Mineral-water Interface Research Articles

Elucidating Phosphate and Cadmium Cosorption Mechanisms on Mineral Surfaces with Direct Spectroscopic and Modeling Evidence.

The simultaneous sorption of cations and anions at the mineral-water interface can substantially alter their individual sorption characteristics; however, this phenomenon lacks a mechanistic understanding. Our study provides direct spectroscopic and modeling evidence of the molecular cosorption mechanisms of the cadmium ion (Cd2+) and phosphate (P) on goethite and layered manganese (Mn) oxide of birnessite, through in situ attenuated total reflection Fourier-transform infrared (ATR-FTIR), P K-edge X-ray absorption near-edge structure (XANES) spectroscopy, and surface complexation modeling. Phosphate synergistically cosorbed with Cd on goethite predominantly through P-bridged ternary complexes (≡Fe-P-Cd) and electrostatic interactions at wide pH conditions. Likewise, P and Cd exhibited synergistic cosorption on birnessite by forming P-bridged ternary complexes (≡Mn-P-Cd) and weak competitive sorption at the layer edge sites. As pH and Cd loading increased, the surface P species transitioned from a binary complex to a ternary complex and/or Cd3(PO4)2 precipitate for both goethite and birnessite. Compared to that in solution at pH 8, the formation of Cd3(PO4)2 was inhibited by the presence of goethite and birnessite, ascribed to the specific adsorption of P and Cd, more pronounced in birnessite due to the stronger sorption of Cd at its vacant sites. The discovered cosorption mechanisms of P and Cd have important implications for understanding and predicting their mobility and availability in Cd-contaminated settings.

Enhancing aqueous carbonation via co-milled serpentine and wollastonite: Effects of mechanochemical activation

Carbon dioxide (CO2) storage through aqueous mineral carbonation is recognized as a promising technology for geochemical carbon removal. Previous studies predominantly focused on individual alkaline earth silicates, such as wollastonite or serpentine, overlooking their interactive effects on carbonation processes. To address this knowledge gap, we conducted aqueous carbonation tests using individually ball-milled serpentine (m-serpentine), wollastonite (m-wollastonite), mixtures of ball-milled serpentine and wollastonite (m-serpentine + m-wollastonite), and the co-milled serpentine and wollastonite (m-(serpentine + wollastonite)). The carbonation of (m-serpentine + m-wollastonite) involved the formation of a combination of calcite (CaCO3) and magnesite (MgCO3), suggesting that no significantly interactive effect between the serpentine and wollastonite. In contrast, carbonating m-(serpentine + wollastonite) results in the precipitation of Mg-bearing calcite ((Mg, Ca)CO3). Upon quantification, the carbonation degrees of m-(serpentine + wollastonite) is relatively higher than that of (m-serpentine + m-wollastonite). During the carbonation of m-(serpentine + wollastonite), the combination of serpentine and wollastonite facilitates mutual dissolution, leading to the release of more cations. However, these released ions do not diffuse into the bulk carbonating solution; instead, carbonation occurs exclusively at the mineral-water interface. Consequently, the co-milling process, merging Ca-rich wollastonite into Mg-rich serpentine, induces the formation of (Mg, Ca)SiO3. These novel insights into aqueous carbonation using a combination of Mg-containing and Ca-containing minerals underscore the significant role of mineral-mineral reactions in CO2 mineralization.

Coordination structures and stabilities of Am(III) adsorption complexes at kaolinite(0 0 1)-water interface

Understanding the structures and stabilities of actinide species is crucial for comprehending the sorption mechanisms at mineral–water interfaces. However, the relevant molecular-level fundamental aspects of actinide coordination chemistry at the mineral–water interface remain unclear. We herein conduct a systematic theoretical study of coordination structures and adsorption energies of Am3+ and Am(OH)2+ sorption complexes at the kaolinite(001)-water interface by integrating static density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. Computational results show that stable outer- and inner-sphere adsorption complexes are respectively formed through hydrogen bonding and coordinate bonding with surface aluminol groups. The most stable inner-sphere species are predicted to be tridentate surface complexes with an eight-folded coordination structure in the first coordination sphere of Am(III). This work deepens the understanding of Am(III) adsorption and complexation behaviors at the mineral–water interface, providing essential insights for actinide migration in natural environments and nuclear waste disposal. The synergy between static DFT calculations for initial screening and AIMD simulations for comprehensive dynamic analysis in this work enhances the efficiency and accuracy of theoretical predictions for actinide environmental chemistry and can be helpful for the broader research fields of geochemistry and environmental science.

A Fusion-Growth Protocell Model Based on Vesicle Interactions with Pyrite Particles.

Protocell models play a pivotal role in the exploration of the origin of life. Vesicles are one type of protocell model that have attracted much attention. Simple single-chain amphiphiles (SACs) and organic small molecules (OSMs) possess primitive relevance and were most likely the building blocks of protocells on the early Earth. OSM@SAC vesicles have been considered to be plausible protocell models. Pyrite (FeS2), a mineral with primitive relevance, is ubiquitous in nature and plays a crucial role in the exploration of the origin of life in the mineral-water interface scenario. "How do protocell models based on OSM@SAC vesicles interact with a mineral-water interface scenario that simulates a primitive Earth environment" remains an unresolved question. Hence, we select primitive relevant sodium monododecyl phosphate (SDP), isopentenol (IPN) and pyrite (FeS2) mineral particles to build a protocell model. The model investigates the basic physical and chemical properties of FeS2 particles and reveals the effects of the size, content and duration of interaction of FeS2 particles on IPN@SDP vesicles. This deepens the understanding of protocell growth mechanisms in scenarios of mineral-water interfaces in primitive Earth environments and provides new information for the exploration of the origin of life.

Unsaturation triggers specific adsorption performance of water films in the clay nanopores

Soil is typically unsaturated, with water films covering the soil particles playing a crucial role in soil mechanics, structure, and element transport. However, the unusual behavior of these water films and the underlying mechanisms are not yet fully understood. This study, which used molecular dynamics methods, sheds light on the distinct interactions between water films and clay surfaces under unsaturation. At the water-mineral interface, water molecules formed a layered structure, while they rearranged as a meniscus as the unsaturation extent increased. On the other hand, unsaturation had a significant impact on the location of water molecules at the water-vapor interface, but only a limited effect at the water-mineral interface. The water’s orientational ordering and hydrogen bonding interactions were significantly affected by changes in relative humidity (RH). Based on the distance-dependent diffusion coefficient, the water molecules within the water film were classified into three types: WT1 (< 5 Å) had faster diffusivity at higher RH, WT2 (5–6 Å) had comparable diffusivity at any RH, and WT3 (> 6 Å) had faster diffusivity at intermediate RH. This classification was supported by the retention dynamics analysis. The specific behaviors mentioned above, which are associated with unsaturation, are closely linked to Na+ hydration. This is because the interaction between water and Na+ is more pronounced than the interaction between water and minerals or Cl−. The results indicate that unsaturation triggers specific adsorption behaviors of water films that cover the clay surfaces. These behaviors should be considered in interfacial processes and environmental engineering.

Dynamic dissolution of Cm3+ ions incorporated at the calcite-water interface: an ab initio molecular dynamics simulation study.

The stability of actinide-mineral solid solution in a water environment is critical for assessing the safety of nuclear-waste geological repositories and studying actinide migration in natural systems. However, the dissolution behavior of actinide ions incorporated at the mineral-water interface is still unclear at the atomic level. Herein, we present metadynamics simulations of the reaction pathways, thermodynamics and kinetics of trivalent curium ions (Cm3+) dissolving from calcite surfaces. Cm3+ ions incorporated in different calcite surfaces (i.e., terrace and stepped surfaces) with distinct coordination environments have different reaction pathways, free energy barriers and free energy changes. We found that Cm dissolution from a stepped surface is more favorable than that from a terrace surface, both thermodynamically and kinetically. In addition, water molecules seem to promote the detachment of curium ions from the surface by exerting a pulling force via water coordination with Cm3+ and a pushing force via proton migration to the surface layer and water diffusion in the vacant Cm site. Thus, the findings from this work prove to be a milestone in revealing the dynamic dissolution mechanism of trivalent actinides from minerals and would also help predict the dissolution behaviors of other metal ions at the solid-water interface in chemical and environmental sciences.

Atomic structure and water arrangement on K-feldspar microcline (001).

The properties of clouds, such as their reflectivity or their likelihood to precipitate, depend on whether the cloud droplets are liquid or frozen. Thus, understanding the ice nucleation mechanisms is essential for the development of reliable climate models. Most ice nucleation in the atmosphere is heterogeneous, i.e., caused by ice nucleating particles such as mineral dusts or organic aerosols. In this regard, K-feldspar minerals have attracted great interest recently as they have been identified as one of the most important ice nucleating particles under mixed-phase cloud conditions. The mechanism by which feldspar minerals facilitate ice nucleation remains, however, elusive. Here, we present atomic force microscopy (AFM) experiments on microcline (001) performed in an ultrahigh vacuum and at the solid-water interface together with density functional theory (DFT) and molecular dynamics (MD) calculations. Our ultrahigh vacuum data reveal features consistent with a hydroxyl-terminated surface. This finding suggests that water in the residual gas readily reacts with the surface. Indeed, the corresponding DFT calculations confirm a dissociative water adsorption. Three-dimensional AFM measurements performed at the mineral-water interface unravel a layered hydration structure with two features per surface unit cell. A comparison with MD calculations suggests that the structure observed in AFM corresponds to the second hydration layer rather than the first water layer. In agreement with previous computation results, no ice-like structure is seen, questioning an explanation of the ice nucleation ability by lattice match. Our results provide an atomic-scale benchmark for the clean and water-covered microcline (001) plane, which is mandatory for understanding the ice nucleation mechanism on feldspar minerals.

Regulation of SiO2 Nanoparticles on the Adsorptive Fractionation of Dissolved Organic Matter by Goethite.

SiO2 nanoparticles (SiO2NPs) are most widely available and coexisting with DOM at the mineral-water interface; however, the role of SiO2NPs in DOM fractionation and the underlying mechanisms have not been fully understood. Using Fourier transform ion cyclotron resonance mass spectrometry, combined with Fourier transform infrared spectroscopy and X-ray adsorption fine structure spectroscopy, was employed to investigate the adsorptive fractionation of litter layer-derived DOM on goethite coexisting with SiO2NPs under different pH conditions. Results indicated that the inhibitory effect of the coexisting SiO2NPs on OM sorbed by goethite was waning as environmental pH increased due to the reduced steric interactions and the concurrent elevated hydrogen bonding/hydrophobic partitioning interactions on the goethite surface. We observed the coexisting SiO2NPs inhibited the adsorption of high carboxylic-containing condensed aromatic/aromatics compounds on goethite under different pH conditions while improving the adsorption of highly unsaturated aliphatic/phenolic and carbohydrate-like compounds in an alkaline and/or circumneutral environment. More nitrogen-containing structures may favor the adsorption of phenolic and nonaromatic compounds to goethite by counteracting the negative effect of SiO2NPs. These findings suggest that DOM sequestration may be significantly regulated by the coexisting SiO2NPs at the mineral-water interface, which may further influence the carbon-nitrogen cycling and contaminant fate in natural environments.

Photobleaching affects the carbon sequestration of dissolved black carbon on ferrihydrite: Perspective from molecular fractionation

Photobleaching generally changes the structure and properties of dissolved black carbon (DBC), which further affects distribution of DBC at mineral-water interface. Here, we investigated the effect mechanism by which DBC photobleaching on its sequestration on ferrihydrite (Fh) from perspective of molecular fractionation. Results indicated that continuous sunlight irradiation led to the photolysis of aromatic humic- and fulvic-like components and the carboxylation of the functional structure. DBC could be considerably sequestered on the Fh surface, and photobleached DBC (pDBC) with longer sunlight irradiation durations had lower adsorption capacity on Fh. The photo-absorption and photo-activity ability of residual DBC/pDBCs after adsorption significantly weakened, indicating that the photo-liable components with great photochemical properties were preferentially sequestered on Fh during adsorption fractionation at Fh-water interface. Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) results showed high molecular weight, high O contents and high unsaturation compounds (such as polycyclic aromatics and polyphenols) were preferentially sequestered on Fh through ligand exchange between iron-coordinated hydroxyl and substituted carboxyl/hydroxyl in DBC. Among high unsaturation compounds, aromatic ring structures (C=C) were with greater affinity with Fh surface than CO in carboxyl/ester/quinone. Photobleaching caused the decrease in aromatic ring structures and the increase in CO in carboxyl, which was the key for weakening of sequestration of pDBC on Fh. Our findings prove that the photo-liable components of DBC are more tend to be sequestered on mineral, and promote the understanding of geochemical behavior of DBC in the solid earth interfaces.

Adsorption behavior of soil fulvic acid on crystal faces of kaolinite and goethite: Described by CD-MUSIC model

The interaction between organic matter (OM) and minerals has significant impacts on the mineralization process and rate of OM, and can protect part of organic carbon in soils. In this study, the complex species of fulvic acid (FA) on the surface of minerals (kaolinite and goethite) and the corresponding thermodynamic characteristics were investigated with the CD-MUSIC model and isothermal titration calorimetry. With increasing pH, the adsorption of kaolinite for FA increased at pH < 5.5 and decreased at pH > 5.5, which might be due to the binding of carboxyl groups of FA onto the positively charged sites of O-face and edge-face. However, that of goethite consistently decreased with increasing pH from 3.5 to 9.0 due to an increase in electrostatic repulsion. The fraction of FA was mainly adsorbed on the edge-face and O-face to form inner sphere complexes on kaolinite and outer sphere complexes on goethite. Molar adsorption enthalpies indicated that FA was adsorbed through two site types on kaolinite, while that was one site type on goethite. In addition, the molar enthalpy was more closely associated with inner sphere complexation for kaolinite, while with outer sphere complexation for goethite. The findings shed new light on the adsorption behavior and complexation mechanism of OM on the crystal faces of mineral-water interface.

Inorganic Hydrogeochemistry in the 21st Century.

Chemical and isotopic processes occur in every segment of the hydrological cycle. Hydrogeochemistry-the subdiscipline that studies these processes-has seen a transformation from "witch's brew" to credible science since 2000. Going forward, hydrogeochemical research and applications are critical to meeting urgent societal needs of climate change mitigation and clean energy, such as (1) removing CO2 from the atmosphere and storing gigatons of CO2 in soils and aquifers to achieve net-zero emissions, (2) securing critical minerals in support of the transition from fossil fuels to renewable energies, and (3) protecting water resources by adapting to a warming climate. In the last two decades, we have seen extensive activity and progress in four research areas of hydrogeochemistry related to water-rock interactions: arsenic contamination of groundwater; the use of isotopic and chemical tracers to quantify groundwater recharge and submarine groundwater discharge; the kinetics of chemical reactions and the mineral-water interface's control of contaminant fate and transport; and the transformation of geochemical modeling from an expert-only exercise to a widely accessible tool. In the future, embracing technological advances in machine learning, cyberinfrastructure, and isotope analytical tools will allow breakthrough research and expand the role of hydrogeochemistry in meeting society's needs for climate change mitigation and the transition from fossil fuels to renewable energies.

Ion-Specific Interactions at a Mineral-Water Interface Revealed by Surface-Sensitive Spectroscopy under Flow Conditions

Ion-Specific Interactions at a Mineral-Water Interface Revealed by Surface-Sensitive Spectroscopy under Flow Conditions

RNA Hydrolysis at Mineral-Water Interfaces.

As an essential biomolecule for life, RNA is ubiquitous across environmental systems where it plays a central role in biogeochemical processes and emerging technologies. The persistence of RNA in soils and sediments is thought to be limited by enzymatic or microbial degradation, which occurs on timescales that are orders of magnitude faster than known abiotic pathways. Herein, we unveil a previously unreported abiotic pathway by which RNA rapidly hydrolyzes on the timescale of hours upon adsorption to iron (oxyhydr)oxide minerals such as goethite (α-FeOOH). The hydrolysis products were consistent with iron present in the minerals acting as a Lewis acid to accelerate sequence-independent hydrolysis of phosphodiester bonds comprising the RNA backbone. In contrast to acid- or base-catalyzed RNA hydrolysis in solution, mineral-catalyzed hydrolysis was fastest at circumneutral pH, which allowed for both sufficient RNA adsorption and hydroxide concentration. In addition to goethite, we observed that RNA hydrolysis was also catalyzed by hematite (α-Fe2O3) but not by aluminum-containing minerals (e.g., montmorillonite). Given the extensive adsorption of nucleic acids to environmental surfaces, we anticipate previously overlooked mineral-catalyzed hydrolysis of RNA may be prevalent particularly in iron-rich soils and sediments, which must be considered across biogeochemical applications of nucleic acid analysis in environmental systems.

Experimental and Machine Learning Studies on Chitosan-Polyacrylamide Copolymers for Selective Separation of Metal Sulfides in the Froth Flotation Process

The froth flotation process is extensively used for the selective separation of valuable base metal sulfides from uneconomic associated minerals. However, in this complex multiphase process, various parameters need to be optimized to ensure separation selectivity and peak performance. In this study, two machine learning (ML) models, artificial neural network (ANN) and random forests (RF), were used to predict the efficiency of in-house synthesized chitosan-polyacrylamide copolymers (C-PAMs) in the depression of iron sulfide minerals (i.e., pyrite) while valuable base metal sulfides (i.e., galena and chalcopyrite) were floated using nine flotation variables as inputs to the models. The prediction performance of the models was rigorously evaluated based on the coefficient of determination (R2) and the root-mean-square error (RMSE). The results showed that the RF model was able to produce high-fidelity predictions of the depression of pyrite once thoroughly trained as compared to ANN. With the RF model, the overall R2 and RMSE values were 0.88 and 4.38 for the training phase, respectively, and R2 of 0.90 and RMSE of 3.78 for the testing phase. As for the ANN, during the training phase, the overall R2 and RMSE were 0.76 and 4.75, respectively, and during the testing phase, the R2 and RMSE were 0.65 and 5.42, respectively. Additionally, fundamental investigations on the surface chemistry of C-PAMs at the mineral–water interface were conducted to give fundamental insights into the behavior of different metal sulfides during the flotation process. C-PAM was found to strongly adsorb on pyrite as compared to galena and chalcopyrite through zeta potential, X-ray photoelectron spectroscopy (XPS), and adsorption density measurements. XPS tests suggested that the adsorption mechanism of C-PAM on pyrite was through chemisorption of the amine and amide groups of the polymer.

Inhibition of Strontium Adsorption and Desorption by Ethylenediaminetetraacetic Acid at the Barite (001)–Water Interface

Understanding the sorption behavior of ions at the mineral–water interface is important to determine the fate of elements in the environment. Here, we used barite to understand metal and organic molecule interactions with ionic crystals as organic molecules are used to remove scale that can form during oil recovery in sulfate-rich settings. The sorption behavior of strontium (Sr) on the (001) surface in the presence of ethylenediaminetetraacetic acid (EDTA) was measured using in situ specular X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR). Based on the XR results, the presence of EDTA disrupts the barite surface structure, particularly that of the top two monolayers. A maximum of 0.7 (±0.2) EDTA molecules per surface unit cell are adsorbed, though the exact amount cannot be distinguished from that of other adsorbed species, such as Ba2+ and H2O. Based on the RAXR results, the presence of EDTA inhibits Sr incorporation into the barite surface and binds with Sr in solution to limit the amount of Sr2+ in solution. The Sr-EDTA2– complex then binds with barium ions at the barite surface, presumably in a bi-nuclear, bi-dentate state. Desorption of the Sr was also measured in the presence of EDTA. The desorption experiments show that ∼75% of the sorbed strontium was removed following extended reactions with EDTA and deionized water. There were minimal changes in the surface structure following desorption measurements implying that changes following Sr sorption in the presence of EDTA may be irreversible.

Theoretical insights into the coordination structures, stabilities and electronic spectra of Cm3+ species at the gibbsite-water interface: A computational study combing ab initio molecular dynamics and wave function theory

The information of structure and stability of actinide species is key to understand the sorption mechanism of actinides at mineral–water interface. Such information is approximately derived from experimental spectroscopic measurements and needs to be accurately obtained by a direct atomic-scale modelling. Herein, systematic first-principles calculations and ab initio molecular dynamics (AIMD) simulations are carried out to study the coordination structures and absorption energies of Cm(III) surface complexes at gibbsite-water interface. Eleven representative complexing sites are investigated. The most stable Cm3+ sorption species are predicted to be a tridentate surface complex in weakly acidic/neutral solution condition and a bidentate one in the alkaline solution condition. Moreover, luminescence spectra of the Cm3+ aqua ion and the two surface complexes are predicted based on the high-accuracy ab initio wave function theory (WFT). The results give a gradually decreasing emission energy in good agreement with experimental observation of a red shift of peak maximum with pH increasing from 5 to 11. This work is a comprehensive computational study involving AIMD and ab initio WFT methods to gain the coordination structures, stabilities, and electronic spectra of actinide sorption species at the mineral–water interface, thus providing important theoretical support for geological disposal of actinide waste.

Molecular Origin of Wetting Characteristics on Mineral Surfaces

Accurate determination of the wetting characteristics on mineral surfaces is critical for many natural processes and industrial applications where multiphase flow in porous media is involved. The wetting behaviors on mineral surfaces are controlled by water-mineral interactions, giving rise to various wetting characteristics, including contact line advancement, formation of precursor films, etc. However, a fundamental understanding of wetting characteristics on different mineral surfaces is still lacking at the molecular level. Here, utilizing a comprehensive set of molecular dynamics simulations, we investigate the wetting characteristics of water on various mineral surfaces and obtain the corresponding water-mineral interaction properties (including the areal density of water-mineral interaction energy and the work of adhesion of the water-mineral interface), mineral wettability, and structural and diffusion properties of water molecules near the surface. We show that the diffusion properties of water molecules on mineral surfaces play an important role in wetting characteristics. We find that the contact line tends to advance forward in the jumping mode or the rolling mode during the wetting process, which depends on the diffusion capacity of the water molecules on mineral surfaces. The corresponding evolution of the solid-liquid friction coefficient during dynamic spreading is also analyzed. We further demonstrate the strong impact of isomorphic substitution and charge-balancing counterions on wetting characteristics on the surfaces of clay minerals. It is shown that the introduction of charge-balancing counterions can shift the mineral surface from strongly hydrophilic to strongly hydrophobic and lead to completely different wetting characteristics. Our results provide a clearer picture of the molecular underpinnings in mineral wetting phenomena and deepen the understanding of the control of water-mineral interactions on the wetting properties.

Understanding surface complexation of antimony on Mg(OH)2: Insights from first-principles molecular dynamics

Sorption processes at the mineral–water interface are of great importance in dominating the fate and availability of metalloid contaminants in natural environment. Aiming at a thorough understanding of the complexation of antimony (Sb) on metal hydroxide, we conducted first-principles molecular dynamic (FPMD) simulations and batch adsorption experiments to elucidate the quantitative mechanism of Sb complexation on Mg(OH)2. Batch experiments showed the sorption of Sb(III) is nearly pH-independent, while increasing pH markedly weakened Sb(V) sorption; the measured sorption isotherm curves were well fitted by Langmuir model. Subsequently, molecular-level mechanism of Sb(V)/Sb(III) on brucite basal and edge surfaces were revealed by FPMD, including microscopic surface reactive sites, local complexing structures and coordination geometries, and complexing free energies. Results showed that Sb(III)/Sb(V) can form outer-sphere complexation on basal surface by hydrogen bonding. On edge surface, Sb(III)/Sb(V) formed stable inner-sphere mononuclear monodentate and binuclear bidentate complexes. The calculated free energies indicated that the binuclear bidentate complexing was more favorable than monodentate structure, and the complexation of Sb(III) was more stable than Sb(V). Accordingly, reaction pathway of the ligand exchange and thermodynamic stability of the different inner-sphere complexes were clarified. This study provides theoretical basis for evaluating the environmental risk of Sb and improving the engineering efficiency of Sb-contaminated water management.

Novel insights into the temporal molecular fractionation of dissolved black carbon at the iron oxyhydroxide - water interface

As the most reactive and mobile fraction of black carbon, dissolved black carbon (DBC) inexorably interacts with minerals in the biosphere. Nevertheless, the research on the mechanisms and compositions of DBC assembly at the mineral-water interface remains limited. In this study, we revealed the “kinetic architecture” of DBC on iron oxyhydroxide at novel insights based on quantitative and qualitative approaches. The results indicated that high molecular weight, highly unsaturated, oxygen-rich (such as carboxyl-rich fraction, phenolics), aliphatics, and long C chains compounds were preferentially adsorbed on the iron oxyhydroxide. 2D-COS analyses directly disclosed the sequential fractionation: aromatic and phenolic groups > aliphatic groups, and few aromatics were continuously adsorbed after the rapid adsorption. Quantitative determinations identified that aromatic and phenolic components were adsorbed rapidly over the first 60 min, while aromatics achieved the dynamic equilibrium until ∼300 min, which was consistent with the 2D-COS observations. Our findings supported the hypothesis that “mineral-OM” and “OM-OM” interactions worked simultaneously, and the adsorption might be co-driven by ligand exchange, hydrophobic interactions, and other mechanisms. This work provided the theoretical basis for organic carbon storage and turnover, and it was valuable for predicting the behaviors and fates of contaminants at the soil-water interface and surface water.

Kinetics and energetics of pharmacolite mineralization via the classic crystallization pathway

Pharmacolite (CaHAsO4·2H2O) mineralization is an important process controlling arsenate mobility in carbonate areas but is poorly understood in terms of crystallization mechanism and kinetics. The present study intends to investigate pharmacolite formation initiated by heterogenous nucleation through in situ observations of the mineral–water interface. Experiments were performed by exposing gypsum substrate to solutions supersaturated with respect to pharmacolite followed by atomic force microscopy imaging to record changes in surface morphology and topography. The data are used to determine growth mode, step speed, and the rate of step birth. Experimental results show the crystallization is achieved by direction-specific mono-molecular layer growth via 2D surface nucleation or spiral hillock development in accord with the classical crystallization model. Subsequent theoretical analyses allow to determine step energies and kinetic coefficients in major growth directions on (010) and indicate that [001] steps are energetically the most stable and morphologically the most prominent while [100] and [101] steps are controlled either by thermodynamic or kinetics. Gypsum plays an important role in aiding pharmacolite formation through epitaxy as the two minerals share a range of structural commonalities. The notably reduced supersaturation needed in substrate-assisted pharmacolite crystallization relative to bulk solution nucleation suggests gypsum may significantly reduce the energy barrier for the mineralization reactions and hence may find applications in As remediation practice.