Nanoscale Forces between Basal Mica Surfaces in Dicarboxylic Acid Solutions: Implications for Clay Aggregation in the Presence of Soluble Organic Acids.
ABSTRACT: The stability of organomineral aggregates in soils has a key influence on nutrient cycling, erosion, and soil productivity. Both clay minerals with distinct basal and edge surfaces and organic molecules with reactive functional groups offer rich bonding environments. While clay edges often promote strong inner-sphere bonding of -COOH-laden organics, we explore typically weaker, outer-sphere bonding of such molecules onto basal planes and its significance in organomineral interactions. In this surface force apparatus study, we probed face-specific interactions of negatively charged mica basal surfaces in solutions containing carboxyl-bearing, low-molecular-weight dicarboxylic acids (DAs). Our experiments provide distance-resolved, nanometer-range measurements of forces acting between two (001) mica surfaces and simultaneously probe DA adsorption. We show that background inorganic ions display crucial importance in nanoscale forces acting between basal mica surfaces and in DA adsorption: Na+ contributes to strong repulsion and little binding of dicarboxylic anions, while small amounts of Ca2+ are sufficient to screen the basal surface charge of mica, facilitate strong adhesion, and enhance dicarboxylic anion adsorption by acting as cationic bridges. Despite reversible and weak adsorption of DAs, we resolve their multilayer binding via assembly of hydrophobic chains in the presence of Ca2+, pointing the importance of abundant, less reactive basal clay surfaces in organomineral interactions.
Project description:The relative wettability of oil and water on solid surfaces is generally governed by a complex competition of molecular interaction forces acting in such three-phase systems. Herein, we experimentally demonstrate how the adsorption of in nature abundant divalent Ca(2+) cations to solid-liquid interfaces induces a macroscopic wetting transition from finite contact angles (? 10°) with to near-zero contact angles without divalent cations. We developed a quantitative model based on DLVO theory to demonstrate that this transition, which is observed on model clay surfaces, mica, but not on silica surfaces nor for monovalent K(+) and Na(+) cations is driven by charge reversal of the solid-liquid interface. Small amounts of a polar hydrocarbon, stearic acid, added to the ambient decane synergistically enhance the effect and lead to water contact angles up to 70° in the presence of Ca(2+). Our results imply that it is the removal of divalent cations that makes reservoir rocks more hydrophilic, suggesting a generalizable strategy to control wettability and an explanation for the success of so-called low salinity water flooding, a recent enhanced oil recovery technology.
Project description:Flavylium cations are synthetic analogues of anthocyanins, the natural plant pigments that are responsible for the majority of the red, blue, and purple colors of flowers, fruits, and leaves. Unlike anthocyanins, the properties and reactivity of flavylium cations can be manipulated by the nature and position of substituents on the flavylium cation chromophore. Currently, the most promising strategies for stabilizing the color of anthocyanins and flavylium cations appear to be to intercalate and/or adsorb them on solid surfaces and/or in confined spaces. We report here that hybrid pigments with improved thermal stability, fluorescence, and attractive colors are produced by the cation-exchange-mediated adsorption of flavylium cations (FL) on two synthetic clays, the mica-montmorillonite SYn-1, and the laponite SYnL-1. Compared to the FL/SYn-1 hybrid pigments, the FL/SYnL-1 pigments exhibited improved thermal stability as judged by color retention, better preferential adsorption of the cationic form of FL1 at neutral to mildly basic pH (pH 7-8), and lower susceptibility to color changes at pH 10. Although both clays adsorb the cationic form on their external surfaces, SYnL-1 gave more evidence of adsorption in the interlayer regions of the clay. This interlayer adsorption appears to be the contributing factor to the better properties of the FL/SYnL-1 hybrid pigments, pointing to this clay to be a promising inorganic matrix for the development of brightly colored, thermally more stable hybrid pigments based on cationic analogues of natural plant pigments.
Project description:Given the high surface reactivity of clay minerals, it is assumed that flocculation will lead to metal accumulation in marginal marine settings. However, the degree of metal sorption to clays is impacted by solution pH and ionic strength, and it remains unknown whether riverine clays indeed serve as a metal sink once they encounter seawater where pH and ionic strength markedly increase. Here, we conducted cadmium (Cd) adsorption experiments to three types of common clay minerals - kaolinite, illite and montmorillonite. We found that 20-30% of Cd from illite and montmorillonite surfaces were desorbed when transitioning from freshwater to seawater pH and ionic strength conditions, while kaolinite showed no discernible differences. Synchrotron X-ray adsorption spectroscopy confirmed that Cd release corresponded to a change in bonding from outer- to inner-sphere complexes when clays encountered seawater pH and ionic strength conditions. If other trace nutrients (such as Cu, Zn, Co) adsorbed onto riverine clay minerals behave in a similar manner to Cd, we speculate that their desorption in marginal marine settings should exert a significant impact on the productivity of the biosphere.
Project description:We report our studies on the adsorption properties of double-stranded DNA molecules on mica surfaces in a confined environment using a surface force apparatus. Specifically, we studied the influence of cation species and concentrations on DNA adsorption properties. Our results indicated that divalent cations (Mg(2+) and Co(2+)) preferred to form uniform and moderately dense DNA layers on a mica substrate. By measuring the interactions between DNA-coated mica and bare mica in an aqueous solution, obvious adhesion was observed in a cobalt chloride solution, possibly due to the ion-correlation attraction between negatively charged DNA and the mica surface. Furthermore, the interaction differences that were observed with MgCl2 and CoCl2 solutions reveal that the specific adsorption behaviors of DNA molecules on a mica substrate were mediated by these two salts. Our results are helpful to elucidate the dynamics of DNA binding on a solid substrate.
Project description:The adsorption of atenolol (AT) from aqueous solutions by Ca-montmorillonite (SAz-2) was investigated in batch studies under different physicochemical conditions. The AT existed in neutral un-dissociated form at pH 10, and was adsorbed on dioctahedral smectite (SAz-2) obeying the Langmuir isotherm with a maximum adsorption capacity of 330 mmol/kg. The kinetic adsorption suggested that both strong and weak adsorption sites existed on SAz-2 and participated in the adsorption mechanisms. The amount of exchangeable cations desorbed from SAz-2 during AT adsorption was linearly correlated with the amounts of adsorbed AT having slopes of 0.43, which implied that a cation exchange based adsorption mechanism was also in place. A comprehensive basal spacing change of SAz-2 was observed after AT adsorption on the clay mineral when tested with or without AT recrystallization. The intercalation of AT into the SAz-2 interlayers did not result in swelling due to the low adsorption capacity of the drug. Prominent interactions between the pharmaceutical molecule and SAz-2 were evidenced by apparent shifts of the infrared absorption bands after adsorption. The interlayer configurations and hydrogen bonding of AT on SAz-2 were also supported by infrared, X-ray diffraction and thermogravimetric analyses. This study suggested that SAz-2 is an excellent material to remove not only AT from pharmaceutical wastewater, but can potentially remove many other β-receptor blocker drugs. The results helped us to understand the possible interlayer configurations and adsorption mechanisms of the drugs on natural clay mineral based adsorbents.
Project description:This study investigates the adsorption mechanism differences among four nitrogenous dyes, sulforhodamine G (SRG), uncharged/deprotonated rhodamine B (RhB), orange II (Or II) and methyl blue (MB) by montmorillonite (MMT). MMT adsorption capacity for cationic MB was three times that of uncharged RhB and anionic SRG, while anionic Or II was not absorbed. Colloidal MMT particles have two types of surfaces, basal and edge, that interact with nitrogenous dyes very differently. The surface acidity of MMT was characterized with the pyridine adsorption method using in-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS). Adsorption of cationic MB was compared with the adsorption of RhB. In-situ attenuated total reflectance Fourier transform infrared (in-situ ATR-FTIR) spectroscopy indicated that a nitrogen atom on RhB complexes with a metal hydroxyl on an MMT edge through a water bridge. The highly polar edge hydroxyl is important to hydrogen bond formation. Cation ion exchange and washing experiments, as well as studies on the effect of temperature, pH and ionic strength on adsorption further clarified the adsorption mechanism. Our results provide insights into the effects of molecular structure on the adsorption of nitrogenous dyes by clay and the role of edge surfaces in the adsorption process.
Project description:Hygroscopic properties and chemical reactivity of secondary organic aerosols (SOA) influence their overall contribution to the indirect effect on the climate. In this study, we investigate the hygroscopic properties of organic and organometallic polymeric particles, namely polycatechol, polyguaiacol, Fe-polyfumarte, and Fe-polymuconate. These particles efficiently form in iron-catalyzed reactions with aromatic and aliphatic dicarboxylic acid compounds detected in field-collected SOA. The structure of surface water was studied using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and the uptake of gas water was quantified using quartz crystal microbalance (QCM) as a function of relative humidity. Spectroscopic data show that water bonding with organic functional groups acting as hydrogen bond acceptors causes shifts in their vibrational modes. Analysis of the hydroxyl group stretching region revealed weak and strong hydrogen bonding networks that suggest cluster formation reflecting water-water and water-organics interactions, respectively. A modified Type II multilayer Brunauer-Emmett-Teller adsorption model described the adsorption isotherm on the nonporous materials, polycatechol, polyguaiacol, and Fe-polymuconate. However, water adsorption on porous Fe-polyfumarate was best described using a Type V adsorption model, namely the Langmuir-Sips model that accounts for condensation in pores. The data revealed that organometallic polymers are more hygroscopic than organic polymers. The implications of these investigations are discussed in the context of the chemical reactivity of these particles relative to known SOA.
Project description:Both Fe(III)-bearing clay minerals and humic acids (HAs) are abundant in the soils and sediments. Previous studies have shown that bioreduction of structural Fe(III) in clay minerals could be accelerated by adding anthraquinone compound as a redox-active surrogate of HAs. However, a quinoid analogue could not reflect the adsorption and complexation properties of HA, and little is known about the effects of real HAs at environmental concentration on bioreduction of clay minerals. Here, it was shown that 10-200?mg l<sup>-1</sup> of natural or artificially synthesized HAs could effectively stimulate the bioreduction rate and extent of Fe(III) in both iron-rich nontronite NAu-2 and iron-deficient montmorillonite SWy-2. After adsorption to NAu-2, electron-transfer activities of different HA fractions were compared. Additionally, Fe(II) complexation by HAs also contributed to improvement of clay-Fe(III) bioreduction. Spectrosopic and morphological analyses suggested that HA addition accelerated the transformation of NAu-2 to illite, silica and siderite after reductive dissolution.
Project description:The specific interaction of ions with macromolecules and solid-liquid interfaces is of crucial importance to many processes in biochemistry, colloid science, and engineering, as first pointed out by Hofmeister in the context of (de)stabilization of protein solutions. Here, we use contact angle goniometry to demonstrate that the macroscopic contact angle of aqueous chloride salt solutions on mica immersed in ambient alkane increases from near-zero to values exceeding 10°, depending on the type and concentration of cations and pH. Our observations result in a series of increasing ability of cations to induce partial wetting in the order Na<sup>+</sup>, K<sup>+</sup> < Li<sup>+</sup> < Rb<sup>+</sup> < Cs<sup>+</sup> < Ca<sup>2+</sup> < Mg<sup>2+</sup> < Ba<sup>2+</sup>. Complementary atomic force microscopy measurements show that the transition to partial wetting is accompanied by cation adsorption to the mica-electrolyte interface, which leads to charge reversal in the case of divalent cations. In addition to electrostatics, hydration forces seem to play an important role, in particular for the monovalent cations.
Project description:Excess phosphate in water is known to cause eutrophication, and its removal is imperative. Nanoclay minerals are widely used in environmental remediation due to their low-cost, adequate availability, environmental compatibility, and adsorption efficiency. However, the removal of anions with nanoclays is not very effective because of electrostatic repulsion from clay surfaces with a net negative charge. Among clay minerals, halloysite nanotubes (HNTs) possess a negatively charged exterior and a positively charged inner lumen. This provides an increased affinity for anion removal. In this study, HNTs are modified with nano-scale iron oxide (Fe2O3) to enhance the adsorption capacity of the nanosorbent. This modification allowed for effective distribution of these oxide surfaces, which are known to sorb phosphate via ligand exchange and by forming inner-sphere complexes. A detailed characterization of the raw and (Fe2O3) modified HNTs (Fe-HNT) is conducted. Influences of Fe2O3 loading, adsorbent dosage, contact time, pH, initial phosphate concentration, and coexisting ions on the phosphate adsorption capacity are studied. Results demonstrate that adsorption on Fe-HNT is pH-dependent with fast initial adsorption kinetics. The underlying mechanism is identified as a combination of electrostatic attraction, ligand exchange, and Lewis acid-base interactions. The nanomaterial provides promising results for its application in water/wastewater treatment.