplets and particles. It is found that the droplet charge density can be well compensated by particle concentration along the stabilization boundary, and the OID emulsion still follows the DLVO stabilization. Particles tend to surround droplets at large distances but may form a monolayer between approaching droplets at shorter distances, which significantly reduces the van der Waals attraction between droplets. In addition, the induced auxiliary droplet–particle repulsion is proportional to the number of particles per unit area of droplet surfaces, which together with the droplet–droplet repulsion ensures a large total repulsion preventing droplets from flocculation and coalescence. This work explains quantitatively the stabilization of OID emulsions, which have potential applications in emulsion products such as foods, cosmetics, pesticides, and various industrial emulsion systems. Moreover, the development of the OID emulsions represents an important advancement in green chemistry as it substantially reduces the required amounts of emulsifiers and their environmental impact after use.

Transport of microplastics treated with dielectric barrier discharge (DBD) plasma in saturated porous media

The performance of discharge plasma in treating organic pollutants and micro-organisms in water is impressive. When discharge plasma is used to treat polluted water containing organic pollutants and microorganisms, the presence of a certain amount of microplastics (MPs) in the water is unavoidable due to the complexity of the components contained in the water and the prevalence of MPs. MPs, as one of the pollutants that are difficult to be degraded by discharge plasma, undergo physical and chemical changes that increase their risk in the environment after treatment. Therefore, it is necessary to understand the fate of MPs after being treated with discharge plasma. In this study, the surface morphology of plastics before and after discharge plasma treatment was observed by scanning electron microscopy (SEM). The plastics after discharge plasma treatment were characterized by Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) to determine the changes in oxygen-containing functional groups on the surface. The recovery of microplastics (MPs) in saturated porous media under different physicochemical and plasma oxidation conditions was investigated by column experiments. It has been shown that MPs exhibit increased recovery under conditions of increased flow rate and pH. A decrease in recovery was observed at elevated ionic strength and co-existing cation valence. High voltages and low air flow rates increase the oxidation of MPs by increasing the thermal effects of the dielectric barrier discharge (DBD) plasma system, the amount of reactive oxygen species (ROS) and the intensity of ultraviolet ray (UV) irradiation. The mobility of MPs is enhanced by a combination of these factors. The advection–dispersion equation (ADE) fits the transport data of MPs well. The interaction energy between quartz sand and MPs was calculated using the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. This study provides a new perspective on the potential risks of discharge plasma in water treatment.

High salinity restrains microplastic transport and increases the risk of pollution in coastal wetlands

Microplastics (MPs) pollution in coastal wetlands has attracted global attention. However, few studies have focused on the effect of soil properties and structure on MP transport in coastal wetlands. Salinity is one of the most pivotal environmental factors and varies in coastal wetlands. Here, we conducted column experiments and employed fluorescent labeling combined with Derjaguin–Landau–Verwey–Overbeek (DLVO) theoretical calculations to reveal the vertical transport behavior of MPs. Specifically, we investigated the influence of five salinity levels (0, 0.035, 0.35, 3.5, and 35 PSU) on MP transport in different coastal wetlands soils and a sand through the X-ray photoelectron spectroscopy and nondestructive computed tomography technique. The results indicated that the migration capability of MPs in soils is significantly lower than in quartz sand, and that the migration capability varies depending on the soil type. This variability may be due to soil minerals and microporous structures providing numerous attachment sites for MPs and may be explained by the DLVO energy barrier of MP-Soil (6568–7767 KT) and MP-sand (5250 KT). Salinity plays a crucial role in modifying the chemical properties of pore water (i.e., zeta potential) as well as altering the soil elemental composition and pore structure. At 0 PSU, the maximum C/C0 of MPs through the sand, Soil 1, and Soil 2 transport columns were 37.86 ± 2.36 %, 23.96 ± 1.71 %, and 3.94 ± 0.68 %, respectively. When salinity increased to 3.5 PSU, MP mobility decreased by over 20 %. Additionally, a salinity of 35 PSU may alter the soil pore distribution, thereby changing water flow paths and velocities to constrain the migration of MPs in soils. These findings could provide valuable insights into understanding the environmental behavior and transport mechanisms of MPs, and lay a solid scientific basis for accurately simulating and predicting the fate of MPs in coastal wetland water–soil systems. We highlight the effect of salinity on the fate of MPs and the corresponding priority management of MPs risks under the background of global climate change.

Alteration of cement rheological properties and setting-hardening: Novel insight into the impact of polyaluminum sulfate

The accelerator significantly influences the setting and hardening performance of shotcrete, in order to develop novel setting components, this study investigates the underlying mechanisms through which polyaluminum sulfate (PAS) facilitates the setting of cement paste. QXRD, Isothermal calorimetry, Zeta potential and Rheological test were employed to analyze the effects of PAS addition on the setting and hardening behavior, hydration kinetics, and rheological properties of cement paste. When the dosage of PAS is 10 %, the initial and final setting times are reduced by 54.39 % and 38.57 % respectively, meanwhile the compressive strength after 6 hours increases by 659.09 %. The influence of PAS on cement setting acceleration and rheological properties were analyzed using the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and the Water Film Thickness (WFT) theory. PAS leads to an acceleration in particle aggregation rate and an increase in shear stress and plastic viscosity of the cement paste. Furthermore, the accelerated hydration effect of PAS promotes the formation of additional hydration products, strengthens the interparticle connectivity, and facilitates the formation of a rigid network. This study highlights a novel pathway for understanding the rapid setting mechanism of aluminum-based accelerators.

Cooperative aggregation of gold nanoparticles on phospholipid vesicles is electrostatically driven.

Gold nanoparticles (AuNP) are known to aggregate on the surface of lipid vesicles, yet the molecular mechanism behind this phenomenom remains unclear. In this work, we have investigated the binding behaviour of AuNPs, synthesized with pulsed laser ablation, to phospholipid vesicles under varying conditions of ionic strength (KCl concentration) and NP to vesicle ratios. Our observations reveal a strong influence of electrolyte concentration on AuNP aggregation mediated by vesicles. Notably, cluster formation is observed even at less than one AuNP per vesicle ratio at low enough ionic strengths. These results evidence a binding mechanism governed by electrostatic attraction with a distinct cooperative behaviour at very low salt concentrations, resulting in a significant increase in nanoparticle clustering. This behaviour is quantitatively analysed through a model that incorporates the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, considering the electrical double layer attraction between dissimilar, non-oppositely charged objects. This study not only provides insight into the fundamental understanding of nanoparticle-vesicle interactions but also suggests potential strategies for controlling nanoparticle assembly in biological and synthetic systems by tuning the ionic strength.

Influence of buffer on colloidal stability, microstructure, and rheology of cellulose nanocrystals in hyaluronic acid suspensions

Hyaluronic acid (HA) is a natural biopolymer found in various human tissues, while cellulose nanocrystals (CNCs) extracted from pulp fibers have unique rheological properties and biocompatibility. Due to the superior biomechanical properties of CNC and HA, a CNC-based HA suspension may be useful in biomedical applications. While buffers are an essential constituent of any suspension used for biomedical applications to maintain the desired pH level, they can significantly affect the properties of the suspension, including colloidal stability, microstructure, and rheological characteristics.To our knowledge, this is the first study analyzing the influence of buffer solutions on the suspension characteristics of HA/CNC systems, integrating both theoretical and experimental approaches. The results revealed an alignment between predictions of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and results from experiments characterizing a buffer-specific trend in colloidal stability. Suspensions with a higher energy barrier showed higher colloidal stability, with a lower tendency for phase separation and agglomerate formations. The microstructural analysis of CNC tactoids in the suspension revealed the existence of the hedgehog defect when dispersed in different buffer solutions. The defect is predicted to be caused by the pH-dependent protonation and deprotonation of HA. Furthermore, steady shear viscometry showed a microstructural-dependent shear viscosity trend, which, in turn, depends on the buffer solution.The study provides novel insights into the microstructural and bulk properties of HA and CNC suspensions in various buffer solutions. The results highlight the importance of solvent choice in tailoring the properties of the suspension for specific biomedical applications. These findings may be helpful in formulating HA and CNC suspensions for different biomedical applications, including drug delivery systems and viscosupplement injections.

Investigating the Feasibility of EOR While Preloading Parent Wells to Mitigate Fracture Hits: An Experimental and Modeling Study

Summary During a fracturing operation in an infill (child) well, pressure and fluid communication between this well and a nearby parent well, known as fracture hits (FHs), can impair the production performance of both wells. A cost-effective strategy to mitigate the FH is to preload the parent well with water during the fracturing of the child well. It has been hypothesized that the production performance of the parent well can be enhanced by the preloading process if proper additives are used in the injected water. We develop a laboratory protocol to physically simulate primary production and surfactant preloading stages using Montney core and fluid samples under reservoir conditions. We investigate the role of wettability alteration, interfacial tension (IFT) reduction, and surfactant’s chemical stability on the performance of enhanced oil recovery (EOR) during the preloading process. An analytical model is developed to predict the volume of leaked-off surfactant and recovered oil using measured pressure-decline data from the preloading stage. This study only focuses on the interactions of preloading fluid with the parent well’s matrix and does not consider the child-parent well interference. Our results demonstrate that 31.8% of the oil is recovered during primary production from large inorganic pores under solution-gas drive mechanism. Under countercurrent imbibition, a nonionic surfactant leaks off into the smaller organic and inorganic pores and recovers an additional 11.8% oil from a depleted core during preloading. The analytical model estimates oil recovery factors close to the experimental data determined by material balance. Core visualizations demonstrate a population of small oil droplets on the rock surface under reservoir conditions. While IFT is reduced to nearly the same extent by either surfactant, only the wettability-altering surfactant yields incremental oil recovery. Zeta-potential measurements indicate that while neither surfactant alters the rock-water surface charge, the wettability alteration is achieved by modifying the oil-water surface charge even at concentrations above the critical micelle concentration (CMC). Based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the repulsive electrostatic double-layer (EDL) forces are intensified with an increase in surfactant concentration, resulting in enhanced stability of the water film on the rock surface and increased hydrophilicity. Under elevated temperatures, we observe two phenomena, which can adversely affect the performance of a nonionic surfactant: (a) agglomeration of surfactant particles due to reduced solubility in water, reducing pore accessibility, and (b) chemical decomposition of the surfactant, affecting its ability for IFT reduction and wettability alteration.

Interfacial interactions of nanoscale zero-valent iron particles with clay minerals in the aquatic environments: Experimental and theoretical calculation study

The environmental transport and fate of nanoscale zero-valent iron particles (nZVI) in soil and groundwater can be altered by their hetero-aggregation with clay mineral particles (CMP). This study examines the interactions between bare or carboxymethyl cellulose (CMC)-coated nZVI with typical CMP, specifically kaolinite and montmorillonite. Methods include co-settling experiments, aggregation kinetic studies, electron microscopy, Derjaguin–Landau–Verwey–Overbeek (DLVO) and extended DLVO (EDLVO) energy analysis, and density functional theory calculations, focusing on the pH dependency of these interactions. The EDLVO theory effectively described the interactions between nZVI and CMP in aquatic environments. Under acidic conditions (pH 3.5), the interfacial interaction between bare nZVI and kaolinite is regulated by van der Waals forces, while complexation, van der Waals forces, and electrostatic attraction govern the interaction of bare nZVI with montmorillonite, primarily depositing on the SiO face. In contrast, the positively charged AlO face and edge of CMP are the main deposition sites for CMC-coated nZVI through hydrogen bonding, van der Waals forces, and electrostatic attraction. At neutral (pH 6.5) and alkaline (pH 9.5) conditions, both bare and CMC-coated nZVI predominantly attach to the AlO face and edge, facilitated by complexation or hydrogen bonding, alongside van der Waals forces. The attachment of CMC-coated nZVI to CMP surfaces shows reversible aggregation or deposition due to the steric repulsion from the CMC coating. These findings hold significant implications for the environmental applications and risk of nZVI.

Impact of ionic strength on goethite colloids co-transported with arsenite (As3+) through a saturated sand column under anoxic condition: Experiment and mathematical modeling

The knowledge about co-transport of goethite and As3+ to investigate the effect of goethite colloids on As3+ transport under various degrees of seawater intrusion, particular extremely conditions, in groundwater environment is still limited. The main objective is to investigate the influence of seawater intrusion on the sorption, migration, and reaction of As3+and goethite colloids into sand aquifer media under anoxic conditions by using the bench-scale and reactive geochemical modeling. The research consisted of two parts as follows: 1) column transport experiments consisting of 8 columns, which were packed by using synthesis groundwater at IS of 0.5, 50, 200, and 400 mM referring to the saline of seawater system in the study area, and 2) reactive transport modeling, the mathematical model (HYDRUS-1D) was applied to describe the co-transport of As3+ and goethite. Finally, to explain the interaction of goethite and As3+, the Derjaguin-Landau-Verwey-Overbeek (DLVO) calculation was considered to support the experimental results and HYDRUS-1D model. The results of column experiments showed goethite colloids can significantly inhibit the mobility of As3+ under high IS conditions (>200 mM). The Rf of As3+ bound to goethite grows to higher sizes (47.5 and 65.0 μm for 200 and 400 mM, respectively) of goethite colloid, inhibiting As3+ migration through the sand columns. In contrast, based on Rf value, goethite colloids transport As3+ more rapidly than a solution with a lower IS (0.5 and 50 mM). The knowledge gained from this study would help to better understand the mechanisms of As3+ contamination in urbanized coastal groundwater aquifers and to assess the transport of As3+ in groundwater, which is useful for groundwater management, including the optimum pumping rate and long-term monitoring of groundwater quality.

A cost-effective purification strategy of ultra-long AgNWs for enhancing stability and durability of AgNWs/PU sensor

A large amount of silver nanoparticles (AgNPs) and short-sized silver nanowires (AgNWs) were produced in the reaction of AgNW synthesis by the polyol method. These impurities immensely affected the practical application of AgNWs dispersion. To promote the electrical property of AgNWs, it is necessary to develop a cost-effective method to separate impurities in AgNWs dispersion. Herein, we developed a new purification strategy called centrifugation-sedimentation separation-centrifugation to purify the ultra-long AgNWs (average length of 98.26 μm and the aspect ratio of 1240) synthesized by an improved polyol method. The yield of sedimentation separation was up to 78.1 % in this strategy. Based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the sedimentation mechanism of the ultra-long AgNWs and impurities was systematically investigated. The AgNWs/polyurethane (PU) composite foam prepared by the impregnation method with purified ultra-long AgNWs demonstrated a superior conductivity of 13227 S/m, which was twice than that of the composite foam with unpurified ultra-long AgNWs. The resistance variation of the purified ultra-long AgNWs-5/PU sensor was only elevating 11 % after 100 cycles of 100 % strain compression at 1 Hz frequency, while the AgNWs-5/PU sensor prepared from commercial 20 μm AgNWs showed a resistance change of up to 492 %. Our study provides a low-cost, highly selective, and efficient purification strategy for ultra-long AgNWs dispersions, and also demonstrates that ultra-long AgNWs can enhance the sensing stability and durability of AgNWs/PU foam sensors.

Transport and retention of nanobubbles in saturated porous media: Overlooked role of grain size and shape

Nanobubbles (NBs) are widely used in groundwater pollution treatment due to their unique properties such as small size and high gas mass transfer rate. Therefore, the transport behavior of NBs in the groundwater environment has attracted more attention. Due to the diversity and complexity of aquifer media in the natural environment, grain sands with different sizes and shapes are ubiquitous. Thus, consideration of grain size and shape in porous media is crucial to predict and evaluate the transport and fate of NBs in soil and groundwater systems. This work investigated the stability of NBs in pure water. The transport behavior and mechanism of NBs under different grain sizes and shapes were demonstrated by the column experiment, microscopic observation, and numerical simulation. The results showed that NBs had excellent stability, remaining in solution for more than 10 days. The retention of NBs in coarse, medium and fine sands was 23.5 %, 43.8 % and 50.8 %, respectively. The retention in sphere sands, oval sands and irregular sands was 22.9 %, 24.0 % and 43.8 %, respectively. The smaller grain size and roundness limited the NBs transport in the saturated porous media, which was mainly due to the complexity of the flow channel and the narrowing of the pore throat of fine sands and angular shape of irregular sand that would hinder the NBs transport. This was proved by the Derjaguin − Landau − Verwey − Overbeek (DLVO) theory and ultra − depth − of − field microscope. The BTCs of NBs were fitted by the one − site deposition model (only attachment) and two − site deposition model (attachment and straining), and it was found that two − site deposition model showed a better fit. The straining rate (kstr) was greater than the attachment rate (katt) in different grain sizes and shapes media, indicating that the retention mechanism of NBs in porous media was a synergistic mechanism dominated by pore straining and supplemented by electrostatic attraction.

New Insights into Aggregation Behaviors of the UV-Irradiated Dissolved Biochars (DBioCs) in Aqueous Environments: Effects of Water Chemistries and Variation in the Hamaker Constant.

The aggregation behavior of ubiquitous dissolved black carbon (DBC) largely affects the fate and transport of its own contaminants and the attached contaminants. However, the photoaging processes and resulting effects on its colloidal stability remain yet unknown. Herein, dissolved biochars (DBioCs) were extracted from common wheat straw biochar as a proxy for an anthropogenic DBC. The influences of UV radiation on their aggregation kinetics were systematically investigated under various water chemistries (pH, electrolytes, and protein). The environmental stability of the DBioCs before and after radiation was further verified in two natural water samples. Hamaker constants of pristine and photoaged DBioCs were derived according to Derjaguin-Landau-Verwey-Overbeek (DLVO) prediction, and its attenuation (3.19 ± 0.15 × 10-21 J to 1.55 ± 0.07 × 10-21 J after 7 days of radiation) was described with decay kinetic models. Pearson correlation analysis revealed that the surface properties and aggregation behaviors of DBioCs were significantly correlated with radiation time (p < 0.05), indicating its profound effects. Based on characterization and experimental results, we proposed a three-stage mechanism (contended by photodecarboxylation, photo-oxidation, and mineral exposure) that DBioCs might experience under UV radiation. These findings would provide an important reference for potential phototransformation processes and relevant behavioral changes that DBC may encounter.

Molecular Mechanisms of Sorbed Ion Effects during Boehmite Particle Aggregation.

Classical theories of particle aggregation, such as Derjaguin-Landau-Verwey-Overbeek (DLVO), do not explain recent observations of ion-specific effects or the complex concentration dependence for aggregation. Thus, here, we probe the molecular mechanisms by which selected alkali nitrate ions (Na+, K+, and NO3-) influence aggregation of the mineral boehmite (γ-AlOOH) nanoparticles. Nanoparticle aggregation was analyzed using classical molecular dynamics (CMD) simulations coupled with the metadynamics rare event approach for stoichiometric surface terminations of two boehmite crystal faces. Calculated free energy landscapes reveal how electrolyte ions alter aggregation on different crystal faces relative to pure water. Consistent with experimental observations, we find that adding an electrolyte significantly reduces the energy barrier for particle aggregation (∼3-4×). However, in this work, we show this is due to the ions disrupting interstitial water networks, and that aggregation between stoichiometric (010) basal-basal surfaces is more favorable than between (001) edge-edge surfaces (∼5-6×) due to the higher interfacial water densities on edge surfaces. The interfacial distances in the interlayer between aggregated particles with electrolytes (∼5-10 Å) are larger than those in pure water (a few Ångströms). Together, aggregation/disaggregation in salt solutions is predicted to be more reversible due to these lower energy barriers, but there is uncertainty on the magnitudes of the energies that lead to aggregation at the molecular scale. By analyzing the peak water densities of the first monolayer of interstitial water as a proxy for solvent ordering, we find that the extent of solvent ordering likely determines the structures of aggregated states as well as the energy barriers to move between them. The results suggest a path for developing a molecular-level basis to predict the synergies between ions and crystal faces that facilitate aggregation under given solution conditions. Such fundamental understanding could be applied extensively to the aggregation and precipitation utilization in the biological, pharmaceutical, materials design, environmental remediation, and geological regimes.

Recovery of biochar particles laden with lead in saturated porous media by DC electric field

The co-transport behavior of environmental pollutants with biochar particles has aroused great interests from researchers due to the concerns about pollutant diffusion and environmental exposure after biochar is applied to soil. In this work, the recovery and co-transport behavior of biochar micron-/nano-particles (BCMP and BCNP) and lead (Pb2+) in saturated porous media were investigated under different ionic strength conditions (IS = 1, 5 and 10 mM) under a direct current electric field. The results showed that the electric field could significantly enhance the mobility of Pb adsorbed biochar particles, particularly BCNP. The recovery of Pb laden biochar particles was improved by 1.8 folds, reaching 78.8% at maximum under favorable condition at +0.5 V cm−1. According to the CDE (Convection-Dispersion-Equation) model and DLVO (Derjaguin-Landau-Verwey-Overbeek) theory analysis, the electric field facilitated the transport of Pb carried biochar mainly by increasing the negative charges on biochar surface and improving the repulsive force between biochar and porous media. High IS was favorable for biochar transport under the electric field, but inhibited desorbing Pb2+ from biochar (18% by maximum at IS = 10 mM). By switching the electric field power, a two-stage strategy was established to maximize the recovery of both biochar particles and Pb, where BCNP and Pb recovery were higher than electric field free case by 90% and 35%, respectively. The findings of this study can help build a biochar recovery approach to prevent potential risks from biochar application in heavy metal contaminated soil remediation.

Impact of natural organic matter and inorganic ions on the stabilization of polystyrene micro-particles

The orthokinetic coagulation of irregularly shaped polystyrene micro-particles (PS-MP) was investigated in solutions of inorganic cations with different valence (NaCl, CaCl2, LaCl3) using a coagulation jar test set-up combined with light extinction particle counting. The stabilizing effect of model natural organic matter (NOM from reverse-osmosis (RO-NOM), humic (HA) & fulvic acid (FA)) and of surface water components (SW-NOM) was studied. Collision efficiencies were calculated from the decrease in particle concentration applying first order reaction kinetics. The coagulation of PS-MP followed Derjaguin-Landau-Verwey-Overbeek (DLVO) theory with regard to ionic charge in solution. Highest collision efficiencies were obtained close to the suspected critical coagulation concentrations for CaCl2 (12 mM) and LaCl3 (5.5 mM) whereas for NaCl no CCC was found within the applied concentration range (10–1000 mM). The addition of NOM effectively stabilized PS-MP at low ionic strength (10 mM NaCl) in the order HA > RO-NOM > FA > SW-NOM at concentrations of dissolved organic carbon (DOC) as low as 0.2–0.5 mg/L DOC through electrostatic repulsion. PS-MP were effectively stabilized in 6.1 mg DOC/L of SW-NOM even at high ionic strength (100 mM MgCl2). Coagulation at intermediate ionic strength (10 mM MgCl2) was only observed for SW-NOM concentrations below 0.6 mg/L DOC. The results showed that even low NOM concentrations prevent PS-MP from orthokinetic coagulation in the presence of high ion concentrations. The study provides further insight in the orthokinetic coagulation behavior of PS-MP in the presence of NOM and highlights the importance of NOM for the stabilization of microplastics in aquatic suspensions. Further research is needed to elucidate the behavior of MP in turbulent systems to predict the mobility MP in aquatic systems such as rivers.

Attachment of various-shaped polystyrene microplastics to silica surfaces: Experimental validation of the equivalent Cassini oval extended DLVO model

Microplastics (MPs) vary in shape and surface characteristics in the environment. The attachment of MPs to surfaces can be studied using the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. However, this theory does not account for the shape MPs. Therefore, we investigated the attachment of spherical, pear-shaped, and peanut-shaped polystyrene MPs to quartz sand in NaCl and CaCl2 solutions using batch tests. The attachment of MPs to quartz sand was quantified using the attachment efficiency (alpha). Subsequently, alpha behaviors were interpreted using energy barriers (EBs) and interaction minima obtained from extended DLVO calculations, which were performed using an equivalent sphere model (ESM) and a newly developed equivalent Cassini model (ECM) to account for the shape of the MPs. The ESM failed to interpret the alpha behavior of the three MP shapes because it predicted high EBs and shallow minima. The alpha values for spherical MPs (0.62–1.00 in NaCl and 0.48–0.96 in CaCl2) were higher than those for pear- and peanut-shaped MPs (0.01–0.63 in NaCl and 0.02–0.46 in CaCl2, and 0.01–0.59 in NaCl and 0.02–0.40 in CaCl2, respectively). Conversely, the ECM could interpret the alpha behavior of pear- and peanut-shaped MPs either by changes in EBs or interaction minima as a function of orientation angles and electrolyte ionic strength. Therefore, the particle shape must be considered to improve the attachment analyses.

A Meta-Analysis to Revisit the Property-Aggregation Relationships of Carbon Nanomaterials: Experimental Observations versus Predictions of the DLVO Theory.

Contradicting relationships between physicochemical properties of nanomaterials (e.g., size and ζ-potential) and their aggregation behavior have been constantly reported in previous literature, and such contradictions deviate from the predictions of the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. To resolve such controversies, in this work, we employed a meta-analytic approach to synthesize the data from 46 individual studies reporting the critical coagulation concentration (CCC) of two carbon nanomaterials, namely, graphene oxide (GO) and carbon nanotube (CNT). The correlations between CCC and material physicochemical properties (i.e., size, ζ-potential, and surface functionalities) were examined and compared to the theoretical predictions. Results showed that the CCC of electrostatically stabilized carbon nanomaterials increased with decreasing nanomaterial size when their hydrodynamic sizes were smaller than ca. 200 nm. This is qualitatively consistent with the prediction of the DLVO theory but with a smaller threshold size than the predicted 2 μm. Above the threshold size, the material ζ-potential can be correlated to CCC for nanomaterials with moderate/low surface charge, in agreement with the DLVO theory. The correlation was not observed for highly charged nanomaterials because of their underestimated surface potential by the ζ-potential. Furthermore, a correlation between the C/O ratio and CCC was observed, where a lower C/O ratio resulted in a higher CCC. Overall, our findings rationalized the inconsistency between experimental observation and theoretical prediction and provided essential insights into the aggregation behavior of nanomaterials in water, which could facilitate their rational design.

Environmental colloid behaviors of humic acid - Cadmium nanoparticles in aquatic environments

Humic acid (HA), a principal constituent of natural organic matter (NOM), manifests ubiquitously across diverse ecosystems and can significantly influence the environmental behaviors of Cd(II) in aquatic systems. Previous studies on NOM-Cd(II) interactions have primarily focused on the immobilization of Cd(II) solids, but little is known about the colloidal stability of organically complexed Cd(II) particles in the environment. In this study, we investigated the formation of HA-Cd(II) colloids and quantified their aggregation, stability, and transport behaviors in a saturated porous media representative of typical subsurface conditions. Results from batch experiments indicated that the relative quantity of HA-Cd(II) colloids increased with increasing C/Cd molar ratio and that the carboxyl functional groups of HA dominated the stability of HA-Cd(II) colloids. The results of correlation analysis between particle size, critical aggregation concentration (CCC), and zeta potential indicated that both Derjaguin-Landau-Verwey-Overbeek (DLVO) and non-DLVO interactions contributed to the enhanced colloidal stability of HA-Cd(II) colloids. Column results further confirmed that the stable HA-Cd(II) colloid can transport fast in a saturated media composed of clean sand. Together, this study provides new knowledge of the colloidal behaviors of NOM-Cd(II) nanoparticles, which is important for better understanding the ultimate cycling of Cd(II) in aquatic systems.