Frédéric Loosli

TiO2 nanoparticles aggregation and disaggregation in presence of alginate and Suwannee River humic acids. pH and concentration effects on nanoparticle stability

The behavior of manufactured TiO2 nanoparticles is studied in a systematic way in presence of alginate and Suwannee River humic acids at variable concentrations. TiO2 nanoparticles aggregation, disaggregation and stabilization are investigated using dynamic light scattering and electrophoretic experiments allowing the measurement of z-average hydrodynamic diameters and zeta potential values. Stability of the TiO2 nanoparticles is discussed by considering three pH-dependent electrostatic scenarios. In the first scenario, when pH is below the TiO2 nanoparticle point of zero charge, nanoparticles exhibit a positively charged surface whereas alginate and Suwannee River humic acids are negatively charged. Fast adsorption at the TiO2 nanoparticles occurs, promotes surface charge neutralization and aggregation. By increasing further alginate and Suwannee River humic acids concentrations charge inversion and stabilization of TiO2 nanoparticles are obtained. In the second electrostatic scenario, at the surface charge neutralization pH, TiO2 nanoparticles are rapidly forming aggregates. Adsorption of alginate and Suwannee River humic acids on aggregates leads to their partial fragmentation. In the third electrostatic scenario, when nanoparticles, alginate and Suwannee River humic acids are negatively charged, only a small amount of Suwannee River humic acids is adsorbed on TiO2 nanoparticles surface. It is found that the fate and behavior of individual and aggregated TiO2 nanoparticles in presence of environmental compounds are mainly driven by the complex interplay between electrostatic attractive and repulsive interactions, steric and van der Waals interactions, as well as concentration ratio. Results also suggest that environmental aquatic concentration ranges of humic acids and biopolymers largely modify the stability of aggregated or dispersed TiO2 nanoparticles.

Towards a better understanding on agglomeration mechanisms and thermodynamic properties of TiO2 nanoparticles interacting with natural organic matter

Interaction between engineered nanoparticles and natural organic matter is investigated by measuring the exchanged heat during binding process with isothermal titration calorimetry. TiO2 anatase nanoparticles and alginate are used as engineered nanoparticles and natural organic matter to get an insight into the thermodynamic association properties and mechanisms of adsorption and agglomeration. Changes of enthalpy, entropy and total free energy, reaction stoichiometry and affinity binding constant are determined or calculated at a pH value where the TiO2 nanoparticles surface charge is positive and the alginate exhibits a negative structural charge. Our results indicate that strong TiO2-alginate interactions are essentially entropy driven and enthalpically favorable with exothermic binding reactions. The reaction stoichiometry and entropy gain are also found dependent on the mixing order. Finally correlation is established between the binding enthalpy, the reaction stoichiometry and the zeta potential values determined by electrophoretic mobility measurements. From these results two types of agglomeration mechanisms are proposed depending on the mixing order. Addition of alginate in TiO2 dispersions is found to form agglomerates due to polymer bridging whereas addition of TiO2 in alginate promotes a more individually coating of the nanoparticles.

Effect of electrolyte valency, alginate concentration and pH on engineered TiO2 nanoparticle stability in aqueous solution

Agglomeration and disagglomeration processes are expected to play a key role on the fate of engineered nanoparticles in natural aquatic systems. These processes are investigated here in detail by studying first the stability of TiO2 nanoparticles in the presence of monovalent and divalent electrolytes at different pHs (below and above the point of zero charge of TiO2) and discussing the importance of specific divalent cation adsorption with the help of the DLVO theory as well as the importance of the nature of the counterions. Then the impact of one polysaccharide (alginate) on the stability of agglomerates formed under pH and water hardness representative of Lake Geneva environmental conditions is investigated. In these conditions the large TiO2 agglomerates (diameter>1μm) are positively charged due to Ca(2+) and Mg(2+) specific adsorption and alginate, which is negatively charged, adsorbs onto the agglomerate surface. Our results indicate that the presence of alginate at typical natural organic matter concentration (1-10 mg L(-1)) strongly modifies the TiO2 agglomerate (50 mg L(-1)) stability by inducing their partial and rapid disagglomeration. The importance of disagglomeration is found dependent on the alginate concentration with maximum of disagglomeration obtained for alginate concentration ≥8 mg L(-1) and leading to 400 nm fragments. From an environmental point of view partial restabilization of TiO2 agglomerates in the presence of alginate constitutes an important outcome. Disagglomeration will enhance their transport and residence time in aquatic systems which is an important step in the current knowledge on risk assessment associated to engineered nanoparticles.

Effect of natural organic matter on the disagglomeration of manufactured TiO2 nanoparticles

One major concern in the fate of nanomaterials in aquatic systems is the lack of data on nanomaterial transformations under relevant environmental conditions. The disagglomeration of aggregates composed of manufactured anatase titanium dioxide nanoparticles is investigated here in the presence of alginate and Suwannee River humic acids at varying concentrations using dynamic light scattering and electrophoretic measurements. Stability of TiO2 nanoparticle agglomerates at typical environmental concentrations of natural organic matter is discussed at a pH value corresponding to the point of zero charge of TiO2 nanoparticles. In this scenario, the surface charge of TiO2 is neutralized, allowing the nanoparticles to form large agglomerates. Alginate and Suwannee River humic acids exhibit a negative structural charge under this pH condition and adsorption of both natural polyelectrolytes on the surface of nanoparticle agglomerates leads to disagglomeration and significant redispersion of TiO2 nanoparticles into fragments. Results indicate that both electrostatic forces and steric interactions play key roles during the disagglomeration process and that the physicochemical properties of natural organic matter are found to influence the kinetics and importance of fragmentation in the disagglomeration process. Most importantly, our data indicate that the presence of natural organic matter at typical environmental concentrations induces significant disagglomeration of large submicron nanoparticle agglomerates. Such a result constitutes an important outcome with regards to the risk associated with manufactured nanoparticles by including the possible transformations of the micron size range structures they can form.

Isothermal titration calorimetry as a powerful tool to quantify and better understand agglomeration mechanisms during interaction processes between TiO2 nanoparticles and humic acids

The association processes between engineered TiO2 nanoparticles and Suwannee River humic acids are investigated by isothermal titration calorimetry and by measuring the exchanged heat during the binding process, allowing the determination of thermodynamic (change in enthalpy, Gibbs free energy and entropy) and reaction (binding affinity constant, reaction stoichiometry) parameters. Our results indicate that strong TiO2–Suwannee River humic acid interactions are entropically and enthalpically favorable with exothermic binding reactions and that the mixing order is also an important parameter. High humic acid concentrations induce homoagglomeration (“self”-assembly) and are shown to favor an enthalpically driven association process. Light scattering techniques are also considered to investigate the influence of TiO2 surface charge modifications and agglomeration mechanisms. Patch and bridging mechanisms are found to result in the formation of large agglomerates once charge inversion of TiO2–humic acid complexes is achieved. Moreover, van der Waals interactions are also found to play a significant role during interaction processes due to the amphiphilic character of humic acids.

Impact of alginate concentration on the stability of agglomerates made of TiO2 engineered nanoparticles: Water hardness and pH effects

The stability of engineered nanoparticles in natural aquatic systems is of high interest for environmental risk assessment since an already important quantity of these reactive species is entering aquatic systems. In the present study, an important issue is addressed by investigating (i) the influence of divalent cations and water hardness (Mg2+ and Ca2+) in agglomerate formation and (ii) alginate concentration effect on the stability TiO2 agglomerates formed in environmental freshwater conditions (pH and total hardness) representative of Lake Geneva, France/Switzerland. Our results indicate that the presence of alginate at typical natural organic matter concentration strongly modifies the stability of TiO2 nanoparticle agglomerates by inducing their partial disagglomeration. Significant TiO2 nanoparticles redispersion and formation of small fragments are expected to be induced by alginate adsorbed layer formed at the nanoparticle surfaces within the agglomerates.Graphical Abstract

Formation of complexes between hematite nanoparticles and a non-conventional galactomannan gum. Toward a better understanding on interaction processes.

The physicochemical characteristics of hematite nanoparticles related to their size, surface area and reactivity make them useful for many applications, as well as suitable models to study aggregation kinetics. For several applications (such as remediation of contaminated groundwater) it is crucial to maintain the stability of hematite nanoparticle suspensions in order to assure their arrival to the target place. The use of biopolymers has been proposed as a suitable environmentally friendly option to avoid nanoparticle aggregation and assure their stability. The aim of the present work was to investigate the formation of complexes between hematite nanoparticles and a non-conventional galactomannan (vinal gum--VG) obtained from Prosopis ruscifolia in order to promote hematite nanoparticle coating with a green biopolymer. Zeta potential and size of hematite nanoparticles, VG dispersions and the stability of their mixtures were investigated, as well as the influence of the biopolymer concentration and preparation method. DLS and nanoparticle tracking analysis techniques were used for determining the size and the zeta-potential of the suspensions. VG showed a polydispersed size distribution (300-475 nm Z-average diameter, 0.65 Pdi) and a negative zeta potential (between -1 and -12 mV for pH2 and 12, respectively). The aggregation of hematite nanoparticles (3.3 mg/L) was induced by the addition of VG at lower concentrations than 2mg/L (pH5.5). On the other hand, hematite nanoparticles were stabilized at concentrations of VG higher than 2 mg/L. Several phenomena between hematite nanoparticles and VG were involved: steric effects, electrostatic interactions, charge neutralization, charge inversion and polymer bridging. The process of complexation between hematite nanoparticles and the biopolymer was strongly influenced by the preparation protocols. It was concluded that the aggregation, dispersion, and stability of hematite nanoparticles depended on biopolymer concentration and also on the way of preparation and initial physicochemical properties of the aqueous system.

Effect of surfactants, pH and water hardness on the surface properties and agglomeration behavior of engineered TiO2 nanoparticles

The influence of sodium dodecyl sulfate (SDS) on the stability of TiO2 engineered nanoparticle (ENP) dispersions is investigated under various pH conditions, SDS and divalent cation concentrations. Based on different scenarios and systematic measurements of surface charges and z-average sizes, a detailed mechanistic approach is proposed assuming surfactant adsorption/desorption, charge inversion, cation bridging, specific adsorption, hydrophobic effects, agglomeration and disagglomeration. Adsorption of SDS on oppositely charged TiO2 nanoparticles is found to strongly modify their stability. Formation of large agglomerates can be achieved via several routes: i) in the absence of SDS and by adjusting the pH close to the TiO2 point of zero charge, and ii) in the presence of SDS at a concentration where the positive surface charges of the TiO2 nanoparticles are counterbalanced by the SDS negative charges (charge neutralization). It is also found that hydrophobic interaction mechanisms between the SDS molecules can also promote the formation of large structures. The influence of pH variations on TiO2–SDS electrostatic complexes, formed at low pH, indicates that an excess of SDS is required to prevent the formation of large agglomerates upon pH changes. At low or intermediate SDS concentrations, TiO2 stability is governed by the subtle interplay of SDS adsorption and TiO2 surface charge acid–base properties. The presence of divalent electrolytes (water hardness) is found to reduce the SDS amount adsorbed on TiO2 ENPs and to promote the formation of large micron-sized agglomerates by cation bridging. Our results also indicate that the dispersion preparation protocol is an important issue to consider when ENPs and SDS mixtures have to be prepared and that for the formation of “individually” coated and stable nanoparticles, punctual addition of SDS is required at concentrations higher than the isoelectric point.

Wire‐Active Microrheology to Differentiate Viscoelastic Liquids from Soft Solids

Viscoelastic liquids are characterized by a finite static viscosity and a yield stress of zero, whereas soft solids have an infinite viscosity and a non-zero yield stress. The rheological nature of viscoelastic materials has long been a challenge and is still a matter of debate. Here, we provide for the first time the constitutive equations of linear viscoelasticity for magnetic wires in yield-stress materials, together with experimental measurements by using magnetic rotational spectroscopy (MRS). In MRS, the wires were subjected to a rotational magnetic field as a function of frequency and the motion of the wire was monitored by using time-lapse microscopy. The studied soft solids were aqueous dispersions of gel-forming polysaccharide (gellan gum) at concentrations above the gelification point. It was found that soft solids exhibited a clear and distinctive signature compared with viscous and viscoelastic liquids. In particular, the average wire rotation velocity equaled zero over a broad frequency range. We also showed that the MRS technique is quantitative. The equilibrium elastic modulus was retrieved from the wire oscillation amplitudes, and agrees with polymer-dynamics theory.

Manufactured Nanoparticle Behavior and Transformations in Aquatic Systems. Importance of Natural Organic Matter

Major concerns to elucidate the fate of nanomaterials and manufactured nanoparticles in aquatic systems are related to the lack of data on nanoparticle transformations under relevant environmental conditions. The present article discusses some of the important physicochemical processes controlling the behavior of manufactured nanoparticles in aqueous systems by focusing on their interaction with natural organic matter, which is expected to play a crucial role when adsorbing at the nanoparticle surface. The precise knowledge and consequences of such adsorption processes are important not only to predict the nanoparticle stability and dispersion state but also to evaluate their chemical reactivity and ecotoxicology. Most importantly, findings indicate that the presence of natural organic matter, at typical environmental concentrations, can induce significant disagglomeration of large nanoparticle agglomerates into small fragments. Such a result constitutes an important outcome with regard to the risk associated with the possible transformation and redispersion of large assemblies containing manufactured nanoparticles.