Critical Coagulation Concentration Research Articles

Aggregation of Halloysite Nanotubes in the Presence of Multivalent Ions and Ionic Liquids.

Colloidal stability was investigated in two types of particle systems, namely, with bare (h-HNT) and polyimidazolium-functionalized (h-HNT–IP-2) alkali-treated halloysite nanotubes in solutions of metal salts and ionic liquids (ILs). The valence of the metal ions and the number of carbon atoms in the hydrocarbon chain of the IL cations (1-methylimidazolium (MIM+), 1-ethyl-3-methylimidazolium (EMIM+), 1-butyl-3-methylimidazolium (BMIM+), and 1-hexyl-3-methylimidazolium (HMIM+)) were altered in the measurements. For the bare h-HNT with a negative surface charge, multivalent counterions destabilized the dispersions at low values of critical coagulation concentration (CCC) in line with the Schulze–Hardy rule. In the presence of ILs, significant adsorption of HMIM+ took place on the h-HNT surface, leading to charge neutralization and overcharging at appropriate concentrations. A weaker affinity was observed for MIM+, EMIM+, and BMIM+, while they adsorbed on the particles to different extents. The order HMIM+ < BMIM+ < EMIM+ < MIM+ was obtained for the CCCs of h-HNT, indicating that HMIM+ was the most effective in the destabilization of the colloids. For h-HNT–IP-2 with a positive surface charge, no specific interaction was observed between the salt and the IL constituent cations and the particles, i.e., the determined charge and aggregation parameters were the same within experimental error, irrespective of the type of co-ions. These results clearly indicate the relevance of ion adsorption in the colloidal stability of the nanotubes and thus provide useful information for further design of processable h-HNT dispersions.

The aggregation and charging of natural clay allophane: Critical coagulation ionic strength in the presence of multivalent counter-ions

Allophane is an amorphous aluminosilicate clay mineral which is typically found in young volcanic ash soils. The aggregation-dispersion and charging behaviors of allophane may affect the usability and protection of the volcanic ash soils and surrounding environment. To understand the aggregation-dispersion and charging of natural allophane, dynamic and electrophoretic light scattering experiments were carried out at pH 5 as a function of potassium salt concentration and counter-ion (Cl - , SO 4 2- , Fe(CN) 6 3- , and Fe(CN) 6 4- ) valence. The temporal increase of particle hydrodynamic diameters and electrophoretic mobilities (EPM) were measured, and the stability ratio, critical coagulation concentration (CCC), critical coagulation ionic strength (CCIS), zeta potential, and surface charge density were further obtained. The experimental results of stability ratio and EPM of allophane particles were affected by the counter-ion valence, and the CCCs strongly depended on the counter-ion valence. The behavior was well described by the well-known empirical Schulze-Hardy rule. The allophane particles showed a low surface charge density in the presence of multivalent counter-ions. Thus, Derjaguin-Landau and Verwey-Overbeek (DLVO) theory with the Debye-Huckel (DH) approximation was applied to consider the CCIS. The experimental relationship between CCIS and surface charge density was well explained by DLVO theory by taking account of particle size. We conclude that, in the presence of multivalent counter-ions, the DLVO theory with DH approximation has a good applicability to the aggregation-dispersion of natural clay allophane particles. • Counter-ion valence affects the aggregation and charging of allophane particles. • Tetravalent counter-ion induces charge reversal and re-stabilization of allophane. • Critical coagulation ionic strength vs. surface chare follows DLVO theory. • DLVO theory has a good applicability to the aggregation and dispersion of allophane.

Synergistic Effect of Metal Cations and Visible Light on 2D MoS2 Nanosheet Aggregation.

Aggregation significantly influences the transport, transformation, and bioavailability of engineered nanomaterials. Two-dimensional MoS2 nanosheets are one of the most well-studied transition-metal dichalcogenide nanomaterials. Nonetheless, the aggregation behavior of this material under environmental conditions is not well understood. Here, we investigated the aggregation of single-layer MoS2 (SL-MoS2) nanosheets under a variety of conditions. Trends in the aggregation of SL-MoS2 are consistent with classical Derjaguin-Landau-Verwey-Overbeek (DLVO) colloidal theory, and the critical coagulation concentrations of cations follow the order of trivalent (Cr3+) < divalent (Ca2+, Mg2+, Cd2+) < monovalent cations (Na+, K+). Notably, Pb2+ and Ag+ destabilize MoS2 nanosheet suspensions much more strongly than do their divalent and monovalent counterparts. This effect is attributable to Lewis soft acid-base interactions of cations with MoS2. Visible light irradiation synergistically promotes the aggregation of SL-MoS2 nanosheets in the presence of cations, which was evident even in the presence of natural organic matter. The light-accelerated aggregation was ascribed to dipole-dipole interactions due to transient surface plasmon oscillation of electrons in the metallic 1T phase, which decrease the aggregation energy barrier. These results reveal the phase-dependent aggregation behaviors of engineered MoS2 nanosheets with important implications for environmental fate and risk.

Removal of Tannic Acid Stabilizes CuO Nanoparticles from Aqueous Media by PAFC: Effect of Process Conditions and Water Chemistry.

The increased utilization of CuO nanoparticles (CuO NPs) in various fields has raised concerns about their discharge into water containing a wide range of organic ligands. Moreover, the adsorption of these ligands can stabilize the CuO NPs in drinking water treatment plants. Thus, their removal from potable water is important to mitigate the risk to humans. The present study explored the efficacy of the coagulation–sedimentation (C/S) process for the removal of tannic acid (TA)-stabilized CuO NPs using polyaluminum ferric chloride (PAFC) as a coagulant. Moreover, the influence of process conditions (stirring speed) and water chemistry (i.e., pH and ionic strength (IS)) were also investigated to determine their impact on removal. The results showed that stirring speed in the reaction phase significantly affected the removal due to increased flocculation compared with stirring speed in the mixing phase. In addition, pH and IS affect the colloidal stability and removal efficiency of CuO NPs. A relatively better removal performance (<99%) of CuO NPs was found at lower coagulant dosage in the pH range 6–8. The addition of organic ligands reversed the surface charge potential and enhanced the colloidal stability of CuO NPs, resulting in the destabilization of TA-CuO NPs, thereby reducing the optimum PAFC dosage for removal. By contrast, the IS above the critical coagulation concentration decreased the removal efficiency due to inhibition of the ionic activity of PAFC hydrolysate in the aqueous environment. Fourier transform infrared findings of TA-CuO NPs composite flocs suggest that the primary removal mechanism might be mediated via the combined effect of neutralization, complexation as well as adsorption.

Divalent cations accelerate aggregation of Black phosphorus nanodots

Black phosphorus (BP) nanodots inevitably interact with electrolyte ions because of their extensive applications in many fields. In biomedical applications, BP-nanodots might encounter various salt ions in body fluids and have a propensity to aggregate, further resulting in an enhanced toxicity risk. In this study, the effects of electrolyte cations (Na+, K+, Ca2+, and Mg2+) on the aggregation kinetics of BP-nanodots were investigated by means of dynamic light scattering (DLS). The critical coagulation concentration values of BP-nanodots were determined to be 242.11 mM NaCl, 95.01 mM KCl, 1.92 mM CaCl2, and 5.88 mM MgCl2. Divalent cations accelerated aggregation of BP-nanodots because of the stronger surface charge screening and their bridging with oxidized phosphorus species (PxOy) available on BP-nanodot surfaces. Furthermore, the divalent cations may interact with PxOy to form insoluble complex coatings on the nanoparticle surface and shield the charge. After modification with PEG, BP-nanodots presented enhanced stability in the presence of 2.5 mM CaCl2. This work is of great significance for understanding the aggregation behaviors of ultrasmall nanoparticles such as BP-nanodots in electrolyte solutions and provides insight into their safety assessment associated with biomedical applications.

Co‐aggregation of mixture components of montmorillonite, kaolinite and humus

AbstractSoil particle aggregation is closely related to soil quality and pollutant migration in the environment. Soil is a naturally complex system with multi‐components, including different organic and inorganic particles. However, current studies with respect to particle aggregation by dynamic light scattering (DLS) have centred on single‐component particles. Therefore, the application of DLS to mixture components is an important issue in soil science research. In this study, montmorillonite (Mont), kaolinite (Kaol) and humic acid (HA) particles were mixed in different mass ratios to form two‐ and three‐mixture components, and then the aggregation kinetics of the mixture components in KNO3 solutions were studied by DLS. The results showed that (a) for any given mixing ratio of two‐ and three‐mixture component particles, there was only one critical coagulation concentration (CCC) value observed for the mixture components; (b) the CCCs of the two‐mixture components aggregation were always between the CCC values of each single component in the mixture, and the CCC values of the three‐mixture components aggregation were always between those of the two‐components aggregation. Based on those experimental results we concluded that, for mixture components aggregation, all the components would participate in the aggregation with equal probability, and the aggregation should be driven by the average DLVO forces of the mixture components. Therefore, for the mixture components of natural soil, the soil particle aggregation would be a co‐aggregation process, and the DLS technique would thus be a useful tool to study the real soil aggregation. Meanwhile, HA would decrease soil particle aggregation by increasing the DLVO/XDLVO repulsive forces, rather than promoting soil particle aggregation.Highlights The aggregation of mixture colloids analysed by DLS is an important issue in soil science research. There was only one CCC for mixture colloids with different colloidal components. The aggregation of mixture colloids (soil) is a co‐aggregation process. HA will decrease soil particle aggregation by increasing the DLVO/XDLVO repulsive forces.

Carbon stability and mobility of ball milled lignin- and cellulose-rich biochar colloids

Numerous studies have explored the transport mechanism of biochar colloids in porous medium. However, the effect of feedstock biopolymer compositions and pyrolytic temperature on carbon stability and mobility of biochar colloids is limited. This study prepared four ball milled biochar colloids pyrolyzed from lignin-rich pinewoods and cellulose-rich corn stalks under 300 °C and 500 °C (termed as PW300, PW500, CS300, CS500) and analyzed their differences in the chemical stability and transport behaviors. The results indicated that high contents of lignin in biomass and pyrolytic temperature could enhance the compact aromatic structures of biochar colloids characterized by the elemental composition, FTIR, 13C NMR and XRD analyses. Therefore, PW500 with the strongest chemical stabilities (least C loss of 13%), electronegativity (−44.9 mV vs. −41.6–28.3 mV) and smallest hydrodynamic diameter (608.7 nm vs. 622–997.2 nm) was obtained under ball milling. Moreover, both the critical coagulation concentrations (CCC) and the maximum relative effluent concentration (C/C0) with the NaCl ionic strength of 1 mM were demonstrated to be in the increase order of CS300 (76.1 mM, 70%) < PW300 (183.1 mM, 78%) < CS500 (363.9 mM, 89%) < PW500 (563.1 mM, 95%), which suggested stronger colloidal stability and mobility of PW biochar colloids than those of CS biochar colloids. In addition, the C/C0 for CS300, PW300 and CS500 were about 7.3%–36% lower than that for PW500 with the NaCl ionic strength increasing to 50 mM indicated the notable superiority in the mobility of PW500. These findings can provide new insights toward understanding the transformation and migration, and evaluating the environmental risk of biochar colloids.

Colloidal stability of nanosized activated carbon in aquatic systems: Effects of pH, electrolytes, and macromolecules

Nanosized activated carbon (NAC) is a novel adsorbent with great potential for water reclamation. However, its transport and reactivity in aqueous environments may be greatly affected by its stability against aggregation. This study investigated the colloidal stability of NAC in model aqueous systems with broad background solution chemistries including 7 electrolytes (NaCl, NaNO3, Na2SO4, KCl, CaCl2, MgCl2, and BaCl2), pH 4–9, and 6 macromolecules (humic acid (HA), fulvic acid (FA), cellulose (CEL), bovine serum albumin (BSA), alginate (ALG), and extracellular polymeric substance (EPS)), along with natural water samples collected from pristine to polluted rivers. The results showed that higher solution pH stabilized NAC by raising the critical coagulation concentration from 28 to 590 mM NaCl. Increased cation concentration destabilized NAC by charge screening, with the cationic influence following Ba2+ > Ca2+ > Mg2+ >> Na+ > K+. Its aggregation behavior could be predicted with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory with a Hamaker constant (ACWC) of 4.3 × 10−20 J. The presence of macromolecules stabilized NAC in NaCl solution and most CaCl2 solution following EPS > BSA > CEL > HA > FA > ALG, due largely to enhanced electrical repulsion and steric hindrance originated from adsorbed macromolecules. However, ALG and HA strongly destabilized NAC via cation bridging at high Ca2+ concentrations. Approximately half of NAC particles remained stably suspended for ∼10 d in neutral freshwater samples. The results demonstrated the complex effects of water chemistry on fate and transport of NAC in aquatic environments.

Effect of clay colloid – CuO nanoparticles interaction on retention of nanoparticles in different types of soils: role of clay fraction and environmental parameters

The extensive application of metal oxide nanoparticles (NPs) in various sectors has raised concern about their subsequent release and potentially harmful impacts on the soil system. The present study has addressed the interaction of CuO NPs with bentonite clay colloids (CC) under varying environmental parameters as a model to represent the soil pore water scenario. Based on CuO – CC interaction in model and natural soil solution extracts (SSE), the role of clay fraction and their stability on CuO retention in various types of soils have been evaluated.Results suggested that increasing ionic strength (IS) in the system caused aggregation of CuO NPs, and in the presence of CC, critical coagulation concentration decreased drastically from 27.8 and 17.3 mM to 10.7 and 0.33 mM for NaCl and CaCl2 respectively, due to heteroaggregation in the system. Interestingly, in the SSE, the dominating role of ionic valency, dissolved organic carbon (DOC), and CC was observed in colloidal stabilization over IS. No significant impact of temperature was observed on the stability of CuO NPs both in model and SSE. Further, stability studies in the SSE were correlated with NPs retention behavior in soils. Observations suggest that retention of CuO NPs in soils is a function of binding of the colloidal fraction to the soil, which in turn depends on the colloidal stability. The highest retention was observed in black and laterite soils, whereas lower binding of clay fraction in red soil caused the least retention. A decrease in Kd values after a certain application concentration provided maximum sustainable application concentration of CuO NPs, which may vary with soil properties. Results suggest that the binding of clay and organic matter with a sandy matrix of soil plays a prime role in deciding the overall fate of CuO NPs in the soils.

Aggregation kinetics of UV-aged soot nanoparticles in wet environments: Effects of irradiation time and background solution chemistry

Soot nanoparticles (SNPs) undergo aging processes in aqueous systems, altering their physicochemical properties and affecting their fate and transport. This study investigated the aging effects via ultraviolet irradiation on aggregation kinetics of SNPs in water. The results showed that, compared to fresh SNPs, those irradiated for 1 day aggregated more easily in NaCl and CaCl2 solutions, with reduction of critical coagulation concentrations by 72% and 40%, respectively. Similar phenomena were found in additional six electrolyte solutions, and SNPs irradiated for > 3 days had no measurable difference in aggregation rate. The aggregation-enhancement of irradiated SNPs was more prominent at low electrolyte concentrations and pH > 4. However, in the presence of macromolecules, irradiated SNPs could be stabilized against aggregation via steric hindrance with strength of bovine serum albumin > humic acid > alginate > fulvic acid, whereas alginate further destabilized aged SNPs via calcium bridging. The fitted Hamaker constant increased from 7.8 × 10−20 (fresh) to 1.2 × 10−19 J (7-day irradiated), suggesting that decarboxylation during irradiation may weaken electrical repulsion and enhance van der Waals attraction, promoting aggregation. These results demonstrated the vital role of UV-induced aging in fate and transport of SNPs in wet environments.

Aggregation and Deposition Kinetics of Polystyrene Microplastics and Nanoplastics in Aquatic Environment.

Microplastics (MPs) and nanoplastics (NPs) attract widespread attention due to their final threats to human health. Here, 50 nm and 500 nm polystyrene particles (PS50 and PS500) were selected as the typical NPs and MPs, respectively. Their aggregation kinetics was monitored, and their deposition was investigated on silica and alumina surfaces using quartz crystal microbalance with dissipation monitoring (QCM-D). PS500 has higher critical coagulation concentration (CCC) values than PS50, because of the weaker Brownian diffusion, less particle number and lower collision chance. PS50 has smaller values of critical deposition concentration (CDC) than PS500, indicating the stronger adsorption on silica. Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations explain that PS500 has weaker attachment on silica and slower deposition rate on alumina than PS50. Our results demonstrate that solution chemistry, particle size and mineral surfaces determine the transport and distribution of plastic particles together.

Stability of Boron Nitride Nanosphere Dispersions in the Presence of Polyelectrolytes.

Boron nitride nanospheres (BNNSs) were functionalized with polyelectrolytes. The effect of the polyelectrolyte dose and ionic strength on the charging and aggregation properties was investigated. At appropriate polyelectrolyte doses, charge neutralization occurred, whereas by increasing the dose, charge reversal was observed. The complete coating of the particles was indicated by a plateau in the ζ-potential values, which do not change significantly beyond the dose corresponding to the onset of such a plateau. The dispersions were highly aggregated around the charge neutralization point, while at lower or higher doses, the particles were stable. The salt-induced aggregation experiments revealed that the polyelectrolyte coatings contribute to the colloidal stability of the particles, namely, the critical coagulation concentrations deviated from the one determined for bare BNNSs. The presence of electrostatic and steric interparticle forces induced by the adsorbed polyelectrolyte chains was assumed. The obtained results confirm that the comprehensive investigation of the colloidal stability of BNNS particles is crucial to design stable or unstable dispersions and that polyelectrolytes are suitable agents for both stabilization and destabilization of BNNS dispersions, depending on the purpose of their application.

Effect of counter ion valence and pH on the aggregation and charging of oxidized carbon nanohorn (CNHox) in aqueous solution

Oxidized carbon nanohorn (CNHox) is one of carbon nanomaterials and has attracted attention due to its unique material properties. To clarify the dispersion, aggregation, and charging behaviors of CNHox in aqueous solutions with different valences of counter ions, K+, Ca2+, La3+, and pH, the stability ratio and electrophoretic mobility of CNHox were investigated by electrophoretic light scattering and time-resolved dynamic light scattering techniques. The CNHox showed pH-dependent negative zeta potential probably due to the de-protonation of carboxylic groups on CNHox. Increasing electrolyte concentration and counter ion valence decreased the magnitude of zeta potential by double layer screening and counter ion adsorption. The stability ratio of CNHox showed clear slow aggregation regime, fast aggregation regime, and critical coagulation concentration (CCC). The CCC decreased with increasing the counter ion valence. That is, the aggregation-dispersion of CNHox follows the Schulze-Hardy rule and the Derjaguin-Landau and Verwey-Overbeek (DLVO) theory. Furthermore, the relationship between critical coagulation ionic strength and charge density reasonably agrees with theoretical prediction by the DLVO theory for low surface potential. The DLVO theory is useful for the description of aggregation-dispersion of irreversible aggregates with colloidal size as found for CNHox aggregate, once their zeta potentials are evaluated.

Specific Ion Effects on Aggregation and Charging Properties of Boron Nitride Nanospheres.

The charging and aggregation properties of boron nitride nanospheres (BNNSs) were investigated in the presence of electrolytes of different compositions and valences in aqueous suspensions. The influence of mono- and multivalent cations (counterions) and anions (coions) on the colloidal stability of the negatively charged particles was studied over a wide range of salt concentrations. For monovalent ions, similar trends were determined in the stability and charging of the particles irrespective of the salt composition, i.e., no ion-specific effects were observed. Once multivalent counterions were involved, the critical coagulation concentrations (CCCs) decreased with the valence in line with the direct Schulze–Hardy rule. The dependence indicated an intermediate charge density for BNNSs. The influence of the coions on the CCCs was weaker and the destabilization ability followed the inverse Schulze–Hardy rule. The predominant interparticle forces were identified as electrical double-layer repulsion and van der Waals attraction. These findings offer useful information to design stable BNNS dispersions in various applications, where mono- and multivalent electrolytes or their mixtures are present in the samples.

Accurate Determination of the Quantity and Spatial Distribution of Counterions around a Spherical Macroion.

The accurate distribution of countercations (Rb+ and Sr2+ ) around a rigid, spherical, 2.9-nm size polyoxometalate cluster, {Mo132 }42- , is determined by anomalous small-angle X-ray scattering. Both Rb+ and Sr2+ ions lead to shorter diffuse lengths for {Mo132 } than prediction. Most Rb+ ions are closely associated with {Mo132 } by staying near the skeleton of {Mo132 } or in the Stern layer, whereas more Sr2+ ions loosely associate with {Mo132 } in the diffuse layer. The stronger affinity of Rb+ ions towards {Mo132 } than that of Sr2+ ions explains the anomalous lower critical coagulation concentration of {Mo132 } with Rb+ compared to Sr2+ . The anomalous behavior of {Mo132 } can be attributed to majority of negative charges being located at the inner surface of its cavity. The longer anion-cation distance weakens the Coulomb interaction, making the enthalpy change owing to the breakage of hydration layers of cations more important in regulating the counterion-{Mo132 } interaction.

Accurate Determination of the Quantity and Spatial Distribution of Counterions around a Spherical Macroion

AbstractThe accurate distribution of countercations (Rb+ and Sr2+) around a rigid, spherical, 2.9‐nm size polyoxometalate cluster, {Mo132}42−, is determined by anomalous small‐angle X‐ray scattering. Both Rb+ and Sr2+ ions lead to shorter diffuse lengths for {Mo132} than prediction. Most Rb+ ions are closely associated with {Mo132} by staying near the skeleton of {Mo132} or in the Stern layer, whereas more Sr2+ ions loosely associate with {Mo132} in the diffuse layer. The stronger affinity of Rb+ ions towards {Mo132} than that of Sr2+ ions explains the anomalous lower critical coagulation concentration of {Mo132} with Rb+ compared to Sr2+. The anomalous behavior of {Mo132} can be attributed to majority of negative charges being located at the inner surface of its cavity. The longer anion–cation distance weakens the Coulomb interaction, making the enthalpy change owing to the breakage of hydration layers of cations more important in regulating the counterion–{Mo132} interaction.

Soil colloids affect the aggregation and stability of biochar colloids

The stability of biochar colloids plays an important role in the transport and fate of contaminants and nutrients in soil. This study aimed to investigate the effects of main soil components, kaolin (Kao), goethite (Goe), and humic acid (HA) colloids on the aggregation kinetics of biochar colloids derived from dairy manure (DM), sewage sludge (SS), and wheat straw (WS). The WS biochar colloid had the highest critical coagulation concentration (CCC) (624 mM) than that of SS (200 mM) and DM (75 mM) due to its richest hydroxyl and carboxyl groups, showing the highest stability. Kao markedly improved the stability of DM and SS biochar colloids with 171% and 52.5% increase of CCC, respectively, by increasing the electrostatic repulsion of the system. However, the WS biochar colloid became more aggregated in the presence of Kao since the hydroxyl and carboxyl functional groups in WS biochar colloid could complex with Kao, generating electrostatic shielding. Goe could rapidly combine with biochar colloids via electrostatic attraction, resulting in the aggregation of SS and WS, while the aggregation rate of DM/Goe mixed colloids was inhibited. The HA increased the electrostatic repulsion of all biochar colloids through adsorbed on the surface of biochar colloids, resulting in the increased steric hindrance and stability of biochar colloids, with the CCC increased from 75 to 624 mM to 827–1012 mM. Our findings reveal that soil kaolin, goethite, and humic acid colloids have remarkable effects on the stability and aggregation of biochar colloid, which will advance understanding of the potential environmental fate and behaviors of biochar colloids.

Heteroaggregation of humic acid with montmorillonite in divalent electrolytes: effects of humic acid content and ionic concentration

Clay-humic substance complexes play a major role in controlling the mobility of elements and colloids in natural soils. The purpose of the present study is to explore the different reaction mechanisms induced by cations on the humic acid (HA) and montmorillonite (Mt) heteroaggregation and to analyze the binding mechanism of HA-Mt. HA is extracted from soil and colloidal Mt are prepared as K+-saturated. The aggregation kinetics of HA-Mt composite nanoparticles in Ca(NO3)2, Mg(NO3)2, and Cu(NO3)2 solutions were detected by dynamic light scattering. Furthermore, FT-IR spectroscopy was used to characterize the reactive sites involved in interaction with the metal ions. The results revealed that the order of reaction of these three metal cations with the HA-Mt composite was Cu2+ > Ca2+ > Mg2+, as evident from the total average aggregation rate, critical coagulation concentration, and activation energy. The heteroaggregation process was sensitive to the 1% mass percentage of HA; however, more HA (4% mass percentage) did not significantly affect this process compared with 1% HA. Higher cation concentration and higher HA content (10% mass percentage) were two necessary conditions for promoting HA-Mt heteroaggregation. The vibration peak intensities of the carboxyl group C-O bonds and hydroxyl group O-H bonds of HA were affected by the formation of coordinate bonds with different metal ions. Metal cations were preferentially complexed by the carboxyl groups of HA, and due to its polarization-induced and electric field–enhanced oxidizing properties, Cu2+ has the strongest aggregation ability for HA-Mt, followed by Ca2+ and Mg2+. The HA-Mt heteroaggregation is partially reversible by adjusting electrostatic repulsion. The results of this study improve our understanding of the roles of cations and HA in clay-humic substance interactions.

Colloidal stability and correlated migration of illite in the aquatic environment: The roles of pH, temperature, multiple cations and humic acid

The mobility and environmental risk of colloids and associated pollutants are dependent on their dispersion stability under various conditions. In this work, the stability and correlated migration of illite colloids (IC) were systematically investigated over a wide range of aquatic chemistry conditions. The results showed that IC was aggregation favorable at low pH, low temperature and high ionic strength. The critical coagulation concentration (CCC) of IC increased exponentially with increasing values of r/Z3, following the Schulze-Hardy and Hofmeister series. Humic acid (HA) greatly mitigated colloid aggregation since the attachment of HA on IC surface increased the steric hindrance and electrostatic potential, and the enhancement of stability was linearly correlated with the HA concentration. The Derjaguin-Landau-Verwey-Overbeek (DLVO) model revealed that the interaction force deriving from van der Waals forces and electrostatic double-layer energy evolved as the aquatic chemistry varied, and the reduction in repulsion force between particles facilitated the colloid collision and then aggregation. The migration of IC in the porous sand column was highly correlated with the dispersion stability and filtration effect, the agglomerated colloids were redispersed and released when conditions favored dispersion. The illite colloids acted as efficient carriers for Eu(III) transport. These findings are essential for improving the understanding of the geological fate of environmental colloids and associated radionuclides.

A graphene oxide Cookbook: Exploring chemical and colloidal properties as a function of synthesis parameters

Herein, we describe the synthesis of graphene oxide (GO) over a large range of conditions, exploring the effects of reaction temperature, reaction time, oxidant ratio, and sonication time on the chemical and colloidal properties of the product. As a function of reaction parameters, modified from Hummers’ method, GO products were characterized and described via a suite of spectroscopic, structural, and morphological techniques, including TEM, UV–vis spectroscopy, XPS, Raman spectroscopy, FTIR, and DLS. Average carbon oxidation state and the yield (upon sonication) were chosen as the two criteria to evaluate synthesized GO materials. It was observed that as reaction temperature increased, GO oxidation state and yield of the sonication step both increased. Further, increasing reaction time and oxidant ratio not only increased the oxidation state, but also had a pronounced effect on the final yield. As synthesized, GO with higher degrees of oxidization exhibited higher negative ζ-potential, slightly smaller hydrodynamic diameter, and higher critical coagulation concentration(s). Data sets collectively demonstrate that carbon oxidation state, functional group ratios, and the aggregation kinetics of GO products can be readily controlled by varying processing time and conditions with expected changes in aqueous behavior(s), including stability/aggregation.