Charge Distribution Multisite Complexation Research Articles

Quantitative Insights into Phosphate-Enhanced Lead Immobilization on Goethite.

Despite extensive study, geochemical modeling often fails to accurately predict lead (Pb) immobilization in environmental samples. This study employs the Charge Distribution MUlti-SIte Complexation (CD-MUSIC) model, X-ray absorption fine structure (XAFS), and density functional theory (DFT) to investigate mechanisms of phosphate (PO4) induced Pb immobilization on metal (hydr)oxides. The results reveal that PO4 mainly enhances bidentate-adsorbed Pb on goethite via electrostatic synergy at low PO4 concentrations. At relatively low pH (below 5.5) and elevated PO4 concentrations, the formation of the monodentate-O-sharing Pb-PO4 ternary structure on goethite becomes important. Precipitation of hydropyromorphite (Pb5(PO4)3OH) occurs at high pH and high concentrations of Pb and PO4, with an optimized log Ksp value of -82.02. The adjustment of log Ksp compared to that in the bulk solution allows for quantification of the overall Pb-PO4 precipitation enhanced by goethite. The CD-MUSIC model parameters for both the bidentate Pb complex and the monodentate-O-sharing Pb-PO4 ternary complex were optimized. The modeling results and parameters are further validated and specified with XAFS analysis and DFT calculations. This study provides quantitative molecular-level insights into the contributions of electrostatic enhancement, ternary complexation, and precipitation to phosphate-induced Pb immobilization on oxides, which will be helpful in resolving controversies regarding Pb distribution in environmental samples.

Arsenate and phosphate adsorption onto Mg-Fe layered double hydroxides: The charge-distribution multisite complexation (CD-MUSIC) modeling as a tool to predict competitive oxyanion behavior

The adsorption of arsenate and phosphate onto natural or synthetic layered double hydroxides (LDHs) has emerged as a promising solution to minimize the environmental effects of these compounds in soils and waters. In the present work, the adsorption of these oxyanions onto Mg-Fe LDHs in both single-ion and competitive systems was studied through wet chemistry experiments, solid-state analyses, and advanced surface complexation modeling (SCM). The Mg-Fe LDH showed a good efficiency to remove both As and P, being the pH of the system a major driver for the adsorption levels observed. Adsorption results for competitive systems showed a decrease for both oxyanions compared to the single-ion adsorption systems. The adsorption behavior is mechanistically described using two types of SCM, namely the diffusion layer model (DLM) and the charge-distribution multisite complexation model (CD-MUSIC). The later model captures better the influence of pH and ionic strength on the adsorption of arsenate and phosphate onto LDH in both single-ion and multicomponent systems. The best description of the experimental results was obtained when combining two types of surface complexes, namely monodentate inner-sphere complex at lower pH values and monodentate outer-sphere complex at higher pH values. This model approach provides more detailed information about the surface properties of LDHs, which may be beneficial for future studies dealing with LDHs as reactive phases influencing metal(loid) mobility in water or soil systems.

Antimony immobilization mechanism on schwertmannite: Insights from the microstructure of schwertmannite

Schwertmannite affects the mobility of antimony (Sb) in acid mine drainage, yet the Sb sorption mechanism remains elusive. In this study, the molecular-level mechanism and the driving force of Sb(V) immobilized on schwertmannite were investigated by a combination of wet chemistry, extended X-ray absorption fine structure (EXAFS) analysis, density functional theory (DFT) calculations, and a surface complexation model (SCM). The observed sorption capacity for Sb(V) was as high as 235.63 mg/g. Such remarkable sorption capacity is primarily achieved by the anion exchange reaction and surface complexation reaction of Sb(V) with sulfate and surface/tunnel inner-surface hydroxyl groups, respectively, and the contribution of the anion exchange reaction to Sb(V) immobilization decreases markedly with increasing Sb(V) loading or pH. The loading of Sb(V) appears to be the key parameter controlling its immobilization mechanism on schwertmannite. Low-loaded Sb(V) primarily generates bidentate-mononuclear and bidentate-binuclear surface complexes (adsorption products) and is concurrently partly incorporated into the Fe-O framework of schwertmannite to form a hexadentate-hexanuclear complex (incorporation product). With increasing Sb(V) loading, Sb is primarily adsorbed on the surface and in the tunnel of schwertmannite with the formation of bidentate-mononuclear (dominant) and bidentate-binuclear complexes without incorporation. The inconsistency of the immobilization mechanism is controlled by the amount of released sulfate induced by Sb(V). The substantial system energy reduction caused by the formation of Sb(V) adsorption and incorporation products on the surface and in the tunnel of schwertmannite is the driving force for the stable immobilization of Sb(V) by schwertmannite, and the energy reduction caused by tunnel complexes is far more obvious than that caused by surface complexes. A charge distribution multisite complexation model was established based on bidentate-mononuclear and bidentate-binuclear surface complexes with fitted Log K values of 21.99 ± 0.18 and 12.84 ± 0.92, respectively, which consistently predicted Sb(V) sorption across pH 3.0–9.0 for all involved Sb(V) loadings. In addition, Sb(V) has a strong stabilizing effect on the schwertmannite structure and broadens its pH stability window (pH 3.0–9.0). This study facilitates elucidation of the fate and geochemical cycling of Sb in the mining environment and helps to promote the application of the microstructure of schwertmannite in other studies of microscopic interface chemistry.

Unraveling the Np(V) sorption on ZrO2: A batch, spectroscopic and modeling combined approach

The interactions of the long-lived actinide neptunium with the corrosion product zirconia (ZrO2) have to be considered in the safety assessment of a repository for radioactive waste. The sorption of Np(V) on ZrO2 was investigated in the absence of carbonate at the macroscopic and molecular scale. At the macroscopic level, the Np(V) uptake was independent of ionic strength and the isoelectric point of the pristine zirconia was increased, both suggesting the presence of inner-sphere Np(V) surface complexes. The Np(V) sorption isotherms indicated the presence of strong and weak sorption sites. Molecular level information were derived from in situ attenuated total reflection Fourier-transform infrared spectroscopy and extended X-ray absorption fine structure spectroscopy (EXAFS), which confirmed the presence of Np(V) inner-sphere complexes. EXAFS experiments revealed the formation of a bidentate inner-sphere surface complex in the weak sorption site regime. The derived information at the macroscopic and molecular levels were used to parametrize a charge distribution multi-site complexation (CD-MUSIC) model. The derived thermodynamic constants can help to better predict the environmental fate of Np(V) in the context of nuclear waste repository assessments and can also support the appraisal of safety-relevant scenarios for the extended interim storage of spent nuclear fuel.

Towards building a unified adsorption model for goethite based on direct measurements of crystal face compositions: I. Acidity behavior and As(V) adsorption

We have determined the proton, electrolyte (NaNO3) and arsenate affinity constants on the corresponding surface sites of goethite. An empirical optimization approach was applied using the Charge Distribution Multisite Complexation (CD-MUSIC) model, initially, by simulating an extensive proton adsorption data set obtained from four goethites of specific surface areas (SSAs) spanning from 43 to 89 m2/g. Each goethite showed different crystal face compositions, which were measured previously from independent high resolution electron microscopy observations. Only the capacitance value was left as an additional optimizing parameter. For arsenate adsorption, with the above optimized values fixed, the contributing surface arsenate complexes and their respective affinity constants and charge distributions (CD) were also optimized. A unified set of affinity and CD parameters was obtained, where the only resulting variables among goethites were the capacitance 1, the specific surface area and the crystal face contributions (and thus their reactive surface site densities).It was found that the site density parameter is decisive when data show adsorption maxima, such as in the arsenate adsorption isotherms. The self-consistent modeling approach yielded pKa values of singly-coordinated sites of 8.82, and of triply-coordinated sites of 9.65. Three surface arsenate complexes bound only to singly-coordinated sites were found to describe all experimental data, although only two of them were predominant across the pH and As(V) concentration ranges investigated: a bidentate non protonated (BD) complex, and a protonated monodentate (HMD) one. Charge distribution of surface arsenate complexes was found to significantly influence the optimizations, but increased values of optimized capacitance 1 were found to compensate for previously underestimated surface site density values, to yield almost identical surface affinity and CD parameters.Finally, correlations found between surface site density and capacitance-1 parameters with SSA expanded the applicability of the modeling approach presented, to other goethites with different SSAs than the ones investigated here.

Eu(III) and Am(III) adsorption on aluminum (hydr)oxide minerals: surface complexation modeling

Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals—corundum (α-Al2O3), γ-alumina (γ-Al2O3) and gibbsite (γ-Al(OH)3)—and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al2O3) and γ-alumina (γ-Al2O3) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals.Graphical

Prediction of alkaline earth metal ion adsorption on goethite for various background electrolytes with the CD-MUSIC model

As water scarcity drives the use of more saline water sources, contaminant fate and transport models must capture the impact of high concentrations of alkaline earth metal ions (AEMs) and background electrolytes in these more complex waters. By utilizing macroscopic adsorption data from various electrolyte systems, a Charge Distribution – Multisite Complexation (CD-MUSIC) model, capable of incorporating electrolyte adsorption, was able to accurately simulate the adsorption behavior of alkaline earth metal ions onto goethite. The modeling effort was guided by previous spectroscopic and surface complexation modeling of alkaline earth metal adsorption and built on previous CD-MUSIC modeling that accounted for changes in crystal face contributions to the surface site density as a function of specific surface area. The model was constrained to consider only two dominant surface complex species for each metal ion adsorption reaction. These two species were selected from 44 possible species through objective curve fitting of single-solute macroscopic adsorption data. While most of the alkaline earth metal surface complexes formed outer-sphere complexes at the goethite surface, an inner-sphere species was utilized for Mg2+. With the surface complex species and equilibrium constants obtained from this study, the calibrated model successfully predicted alkaline earth metal ion adsorption over a wide range of solution and surface conditions; the model predictions encompassed a wide range of pH (5–11), solute/solid ratio (1.37 × 10−5– 8.33 × 10−4 mol-solute/g-solid), ionic strengths (0.01 M – 0.7 M), and background electrolytes (Na+, Cs+, Rb+, Cl−, and NO3−) using the same crystal face contribution methodology for site density, capacitance values, and surface acidity constants adopted for proton and cadmium adsorption in previous work (Han and Katz, 2019). Model simulations for a range of background water chemistries demonstrated the potential for Mg2+ to reduce Cd2+ adsorption to goethite in model seawater and oil- and gas-produced waters.

Generic CD-MUSIC-eSGC model parameters to predict the surface reactivity of iron (hydr)oxides

The surface reactivity of iron (hydr)oxides plays a crucial role in controlling their interfacial reactions, for which various surface complexation models have been developed. The diversity of mineralogical properties of iron (hydr)oxides has resulted in a redundancy of model parameters, which hampers the modeling of iron (hydr)oxides in soils and sediments, where goethite, hematite and ferrihydrite dominate the iron (hydr)oxide mass fraction. To capture their combined surface reactivity, optimized generic protonation parameters of the Charge Distribution-Multisite Complexation (CD-MUSIC) extended-Stern-Gouy-Chapman (eSGC) model were derived by reanalyzing literature datasets and tested with some newly synthesized iron (hydr)oxides. It was observed that the proton and monovalent ion affinity constants of the different iron (hydr)oxides were located in a narrow range. For the singly- and triply-coordinated hydroxyl sites the obtained generic log(affinity constants) were 8.3 and 11.7 for the protonation reaction and -0.5 for the reaction with the monovalent background ions. Their combination with fixed site densities of singly-/triply-coordinated hydroxyl sites of 3.45/2.70, 5.00/2.50, and 5.80/1.40 sites/nm2 for goethite, hematite, and ferrihydrite, respectively, provided good results. The Stern layer capacitances of the inner and outer Stern layers were set equal and could be acquired by an empirical correlation with the sample specific surface area (SSA). The CD-MUSIC-eSGC model with the generic model parameters enables good quality predictions of the proton reactivity of iron (hydr)oxides in 1:1 electrolyte solutions regardless of the sample heterogeneity. The advantages of the generic CD-MUSIC-eSGC model are twofold: (1) protonation of iron (hydr)oxides can be described without making use of spectroscopic measurements and proton titrations, and (2) the model calculations are greatly simplified.

Influencing factors and environmental effects of interactions between goethite and organic matter: A critical review

This paper reviews progresses in the interactions between goethite and organic matter (OM) and their environmental effects in recent decades. The interactions mainly include the effect of organic matter on the surface properties and the crystallization of goethite, molecular changes of OM caused by goethite, and their interaction mechanisms, which can be depicted by the commonly used Langmuir model, the charge distribution multi-site complexation model (CD-MUSIC model), ligand charge distribution model (LCD model), and natural organic matter charge distribution model (NOM-CD model). The influencing factors of the interactions are summarized with emphasis on the external, including pH, ionic strength, carbon dioxide (CO2), and the internal, including the structure of OM and iron species. The goethite—OM complexes caused by the interactions will affect migration and transformation of conventional heavy metals and emerging antibiotics. The complexes, as the carrier of carbon and iron, are also the critical parts of the carbon and iron cycles, which are associated with climate change. This review provides a basis for future mechanism studies of formation, transformation, and effects of goethite—OM complexes (particulate OM or carbon-contained minerals) in different environmental systems at a molecular level.

Mechanisms of arsenate and cadmium co-immobilized on ferrihydrite inferred from ternary surface configuration

Elucidating the interfacial interactions of arsenate (AsO43-) and cadmium (Cd) on minerals can better reveal their environmental behavior under various geological settings. Herein, the adsorption of Cd on ferrihydrite (Fh) in the presence of arsenate was investigated through batch experiments, surface complexation, and spectroscopic techniques. We determined the concentration-dependent interactions of Cd (II) and As (V) on each other’s behavior on Fh. Cadmium and arsenate tended to co-precipitate at high Cd/As ratios, whereas adsorption dominated at low Cd/As ratios. Compared with the single-ion system, the coexistence of Cd(II) and As on Fh significantly reduces the respective mobility of Cd(II) and As(V). The results of in situ attenuated total reflection–Fourier-transform infrared spectroscopy and charge distribution multisite complexation modeling revealed that the synergistic effects originated from electrostatic interactions and the formation of a ternary complex. The curve fitting of the spectra revealed three deconvolution peaks at ~ 765 cm−1, ~813 cm−1, and ~ 870 cm−1, which were assigned to As–OX (X = H+, cations, and H2O), As–O–Fe, and As–Oumcomplexed, respectively. After the addition of Cd(II), the intensity of As–OX increased at different pH values, indicating the formation of an As–O–Cd ternary complexes. We infer that two types of surface complex were assembled on the surface of Fh: namely anion-bridged Fe–As–Cd and cation-bridged Fe–Cd–As. These results contribute to our understanding of the behavior of multiple contaminates in an iron-rich environment and are helpful for the development of the corresponding restoration technology.

Competitive adsorption of ofloxacin enantiomers to goethite: experiments and modelling

Environmental contextThe concentration, types and distribution of antibiotics in soils can have environmental effects and can be modelled using laboratory systems. Adsorption of ofloxacin (OFL) and levofloxacin (LEV) enantiomers to goethite can probe this behaviour and each binds differently to the solid phase. The different behaviour of LEV and OFL in relation to solid-solution partitioning will affect their environmental fate. AbstractThe adsorption of ofloxacin enantiomers, namely levofloxacin (LEV) and ofloxacin (OFL), to goethite was investigated using batch experiments. Structural information of aqueous and adsorbed LEV or OFL was obtained with ultraviolet–visible (UV-Vis), three-dimensional excitation–emission matrix (EEM) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopic methods. The results indicated that LEV molecules formed a bridging bidentate complex (≡(FeO)2–LEV) with the surface of goethite, and OFL formed a monodentate complex (≡FeO–OFL). The adsorption of OFL to goethite was stronger than that of LEV, owing to differences in their physicochemical properties and bonding modes. The adsorption of LEV and OFL to goethite in single systems was well simulated using the charge distribution multi-site complexation (CD-MUSIC) model, but their adsorption in the LEV–OFL–goethite systems was overestimated at pH ~5.2 and high concentrations of LEV–OFL mixture (19.59μM), in which the predicted amounts of adsorbed LEV and OFL were higher (20.0, 30.8%) than the experimental results. Compared with the unprotonated LEV or OFL, the protonated (>99.9%) ones were mainly adsorbed to the surface of goethite, and the single species may be used during their following modelling.

Oxygen atom release during selenium oxyanion adsorption on goethite and hematite

Adsorption of selenium oxyanions (selenite and selenate) on soil minerals can mitigate Se ecotoxicity effects by removing Se from water resources. Se oxyanion surface complexation on Fe oxides have been investigated for decades using spectroscopic and surface complex modeling. Here, insights on the Fe-O-Se bonding process on goethite and hematite were gained via integrating our observed batch Se adsorption isotherms, H+ coadsorption with Se, X-ray absorption spectroscopy (XAS)-derived surface complex geometry, surface complexation modeling, and 18O tracing across oxide and aqueous phases Adsorption extents of selenite and selenate on goethite and hematite decreased as pH increased from 3.0 to 7.0 and follows a corresponding decrease in positive zeta potential which offers less electrostatic attraction. Surface complexation geometry was determined with XAS results that indicated the formation of inner-sphere binuclear bidentate selenite complexes and outer-sphere selenate complexes on both oxides within the range of experimental conditions. These surface complexes were sufficient to model Se adsorption isotherms and H+ coadsorption on both oxides at pH 3.0, 5.0, and 7.0 using the Charge Distribution Multi-site Complexation (CD-MUSIC) model. Inner-sphere bidentate selenite complex formation requires release of two O, and by tracing 18O release from 18O-enriched oxides to isotopically normal water, it was found that O release from the oxide surface accounted for 22% and 7% of total adsorption-induced O release for goethite and hematite, respectively, but only at pH 3.0. The remaining O release is assumed to be from adsorbed selenite. Selenate at pH 3.0 also induced a slight increase in 18O enrichment in bulk solution, which is unexpected for selenate's outer-sphere configuration that should produce no O ligand exchange, but instead highlights some spontaneous adsorption-induced oxide O release.

Remediation of antimony-contaminated tap water using granular TiO2 column

Environmental contextAntimony (Sb) contamination from mining is an emergent environmental issue, and there is an urgent need for the development of effective water treatment technology. This study reports a complete Sb remediation strategy using granular titanium dioxide as the adsorbent, and describes adsorbent manufacture, Sb adsorptive removal and regeneration of the adsorbent. The findings highlight a practical way for on-site remediation of Sb-contaminated water. AbstractAntimony (Sb) mining endorses the development of Sb remediation technology to reduce its contamination level and protect public health. In this study, a treatment process based on granular TiO2 was proposed to remediate the Sb-contaminated tap water at mining sites. The Langmuir isotherms indicated that the maximum adsorption capacity on granular TiO2 was 142mgg−1 for SbIII and 43mgg−1 for SbV. The kinetics results suggested that Sb adsorption conformed to the Weber–Morris intraparticle diffusion model. The adsorption of SbV featured the anionic adsorption characteristics, which were significantly inhibited at pH>8. Approximately, 586 bed volumes of tap water with an average SbV concentration of 324µgL−1 were filtered before the effluent concentration exceeded 6µgL−1 using a granular TiO2 column. The PHREEQC program integrated with charge distribution multi-site complexation (CD-MUSIC) modelling and a one-dimensional transport block was performed to predict the SbV breakthrough curve. The results revealed that the existence of Ca2+ significantly promoted SbV adsorption. Furthermore, the breakthrough curves of SbV and Ca2+ were well simulated after considering the effects of Ca2+ adsorption and the Ca-Sb-TiO2 ternary surface complex. Granular TiO2 can be regenerated and reused, and the solid residue from regeneration can be recycled. The insights of this study help to further understand the environmental chemistry of Sb on metal oxides, which provides a practical solution for Sb removal.

A Unified Surface Complexation Modeling Approach for Chromate Adsorption on Iron Oxides.

A multistart optimization algorithm for surface complexation equilibrium parameters (MUSE) was applied to a large and diverse data set for chromate adsorption on iron (oxy)hydroxides (ferrihydrite and goethite). Within the Basic Stern and the charge-distribution multisite complexation (CD-MUSIC) framework, chromate binding constants and the Stern Layer capacitance were optimized simultaneously to develop a consistent parameter set for surface complexation models. This analysis resulted in three main conclusions regarding the model parameters: (a) There is no single set of parameter values that describes such diverse data sets when modeled independently. (b) Parameter differences among the data sets are mainly due to different amounts of total sites, i.e., surface area and surface coverages, rather than structural differences between the iron (oxy)hydroxides. (c) Unified equilibrium constants can be extracted if total site dependencies are taken into account. The implementation of the MUSE algorithm automated the process of optimizing the parameters in an objective and consistent manner and facilitated the extraction of predictive relationships for unified equilibrium constants. The extracted unified parameters can be implemented in reactive transport modeling in the field by either adopting the appropriate values for each surface coverage or by estimating error bounds for different conditions. The evaluation of a forward model with unified parameters successfully predicted chromate adsorption for a range of capacitance values.

Surface complexation modeling of arsenic mobilization from goethite: Interpretation of an in-situ experiment

Abstract Sorption has been recognized as a predominant process for the mobility and transport of arsenic (As) in groundwater. However, the model-based description of the chemical and physical mechanisms controlling As interaction with mineral surfaces under natural hydrochemical conditions remains a formidable challenge. In this study we assess and compare the ability of existing surface complexation models (SCMs), the diffuse double layer model (DDL) and the charge distribution multisite complexation model (CD-MUSIC), to simulate As desorption from goethite in groundwater. We consider the outcomes of an in-situ experiment recently performed in an arsenic-contaminated aquifer of Northern China where As-loaded goethite-coated sand was deployed in 7 monitoring wells. Determination and measurements of As-surface species were carried out over a time period of 80 days in all monitoring wells. Simultaneous calibration of the models with the measurements in the 7 wells was performed to obtain single sets of surface complexation parameters for the DDL and the CD-MUSIC models, respectively. Although the general dynamic pattern of the As release at the site is captured by both models, the approach based on the CD-MUSIC agrees best with the field experimental data without modifications of the surface complexation database compiled from previous studies on goethite. Conversely, calibration of the DDL affinity constants led to substantial improvement in the agreement between model simulations and the considered field dataset. The model outcomes and the exploration of the sensitivity of the goethite surface composition to changes in hydrochemical conditions provide insights into the mechanisms controlling arsenic sorption and their different description in the DDL and the CD-MUSIC models. Both SCMs indicate that PO43− acts as the main competitor for As(V) sorption sites, and that Fe(II) does not have a significant effect on the As(V) release despite its strong affinity for the goethite surface. Neither SCM suggests direct binding of As(III) to goethite. However, the CD-MUSIC model predicts significant formation of a goethite-Fe(II)-As(III) complex under the mildly alkaline conditions of the groundwater at the field site and that such complex is insensitive to phosphate competition. The CD-MUSIC implementation also allows capturing the non-linear charge effects of the major ions, including C a 2+ and M g 2+ , which appear to have important implication in the mechanisms of As sorption at the field site.

Adsorption of Quinolone Antibiotics to Goethite under Seawater Conditions: Application of a Surface Complexation Model.

The assessment of antibiotics mobility under seawater conditions has been rarely studied, as an accurate description of such multicomponent systems is quite challenging. In this study, the adsorption of a widely used quinolone antibiotic in aquaculture, Oxolinic acid (OA), to a synthetic goethite (α-FeOOH) was examined in the presence of major (e.g., Mg2+, SO42-) and trace (e.g., Cu2+) ions naturally occurring in seawater. The OA adsorption can be successfully predicted using a charge distribution multisite complexation model (CD-MUSIC) coupled with the three plane model (TPM). This modeling approach allowed a quantification of the competitive and synergetic effects of different ions in seawater over a large range of environmentally relevant conditions. In addition, the transport of OA in flow-through columns can be well predicted through coupling hydrodynamic parameters and surface complexation constants obtained under seawater conditions. These results may have strong implications for assessment and prediction of the fate of quinolones in sediment-seawater interface systems.

Competitive adsorption of arsenic and fluoride on {2 0 1} TiO2

Elevated arsenic (As) and fluoride (F) in natural water present an urgent environmental concern. The demand for their effective removal underscores the fundamental understanding of their solid-liquid interface chemistry. Herein, the efficiency of {2 0 1} TiO2 in As(III/V) and F was explored using macroscopic and molecular-level techniques. Their adsorption isotherms followed the Langmuir equation, and the maximum adsorption capacity was 50.5, 29.3, and 5.0 mg/g for As(III), As(V) and F, respectively. Their adsorption kinetics of As(III), As(V) and F conformed to the pseudo-second-order model. The XPS and in situ ATR-FTIR results identified that the active adsorption sites on {2 0 1} TiO2 included surface hydroxyl groups, but not oxygen vacancies. As(III/V) and F form bidentate binuclear and monodentate mononuclear structures, respectively, regardless of exposed facets. Integrated with the molecular-level mechanism, the charge distribution multisite complexation model well predicted the pH edge behaviors in mono- and co-component systems. The shift of pHPZC of {2 0 1} TiO2 in competitive adsorption systems signified the formation of inner-sphere complexes. The results of this study shed new lights on the adsorption of coexisting ions using high-index faceted TiO2.

Effect of pH on the mobility of the herbicide MCPA in a sand-goethite column: 1D and 2D reactive transport modeling

Adsorption and transport of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) in a homogeneous sand-goethite system were investigated as a function of pH. Interaction of MCPA with the solid surface was geochemically modeled according to the charge distribution multisite complexation (CD-MUSIC) approach. Based on this calibration, retardation of MCPA transport in column experiments was significantly underestimated by conventional 1D simulations.As a new approach, Positron Emission Tomography (PET) was employed to analyze the flow field, using 18F− as a radiotracer. The observed heterogeneity was reproduced in 2D simulations assuming increased permeability and porosity at the periphery of the column. With this flow model, predicted retardation factors for MCPA were in agreement with the experimental data. Thus, this study demonstrates quantitatively that inconsistencies between static (batch) and dynamic (column) systems can be caused by heterogeneities in fluid flow, i.e., not necessarily by non-equilibrium conditions, which are commonly taken into account. This in turn highlights the need to consider realistic flow fields in studies of contaminant transport in natural matrices.

Capturing the variable reactivity of goethites in surface complexation modeling by correlating model parameters with specific surface area

The development of predictive tools capable of simulating adsorption behavior on goethite (α-FeOOH) surfaces has evolved over the past several decades. Recent research has focused on capturing the variation of surface reactivity and adsorption behavior for different preparations of synthetic goethites. In this research, an approach to estimate modeling parameters based on the specific surface area (SSA) of goethites was established and combined with a Charge Distribution – Multi-site Complexation (CD-MUSIC) surface complexation model. It was assumed that differences in crystal face contributions (CFC), inner-Helmholtz capacitances (C1), and protonation constants of surface oxygens (pKa’s) among different preparations of goethite contribute to the variation of surface reactivity. Thus, correlations of these modeling parameters with the SSA of a range of goethites were identified by comprehensively combining microscopic, macroscopic, and modeling data reported in literature along with adsorption data collected from macroscopic experiments conducted as part of this study. A CD-MUSIC model shown to be capable of accurately predicting adsorption for several metal ions and oxyanion selenite on a 62.9 m2/g SSA goethite served as the basis for the development of the adsorption modeling approach described in this paper. The predictive capability of the newly developed modeling approach was verified by comparing predictions of protons, SeO32−, and Cd2+ adsorption with experimental data from goethites with SSAs ranging between 21.3 and 105 m2/g; in total, 40 adsorption data sets from 13 different goethites were used for model verification. The results from this study indicate that the variation of surface reactivity of goethites can be successfully simulated by changing CFC, C1, and pK2,singly (i.e. second protonation constant of singly-coordinated oxygens on the goethite surface) based on the SSA, which implies that self-consistent adsorption parameters can be applied to predict adsorption behavior over a range of goethite preparations.

Adsorption of Antimonate, Sulfate, and Phosphate by Goethite: Reversibility and Competitive Effects

Core Ideas Sb(V) adsorption by goethite decreases with increasing pH and is unaffected by ionic strength. Sb(V) adsorption is hysteretic. Adsorbed Sb(V) generates a downward shift in the goethite isoelectric point. The adsorption of Sb(V) decreases in the presence of phosphate, but is unaffected by sulfate. Inner sphere mono‐ and bidentate Sb(V) complexation by goethite is predicted. Goethite is a sink for antimonate Sb(OH)6– [Sb(V)] in soil and sediments. The pH‐ and ionic strength (I)‐dependent mass distribution of Sb(V) between adsorbed and solution phases at equilibrium may be used to indirectly infer an adsorption mechanism (inner vs. outer sphere surface complexation) and to develop predictive surface complexation models. The objectives of this study were to characterize the adsorption of Sb(V) by goethite as a function of pH, I, and in the absence or presence of competing ligands, SO4 or PO4. Ligand adsorption was at a maximum in strongly acidic suspensions and decreased with increasing pH. Adsorption envelopes of Sb(V) where not influenced by I, but increasing I decreased SO4 and increased PO4 retention. In strongly acidic suspensions, SO4 and PO4 retention was not influenced by I. Ligand adsorption decreased the isoelectric point (IEP) of goethite from 8.5 to 6.3 [Sb(V)] and 4 (PO4). The adsorption of SO4 did not affect the IEP, although SO4 reduced the zeta potential of goethite when pH < IEP. Antimonate and PO4 adsorption was hysteretic; SO4 adsorption was reversible. Sulfate did not impact Sb(V) retention; adsorbed Sb(V) generated greater negative surface charge, decreasing SO4 adsorption. Both Sb(V) and PO4 competed for adsorption sites, resulted in reduced retention of both in competitive systems. The triple layer formulation of the charge distribution multisite complexation model, coupled with inner sphere surface complexation, was used to describe the adsorption envelopes for Sb(V), SO4, and PO4, and to predict adsorption in competitive systems.