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Models predicting wettability alteration of mineral-brine-oil interfaces during low-salinity-waterflooding (LSW) should account for the elevated temperatures typically found in oil reservoirs. For the first time, high temperature ζ-potential (zeta potential) data for silica are collected and used to interpret surface chemistries and interactions at reservoir-like conditions to predict temperature’s effect on wettability alteration. Mobility data for amorphous silica in varying NaCl(aq) concentrations at 25, 100, and 150 °C and neutral pH were obtained through microelectrophoresis experiments. Calculated ζ-potentials were fit with surface complexation model (SCM) parameters to predict electrical double layer (EDL) parameters based upon the Gouy-Chapman-Stern-Grahame (GCSG) model. ζ-potentials increased with increasing temperature (around 50% increase from 25 to 150 °C) and decreasing NaCl concentrations (10−1–10−4 mol kg−1). These trends, along with Derjaguin-Verwey-Landau-Overbeek (DLVO) theory, suggests that overall repulsive forces extend farther from the surface at low salinity and higher temperatures, implying greater wetting thickness/surface wettability in these environments. The resulting surface concentration calculations suggest that LSW is most impactful up to 10−2 mol kg−1 of salt, and that additional dilution below 10−3 mol kg−1 will negligibly impact oil recovery, particularly at reservoir temperatures above 100 °C. The analysis provides a framework for treating more complex reservoir systems, such as carbonates in multivalent brines.

Detailed analysis of the adsorption of oxalic acid ions, that is, oxalate and hydrogenoxalate, on the rutile (110) surface was carried out using molecular dynamics augmented by free energy calculations and supported by ab initio calculations. The predicted adsorption on perfect nonhydroxylated and hydroxylated surfaces with surface charge density from neutral to +0.208 C/m2 corresponding to pH values of about 6 and 3.7, respectively, agrees with experimental adsorption data and charge-distribution multisite ion complexation model predictions obtained using the most favorable surface complexes identified in our simulations. We found that outer-sphere complexes are the most favorable, owing to strong hydrogen binding of oxalic acid ions with surface hydroxyls and physisorbed water. The monodentate complex, the most stable among inner-sphere complexes, was about 15 kJ/mol higher in energy, but separated by a large energy barrier. Other inner-sphere complexes, including some previously suggested in the literature as likely adsorption structures such as bidentate and chelate complexes, were found to be unstable both by classical and by ab initio modeling. Both the surfaces and (hydrogen)oxalate ions were modeled using charges scaled to 75% of the nominal values in accord with the electronic continuum theory and our earlier parameterization of (hydrogen)oxalate ions, which showed that nominal charges exaggerate ion-water interactions.

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.

The MUlti-start optimization algorithm for Surface complexation Equilibrium (MUSE) algorithm has been developed to optimize the fitting of thermodynamic constants for surface complexation modeling (SCM). Although there is a plethora of software to perform data fitting and determine intrinsic equilibrium constants, the algorithms used are highly dependent on initial values and choice of parameters. This limits their transferability to model other systems, for example, reactive transport processes. With this in mind, a hybridized optimization approach, based on a multistart algorithm combined with a local optimizer, has been developed to allow the simultaneous optimization of SCM parameters and to assess the sensitivity of these parameters to changes in the model assumptions. In this study, the CD–MUSIC formalism with a Basic Stern electrostatic model is utilized to model chromate adsorption on ferrihydrite, although the MUSE algorithm can be applied to any adsorption data set and be implemented in any mode...

Cations in natural solutions significantly impact interfacial processes, particularly dissolution and surface charge measurements for quartz and silica, which are amongst the most naturally abundant and technologically important solids. Thermodynamic parameters for cation-specific interfacial reactions have heretofore been mostly derived instead of directly measured experimentally. This work investigates the energetics of adsorption and exchange reactions of alkali metal (M+) and alkaline earth (M2+) cations with the quartz surface by flow adsorption microcalorimetry, in tandem with in-situ pH measurements. The magnitudes of the heats of adsorption and exchange were found to increase along the Hofmeister series i.e., Li+

Ferrihydrite (FH) plays an important role in controlling the fate and transport of many compounds in nature due to its large surface area and high reactivity. This study is the first attempt to build a surface complexation model using the recently proposed surface structure that incorporates tetrahedrally coordinated Fe atoms (Hiemstra, 2013). The ability of the model to describe the surface charge curves of FH with different preparation methods and Points of Zero Net Proton Charge (PZNPC) is tested. In general, FH particles that have been subject to aging are larger and have lower specific surface area (SSA) and higher PZNPCs. The structural model includes 2 types of singly coordinated (SC) oxygens that are present only on the (1-11) and (1-10) faces and 5 types of triply coordinated (TC) oxygens that are also present on the basal planes (001) and (00-1), for a total of 11 sites. The 11 - site model was able to simulate fresh FH datasets with PZNPC lower than 8.5, but could only simulate higher PZNPCs when the contribution of the more acidic basal planes was minimized. The available microscopic observations do not support this condition, which suggests TC groups on the basal planes likely have log K values higher than the macroscopic PZNPC. We attempted to test this hypothesis through three versions of simplified 3-site models, using SC and one TC on (1-10) and (1-11), with log K 8.0 (equal to fresh FH PZNPC) and one TC group on the basal planes with log K 9.5. This enables fitting of the PZNPC of aged FH datasets by adjusting the face contributions. An unresolved issue is whether this model accurately describes the relative contribution of SC and TC sites to the overall charge, which has implications for accurate description of specific ion adsorption.

Flow microcalorimetry was used to investigate the energetics associated with Rb+, K+, Na+, Cl–, and NO3– exchange at the rutile–water interface. Heats of exchange reflected differences in bulk hydration/dehydration enthalpies (Na+ > K+ > Rb+, and Cl– > NO3–) such that exchanging Na+ or Cl– from the surface was exothermic, reflecting their greater bulk hydration enthalpies. Exchange heats were measured at pH 2, 3.25, 5.8, and 11 and exhibited considerable differences as well as pH dependence. These trends were rationalized with the aid of a molecularly constrained surface complexation model (SCM) that incorporated the inner-sphere binding observed for the cations on the rutile (110) surface. Explicitly accounting for the inner-sphere binding configuration differences between Rb+, K+, and Na+, as well as accompanying differences in negative surface charge development, resulted in much better agreement with measured exchange ratios than by considering bulk hydration enthalpies alone. The observation that cal...

Here, we characterize oxalate adsorption by rutile in NaCl media (0.03 and 0.30 m) and between pH 3 and 10 over a wide temperature range which includes the near hydrothermal regime (10-150 °C). Oxalate adsorption increases with decreasing pH (as is typical for anion binding by metal oxides), but systematic trends with respect to ionic strength or temperature are absent. Surface complexation modeling (SCM) following the CD-MUSIC formalism, and as constrained by molecular modeling simulations and IR spectroscopic results from the literature, is used to interpret the adsorption data. The molecular modeling simulations, which include molecular dynamics simulations supported by free-energy and ab initio calculations, reveal that oxalate binding is outer-sphere, albeit via strong hydrogen bonds. Conversely, previous IR spectroscopic results conclude that various types of inner-sphere complexes often predominate. SCMs constrained by both the molecular modeling results and the IR spectroscopic data were developed, and both fit the adsorption data equally well. We conjecture that the discrepancy between the molecular simulation and IR spectroscopic results is due to the nature of the rutile surfaces investigated, that is, the perfect (110) crystal faces for the molecular simulations and various rutile powders for the IR spectroscopy studies. Although the (110) surface plane is most often dominant for rutile powders, a variety of steps, kinks, and other types of surface defects are also invariably present. Hence, we speculate that surface defect sites may be primarily responsible for inner-sphere oxalate adsorption, although further study is necessary to prove or disprove this hypothesis.

The zeta potential (ZP) is an oft-reported measure of the macroscopic charge state of solid surfaces and colloidal particles in contact with solvents. However, the origin of this readily measurable parameter has remained divorced from the molecular-level processes governing the underlying electrokinetic phenomena, which limits its usefulness. Here, we connect the macroscopic measure to the microscopic realm through nonequilibrium molecular dynamics simulations of electroosmotic flow between parallel slabs of the hydroxylated (110) rutile (TiO2) surface. These simulations provided streaming mobilities, which were converted to ZP via the commonly used Helmholtz-Smoluchowski equation. A range of rutile surface charge densities (0.1 to −0.4 C/m2), corresponding to pH values between about 2.8 and 9.4, in RbCl, NaCl, and SrCl2 aqueous solutions, were modeled and compared to experimental ZPs for TiO2 particle suspensions. Simulated ZPs qualitatively agree with experiment and show that “anomalous” ZP values and i...

A comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF3SO3–) electrolyte media from 25 to 250 °C. Rb+ primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (−0.1 and −0.2 C/m2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitance values and intrinsic Rb+ binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na+ results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched wel...

The effect of particle size on the adsorption of Sr(2+) onto monodisperse nanometer diameter (4, 20, and 40 nm) anatase samples has been evaluated quantitatively with macroscopic experimental studies. The adsorption of Sr(2+) onto the anatase particles was evaluated by potentiometric titrations in NaCl media, at two ionic strengths (0.03 and 0.3 m), and over a wide range of pH (3-11) and surface loadings, at a temperature of 25 °C. Adsorption of Sr(2+) to the surface of the 20 and 40 nm diameter samples was similar, whereas the Sr(2+) adsorption titration curves were shallower for the 4 nm diameter samples. At high pH, the smallest particles adsorbed slightly less Sr(2+) than was adsorbed by the larger particles. At the molecular scale, density functional theory (DFT) calculations were used to evaluate the most stable Sr(2+) surface species on the (101) anatase surface (the predominant crystal face). An inner-sphere Sr-tridentate surface species was found to be the most stable. The experimental data were described with a charge distribution (CD) and multisite complexation (MUSIC) model, with a Basic Stern layer description of the electric double layer. The resulting surface complexation model explicitly incorporated the molecular-scale information from the DFT simulation results. For 20 and 40 nm diameter anatase, the CD value for the Sr-tridentate species was calculated using a bond valence interpretation of the DFT-optimized geometry. The CD value for the 4 nm sample was smaller than that for the 20 and 40 nm samples, reflecting the shallower Sr(2+) adsorption titration curves. The adsorption differences between the smallest and larger anatase particles can be rationalized by water being more highly structured near the 4 nm anatase sample and/or the Sr-tridentate surface species may require more well-developed surface terraces than are present on the 4 nm particles.

Flow microcalorimetry was used to investigate the energetics associated with Rb

The dielectric properties of interfacial water adjacent to the surfaces of hydrophobic graphite and the 110 surface of hydrophilic rutile (α-TiO2) are investigated by means of nonequilibrium molecular dynamics simulations. The dielectric behavior of water is found to arise from its local density and molecular polarizability in response to an external field, and can be rationalized in terms of the number and strength of water–surface and water–water H-bonds. The interplay of local density and polarizability leads to a particularly strong dielectric response, exceeding the external field, of the water layer directly contacting the surfaces, while the second layer exhibits a reduced response. Consequently, dielectric profiles near surfaces cannot be correctly described by implicit solvent models valid for bulk water. The overscreening response of the contact water layer has been observed in previous simulation studies and implies the local permittivity (dielectric constant) of that layer is negative. However...

Adsorption of Rb+, Na+, Sr2+, and Cl– on hydroxylated (110) rutile surfaces was studied by molecular dynamics (MD) simulations. Our previous work was extended to the range of surface charge densities from −0.2 to +0.1 C/m2 (from −0.4 to +0.1 C/m2 for Sr2+) and to temperatures of 25, 150, and 250 °C. These conditions can be linked to experimental surface charge and pH values from macroscopic titrations of rutile powders with surfaces dominated by 110 crystal planes. Simulations revealed that Na+ and Sr2+ adsorb closer to the surface, shifting from predominately bidentate to tetradentate inner-sphere binding with increasing temperature, whereas Rb+ binding is predominately tetradentate at all temperatures. These differences are related to hydration energies, which must be partially overcome for inner-sphere binding and which decrease with increasing temperature and are lowest for Rb+. The interaction of Cl– with the rutile surface is generally less than that for cations because of repulsion by surface oxyge...

Ceftiofur is a third-generation cephalosporin antibiotic that has been widely used to treat bacterial infections in concentrated animal feeding operations (CAFOs). Land application of CAFO waste may lead to the loading of ceftiofur residues and its metabolites to the environment. To understand the potential contamination of the antibiotic in the environment, the degradation kinetics and mechanisms of ceftiofur in solutions blended with and without the recycled water derived from a beef farm were investigated. The transformation of ceftiofur in aqueous solutions in the presence of the CAFO recycled water was the combined process of hydrolysis and biodegradation. The total degradation rates of ceftiofur at 15 °C, 25 °C, 35 °C, and 45 °C varied from 0.4-2.8×10(-3), 1.4-4.4×10(-3), 6.3-11×10(-3), and 11-17×10(-3) h(-1), respectively, in aqueous solutions blended with 1 to 5% CAFO recycled water. Hydrolysis of ceftiofur increased with incubation temperature from 15 to 45 °C. The biodegradation rates of ceftiofur were also temperature-dependent and increased with the application amounts of the recycled CAFO water. Cef-aldehyde and desfuroylceftiofur (DFC) were identified as the main biodegradation and hydrolysis products, respectively. This result suggests that the primary biodegradation mechanism of ceftiofur was the cleavage of the β-lactam ring, while hydrolytic cleavage occurred at the thioester bond. Unlike DFC and ceftiofur, cef-aldehyde does not contain a β-lactam ring and has less antimicrobial activity, indicating that the biodegradation of ceftiofur in animal wastewater may mitigate the potentially adverse impact of the antibiotic to the environment.

The sorption behavior and solid-phase associations of phosphorus (P) in fine-grained sediments (

The acid-base properties of cassiterite (alpha-SnO2) surfaces at 10-50 degrees C were studied using potentiometric titrations of powder suspensions in aqueous NaCl and RbCl media. The proton sorption isotherms exhibited common intersection points in the pH range of 4.0-4.5 under all conditions, and the magnitude of charging was similar but not identical in NaCl and RbCl. The hydrogen bonding configuration at the oxide-water interface, obtained from classical molecular dynamics (MD) simulations, was analyzed in detail, and the results were explicitly incorporated in calculations of protonation constants for the reactive surface sites using the revised MUSIC model. The calculations indicated that the terminal SnOH2 group is more acidic than the bridging Sn2OH group, with protonation constants (log KH) of 3.60 and 5.13 at 25 degrees C, respectively. This is contrary to the situation on the isostructural alpha-TiO2 (rutile), apparently because of the difference in electronegativity between Ti and Sn. MD simulations and speciation calculations indicated considerable differences in the speciation of Na+ and Rb+, despite the similarities in overall charging. Adsorbed sodium ions are almost exclusively found in bidentate surface complexes, whereas adsorbed rubidium ions form comparable numbers of bidentate and tetradentate complexes. Also, the distribution of adsorbed Na+ between the different complexes shows a considerable dependence on the surface charge density (pH), whereas the distribution of adsorbed Rb+ is almost independent of pH. A surface complexation model (SCM) capable of accurately describing both the measured surface charge and the MD-predicted speciation of adsorbed Na+/Rb+ was formulated. According to the SCM, the deprotonated terminal group (SnOH(-0.40)) and the protonated bridging group (Sn2OH+0.36) dominate the surface speciation over the entire pH range of this study (2.7-10). The complexation of medium cations increases significantly with increasing negative surface charge, and at pH 10, roughly 40% of the terminal sites are predicted to form cation complexes, whereas anion complexation is minor throughout the studied pH range.

Metal oxide surface protonation under hydrothermal conditions is summarized. Important concepts and definitions are introduced first, followed by a brief overview of experimental methods and presentation of representative results. Finally, the modeling methods that are most useful in predicting surface protonation behavior between 0 and 300oC are presented and compared.

In this article, we review the sorption of multivalent cations on rutile (alpha-TiO2) powder surfaces in aqueous 1:1 electrolyte media from room temperature to 250 degrees C. All cations are shown to occupy 'inner sphere' sorption sites in contact with surface oxygens and hydroxyl groups, as well as the diffuse portion of the electrical double layer (EDL). Sorption is shown to increase strongly with increasing temperature, and the sorption affinity is strongly-related to cation radius and charge. Macroscopic powder pH-titration results obtained with ORNL's high temperature hydrogen electrode concentration cells can be rationalized with Gouy-Chapman-Stern models of the EDL, augmented by atomic-scale structural and proton affinity data from synchrotron X-ray studies and computational modeling approaches.

The rutile (1 1 0)–aqueous solution interface structure was measured in deionized water (DIW) and 1 molal (m) RbCl + RbOH solution (pH 12) at 25 � C with the X-ray crystal truncation rod method. The rutile surface in both solutions consists of a stoichiometric (1 · 1) surface unit mesh with the surface terminated by bridging oxygen (BO) and terminal oxygen (TO) sites, with a mixture of water molecules and hydroxyl groups (OH � ) occupying the TO sites. An additional hydration layer is observed above the TO site, with three distinct water adsorption sites each having well-defined vertical and lateral locations. Rb + specifically adsorbs at the tetradentate site between the TO and BO sites, replacing one of the adsorbed water molecules at the interface. There is no further ordered water structure observed above the hydration layer. Structural displacements of atoms at the oxide surface are sensitive to the solution composition. Ti

The chemical and electrostatic interactions at mineral-water interfaces are of fundamental importance in many geochemical, materials science, and technological processes; however, the effects of particle size at the nanoscale on these interactions are poorly known. Therefore, comprehensive experimental and characterization studies were completed, to begin to assess the effects of particle size on the surface reactivity and charging of metal-oxide nanoparticles in aqueous solutions. Commercially available crystalline anatase (TiO2) particles were characterized using neutron and X-ray small-angle scattering, electron microscopy, and laser diffraction techniques. The 4 nm primary nanoparticles were found to exist almost exclusively in a hierarchy of agglomerated structures. Potentiometric and electrophoretic mobility titrations were completed in NaCl media at ionic strengths from (0.005 to 0.3) mol/kg, and 25 degrees C, with these two experimental techniques matched as closely as the different procedures permitted. The pH of zero net proton charge (pHznpc, from potentiometric titration) and isoelectric point pH value (pHiep, from electrophoretic mobility titrations) were both in near perfect agreement (6.85 +/- 0.02). At high ionic strengths the apparent pHznpc value was offset slightly toward lower pH values, which suggests some specific adsorption of the Na+ electrolyte ions. Proton-induced surface charge curves of nanocrystalline anatase were very similar to those of larger rutile crystallites when expressed relative to their respective pHznpc values, indicating that the development of positive and negative surface charge away from the pHznpc for nanocrystalline anatase is similar to that of larger TiO2 crystallites.

Adsorption of Zn{sup 2+} at the rutile TiO{sub 2} (110)-aqueous interface was studied with Bragg-reflection X-ray standing waves (XSW), polarization-dependent surface extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations to understand the interrelated issues of adsorption site, its occupancy, ion-oxygen coordination and hydrolysis. At pH 8, Zn{sup 2+} was found to adsorb as an inner-sphere complex at two different sites, i.e., monodentate above the bridging O site and bidentate between two neighboring terminal O sites. EXAFS results directly revealed a four or fivefold first shell coordination environment for adsorbed Zn{sup 2+} instead of the sixfold coordination found for aqueous species at this pH. DFT calculations confirmed the energetic stability of a lower coordination environment for the adsorbed species and revealed that the change to this coordination environment is correlated with the hydrolysis of adsorbed Zn{sup 2+}. In addition, the derived adsorption locations and the occupancy factors of both sites from three methods agree well, with some quantitative discrepancies in the minor site location among the XSW, EXAFS, and DFT methods. Additional XSW measurements showed that the adsorption sites of Zn{sup 2+} were unchanged at pH 6. However, the Zn{sup 2+} partitioning between the two sitesmore » changed substantially, with an almost equal distribution between the two types of sites at pH 6 compared to predominantly monodentate occupation at pH 8.« less

The pH of zero net surface charge (pH pzc ) of the α-TiO 2 (1 1 0) surface was characterized using second-harmonic generation (SHG) spectroscopy. The SHG response was monitored during a series of pH titrations conducted at three NaNO 3 concentrations. The measured pH pzc is compared with a pH pzc value calculated using the revised MUltiSIte Complexation (MUSIC) model of surface oxygen protonation. MUSIC model input parameters were independently derived from ab initio calculations of relaxed surface bond lengths for a hydrated surface. Model (pH pzc 4.76) and experiment (pH pzc 4.8 ± 0.3) agreement establishes the incorporation of independently derived structural parameters into predictive models of oxide surface reactivity.

Sedimentation has severely impacted backwater lakes along the Illinois River. The State of Illinois and the US Army Corps of Engineers are currently involved in a joint effort to address ecosystem degradation within the Illinois River Basin, and excessive sedimentation of backwater lakes and side channels is a primary cause of that degradation. Necessary parts of the overall restoration effort are to adequately characterize both the quality and quantity of backwater lake sediments prior to implementing any restoration efforts, and to identify potential beneficial reuses of dredged sediments. This paper summarizes some of our efforts in these areas with an emphasis on Peoria Lake which has received the most attention to date. Sediment characterization has included detailed bathymetric surveys, sediment dating with 137Cs, chemical and mineralogical characterization of sediments to three meters depth, analysis of recent sediments (to 30 cm depth) for acid-volatile sulfide and simultaneously extracted metals, and analysis of ammonia and toxic metals in sediment pore waters. Dredged sediments have also been used in various trial projects to demonstrate potential handling and beneficial reuse strategies. Some significant findings of these studies are: 1) Long-term sedimentation rates are high, and average 1–3 cm y−1; 2) total concentrations of several trace metals (e.g., Pb, Cd, Ni) and PAH compounds sometimes exceed consensus-based probable effect levels for sensitive sediment-dwelling organisms; 3) pore water dissolved ammonia concentrations in Peoria Lake are potentially toxic to sensitive sediment-dwelling species; and 4) weathered sediments can make productive agricultural soils.

The adsorption of Nd{sup 3+} onto rutile surfaces was examined by potentiometric titration from 25 to 250 C, in 0.03 and 0.30m NaCl background electrolyte. Experimental results show that Nd{sup 3+} sorbs strongly, even at low temperature, with adsorption commencing below the pHznpc of rutile. In addition, there is a systematic increase in Nd{sup 3+} adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexation model, providing a unique geometry for the adsorption of Nd{sup 3+} on rutile. The primary mode of Nd{sup 3+} adsorption was assumed to be the tetradentate configuration found for Y{sup 3+} adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent ''terminal'' and two adjacent ''bridging'' surface oxygen atoms. Similarly, the adsorption of Na{sup +} counterions was also assumed to be tetradentate, as supported by MD simulations of Na{sup +} interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb{sup +}more » adsorption on rutile. Fitting parameters for Nd{sup 3+} adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.« less

A recently developed force field for interactions of water molecules with the (110) surface of rutile (α-TiO2) has been generalized for atomistically detailed molecular dynamics simulations of the interfacial structure of the uncharged mineral surface in contact with liquid SPC/E water at 298 K and 1 atm and for negatively charged surfaces in contact with SPC/E water containing dissolved electrolyte ions (Rb+, Sr2+, Zn2+, Na+, Ca2+, Cl-). Both hydroxylated (dissociative) and nonhydroxylated (associative) surfaces are simulated, since both types of water−surface interactions have been postulated from ab initio calculations and spectroscopic studies under near-vacuum conditions. The positions of water molecules at the interface were found to be very similar for both hydroxylated and nonhydroxylated surfaces, with either terminal hydroxyl groups or associated water molecules occupying the site above each terminal titanium atom. Beyond these surface oxygens, a single additional layer of adsorbed water molecul...

We describe an approach to directly image three-dimensional elemental distributions at the crystal–liquid interface with � 1 A spatial resolution. This method, based on the Fourier synthesis of X-ray standing wave data, is demonstrated by imaging the distribution of Sr 2þ ,Z n 2þ and Y 3þ adsorbed to the rutile (1 1 0)-water interface with no a priori assumptions. The approach resolves distinct sites and is robust for systems with single or multiple simultaneous adsorption sites. The observed ion distributions reveal unexpected differences in the adsorption sites of these cations that are needed to interpret electrical double-layer phenomena using surface complexation models. Published by Elsevier B.V.

The adsorption behavior of metal-(hydr)oxide surfaces can be described and rationalized using a variety of surface complexation models. However, these models do not uniquely describe experimental data unless some additional insight into actual binding mechanisms for a given system is available. This paper presents the results of applying the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three layer description of the electric double layer, to Ca2+ adsorption data on rutile surfaces from 25 to 250°C in 0.03 and 0.30 m NaCl background electrolyte. Model results reveal that the tetradentate adsorption configuration found for Sr2+ adsorbed on the rutile (110) surface in the in situ X-ray standing wave experiments of Fenter et al. (2000) provides a good fit to all Ca2+ adsorption data. Furthermore, it is also shown that equally good fits result from other plausible adsorption complexes, including various monodentate and bidentate adsorption configurations. These results amply demonstrate the utility of in situ spectroscopic data to constrain surface complexation modeling, and the ability of the MUSIC model approach to accommodate this spectroscopic information. Moreover, this is the first use of any surface complexation model to describe multivalent ion adsorption systematically into the hydrothermal regime.

A recently developed high temperature microelectrophoresis cell was employed for ζ-potential measurements at the rutile/aqueous solution interface over a wide range of pH at temperatures of25, 120, and 200 °C. Water, 0.001 mol kg - 1 NaCl(aq), and 0.01 mol kg - 1 NaCl(aq) solutions were tested at these temperatures. The desired pH values were attained by adding either HCl(aq) or NaOH(aq). The obtained experimental data allowed us to estimate isoelectric point pH values (pH i e p ) of 5.26 (′0.45) at 25 \ C,5.13 (′0.37) at 120 °C, and 4.50 (′0.55) at 200 °C. This decrease in pH i e p values with increasing temperature agrees with the decease in point of zero net proton charge (pH z n c p ) pH values (as determined by potentiometric titration) observed for similar rutile powders in our previous studies. ζ-potential data were combined with the proton charge results and rationalized using a surface complexation modeling approach. Modeling results indicate that ζ-potentials are expressed at a distance that is generally equal to (within error) the so-called diffuse double layer thickness (κ - 1 ).

This paper represents a comparison of surface protonation studies of rutile in NaCl media obtained using a conventional glass-electrode autotitrator system from 10 to 50 °C, and hydrogen-electrode concentration cells from 25 to 250 °C [J. Colloid Interface Sci., 200 (1998) 298]. Experimental conditions were matched as closely as possible between the two techniques, permitting a direct comparison of the results. Values for the pH of zero net proton charge (pH znpc ) of the rutile surface obtained at 10 and 35 °C were consistent with the temperature trends observed previously using hydrogen-electrode concentration cells. The pH znpc of rutile decreases systematically from 5.7 to 4.2 as temperature increases from 10 to 250 °C. Moreover, the experimentally determined pH znpc values agree with independent estimates of the pH at the pristine point of zero charge (pH znpc ) calculated from an extension of the revised Multi-Site Complexation (MUSIC) Model of Hiemstra et al. [J. Colloid Interface Sci., 184 (1996) 680]. Surface protonation curves obtained from the glass-electrode titration results were rationalized using surface protonation constants derived from the MUSIC Model, in conjunction with a Basic Stern representation of the electrical double layer (EDL) structure. Best-fit parameters (Stern layer capacitance values, and electrolyte cation and anion binding constants) are consistent with those obtained from fits to titration curves obtained using hydrogen-electrode concentration cells at 25 and 50 °C. Consequently, this comparison demonstrates that independent conventional glass-electrode and hydrogen-electrode concentration cell titrations provide completely compatible results despite the intrinsic differences in the two techniques (pH calibration, equilibration times, stirring rates, gas phase composition, etc).

Fluoroquinolone (FQ) antibacterials are aquatic contaminants of emerging concern (CEC), and adsorption to mineral surfaces is expected to play an important role in the fate, transport, and treatment of FQs. This study characterizes and models the adsorption of a zwitterionic FQ, ofloxacin (OFX), to goethite (α-FeOOH) over a wide range of pH (3–11), OFX concentration (20–500 μM), and electrolyte compositions (0.001–0.1 M NaCl and NaClO 4 ). Comparing OFX adsorption to structural analogues demonstrates that the carboxylate group is essential for binding to goethite. ATR-FTIR measurements indicate that FQs complex to goethite surfaces through carboxylate and carbonyl oxygen atoms, and that ClO 4 − co-adsorbs with OFX. Adsorption of the zwitterionic OFX increases with increasing ionic strength and is enhanced in NaClO 4 relative to NaCl electrolyte, whereas adsorption of a non-zwitterionic analogue is insensitive to ionic strength. A CD-MUSIC (charge distribution-multisite complexation) model, incorporating multiple modes of surface complexation constrained by spectroscopic measurements and the crystallographic distribution of goethite surface sites, yields accurate predictions over wide-ranging solution conditions. According to the model, OFX adsorbs predominantly by inner-sphere complexation on terminal surfaces of the rod-shaped goethite crystals in NaCl electrolyte, and OFX-ClO 4 − ion pairing in NaClO 4 induces formation of additional inner- and outer-sphere surface complexes on multiple crystal faces of goethite.

The revised multisite complexation (MUSIC) model of T. Hiemstra et al. (J. Colloid Interface Sci. 184, 680 (1996)) is the most thoroughly developed approach to date that explicitly considers the protonation behavior of the various types of hydroxyl groups known to exist on mineral surfaces. We have extended their revised MUSIC model to temperatures other than 25 degrees C to help rationalize the adsorption data we have been collecting for various metal oxides, including rutile and magnetite to 300 degrees C. Temperature-corrected MUSIC model A constants were calculated using a consistent set of solution protonation reactions with equilibrium constants that are reasonably well known as a function of temperature. A critical component of this approach was to incorporate an empirical correction factor that accounts for the observed decrease in cation hydration number with increasing temperature. This extension of the revised MUSIC model matches our experimentally determined pH of zero net proton charge pH values (pH(znpc)) for rutile to within 0.05 pH units between 25 and 250 degrees C and for magnetite within 0.2 pH units between 50 and 290 degrees C. Moreover, combining the MUSIC-model-derived surface protonation constants with the basic Stern description of electrical double-layer structure results in a good fit to our experimental rutile surface protonation data for all conditions investigated (25 to 250 degrees C, and 0.03 to 1.0 m NaCl or tetramethylammonium chloride media). Consequently, this approach should be useful in other instances where it is necessary to describe and/or predict the adsorption behavior of metal oxide surfaces over a wide temperature range. Copyright 2001 Academic Press.

The proton-induced surface charge of magnetite was investigated in 0.03 and 0.30 molal sodium trifluoromethanesulfonate solutions from 25°C to 290°C by potentiometric titrations using a stirred hydrogen electrode concentration cell. Pure magnetite with excellent crystallinity was produced by reaction with the Ni/NiO/H2O hydrogen fugacity buffer at 500°C. Inflection points in the 0.03 molal proton sorption isotherms (pHinfl) at 6.50, 6.24, 5.65, 5.47, 5.31 and 5.55 at temperatures of 50°C, 100°C, 150°C, 200°C, 250°C and 290°C, respectively, were used as estimates of the pristine point of zero charge (pHppzc) for modeling purposes. These pHinfl values parallel 1/2 pKw and agree within the assigned uncertainty (±0.3 pH units) at all temperatures with independent estimates of the pHppzc calculated from an extension of 88the revised MUSIC model. The surface charging can be adequately described by a one-pK model with a surface protonation constant fitted to the pHinfl values, and giving the standard state thermodynamic properties log KH,298=7.00, ΔH298°=−32.4±0.8 kJ/mol and constant ΔCp=128±16 J K−1 mol−1, with ΔS298° assumed to be equal to that of rutile protonation (25.5±3.4 J K−1 mol−1. The 0.03 and 0.30 molal proton sorption isotherms also exhibit pHs of common intersection (pHcip) at 6.33, 5.78, 5.37, 4.82, 4.62 and 4.90 at 50°C, 100°C, 150°C, 200°C, 250°C and 290°C, respectively. The difference between the pHcip and pHppzc≅pHinfl values can be related to specific binding of Na+ on the negatively charged surface, which increases with increasing temperature, although the pHcip values may also be affected by dissolution of the solid. The electrical double layer model includes a basic Stern layer capacitance, with specific cation and anion binding at the Stern layer, and a fixed diffuse layer capacitance computed from Guoy–Chapman theory. To fit the steepness and asymmetry of the charging curves above the pHppzc, an additional cation binding constant was invoked, which allows the cation to experience the surface potential. Significant kinetically controlled dissolution of magnetite was observed below the pHppzc, which may be a result of leaching of Fe2+ from the surface, to produce a magnetite+hematite assemblage, despite the high hydrogen partial pressures (ca. 10 bars) used in these experiments.

Calcium adsorption by rutile was studied potentiometrically from 25 to 250 C, at ionic strengths of 0.03 and 0.30 m in NaCl media, using two complementary experimental methodologies. In the first, net proton adsorption in the presence and absence of Ca{sup 2+} was monitored, and in the second, samples were periodically withdrawn during the course of a titration to determine Ca{sup 2+} adsorption directly. These experiments revealed that Ca{sup 2+} adsorption systematically increased with temperature relative to the pH of zero net proton charge in NaCl media alone (pH{sub znpc(NaCl)} - pH). That is, as temperature increased, Ca{sup 2+} adsorption commenced at progressively more positive pH{sub znpc(NaCl)} - pH values. Increasing ionic strength from 0.03 to 0.30 m NaCl suppressed Ca{sup 2+} adsorption at all temperatures as a result of either increased competition from Na{sup +} or greater complexation of Ca{sup 2+} by Cl{sup {minus}}. Finally, there was no apparent trend in the proton stoichiometric ratios (moles H{sup +} released/moles Ca{sup 2+} adsorbed) with increasing temperature. This suggests that the electrostatic and/or chemical processes involved in Ca{sup 2+} adsorption do not change greatly with increasing temperature. Favorable entropic effects, related to the increasing ease of releasing Ca{sup 2+} waters ofmore » hydration, are believed to be primarily responsible for the increase in adsorption with temperature.« less

The effect of particle size on the primary charging behavior of a suite of monodisperse nanometer diameter (4, 20, and 40 nm) anatase samples has been quantitatively examined with macroscopic experimental studies. The experimental results were evaluated using surface complexation modeling, which explicitly incorporated corresponding molecular-scale information from density functional theory (DFT) simulation studies. Potentiometric titrations were completed in NaCl media, at five ionic strengths (from 0.005 to 0.3 m), and over a wide pH range (3-11), at a temperature of 25 °C. From the experimental results, the pH of zero net proton charge (pHznpc) for the 4 and 20 nm diameter samples was 6.42, whereas the pHznpc was 6.22 for the 40 nm sample. The slopes of the net proton charge curves increased with an increase in particle size. Multisite surface complexation and charge distribution (CD) models, with a Basic Stern layer description of the electric double layer, were developed to describe all experimental data. Fits to the experimental data included an inner-sphere Na-bidentate species, an outer-sphere Na-monodentate species, and outer-sphere Cl-monodentate species. DFT simulations found the Na-bidentate species to be the most stable species on the (101) anatase surface (the predominant crystal face). The CD value for the Na-bidentate species was calculated using a bond valence interpretation of the DFT-optimized geometry. The Stern layer capacitance value varied systematically with particle size. The collective experimental and modeling studies show that subtle differences exist in the interface reactivity of nanometer diameter anatase samples. These results should help to further elucidate an understanding of the solid-aqueous solution interface reactivity of nanosized particles.

Irrigation with concentrated animal feeding operation (CAFO) wastewater on croplands has been identified as a major source discharging steroid hormones into the environment. To assess the potential risks on this irrigation practice, the degradation kinetics and mechanisms of 17α-estradiol-3-sulfate were systematically investigated in aqueous solutions blended with dairy wastewater. Dissipation of the conjugated estrogen was dominated by biodegradation under both aerobic and anaerobic conditions. The half-lives for the biodegradation of 17α-estradiol-3-sulfate under aerobic and anaerobic conditions from 15 to 45°C varied from 1.70 to 415 d and 22.5 to 724 d, respectively. Under the same incubation conditions, anaerobic degradation rates of 17α-estradiol-3-sulfate were significantly less than aerobic degradation rates, suggesting that this hormone contaminant may accumulate in anaerobic or anoxic environments. Three degradation products were characterized under both aerobic and anaerobic conditions at 25°C, with estrone-3-sulfate and 17α-estradiol identified as primary metabolites and estrone identified as a secondary metabolite. However, the major degradation mechanisms under aerobic and anaerobic conditions were distinctly different. For aerobic degradation, oxidation at position C17 of the 17α-estradiol-3-sulfate ring was a major degradation mechanism. In contrast, deconjugation of the 17α-estradiol-3-sulfate thio-ester bond at position C3 was a major process initiating degradation under anaerobic conditions.

The concentration of H + which reacts with an adularia surface, [H S + ], was measured with acid-base titrations of adularia powder-water suspensions. Due to the complexity of feldspar surface reactions, it was necessary to calculate a H + mass balance in order to separate the fractions of H + involved in cation exchange reactions, [H ex + ]; dissolution reactions, [H dis + ]; and adsorption at surface hydroxyl sites, [H ads + ]. Reproducibility of acid and base titrations of H S + was pH-dependent, ranging from ±3 μmol H + m −2 at pH 4 to ±1.5 μmol H + m −2 at pH > 6.5. This departure was due to the exchange of K fsp + for H aq + , which was not completely reversible under the conditions of our experiment. Reproducibility of acid and base titration curves for [H ads + ] vs. pH was ± 1.5 μmol m −2 , suggesting the H + adsorption reaction was reversible. Fifteen μmol H + m −2 reacted with the washed feldspar surface during an acid titration from pH 10 to pH 4, in distilled water. 50–60% of the total is attributed to cation exchange, which is estimated to take place at >3 A depth within the surface, suggesting the near-surface is porous, and that H + reacts with sites within the surface pores as well as at the external surface. Less than 5% of [H S + ] was due to [H dis + ], and the remainder to [H ads + ]. [H ex + ] decreases with increasing concentrations of NaCl, presumably because of competition between the solution ions, H + and Na + , for K + exchange sites in the feldspar. [H ex + ] is independent of (CH 3 ) 4 NCl concentrations, suggesting that (CH 3 ) 4 N + cannot compete with H + for the K + exchange sites. The relatively large diameter of (CH 3 ) 4 N + probably prohibits it from penetrating the pores of the adularia surface; therefore, it cannot access exchange sites within the pores which are available to the smaller H + , Na + , and K + ions. Feldspar dissolution rates, often modeled as rate = k H [H ads + ] n , where k H = the rate constant, and n = the reaction order, have been observed to decrease with increasing ionic strength. Because we observe an ionic strength dependence in [H ex + ], rather than [H ads + ], we suggest a rate model where rate = k H [H ex + ] n . This expression emphasizes that dissolution rates are dependent upon K + −H + exchange at the feldspar surface, and that rates decrease with increasing {Na + } due to competition between Na + and H + for the surface exchange site.

The surface complexation behavior of ofloxacin (OFX), a zwitterionic fluoroquinolone antibiotic, to nano-anatase titanium dioxide (TiO(2)) was characterized. OFX adsorption in aqueous TiO(2) suspensions was measured as a function of pH, OFX concentration, and electrolyte type and concentration, and structural information was derived from in situ spectroscopic observations. An ultraviolet-visible spectral red shift upon OFX adsorption indicated formation of inner-sphere coordination complexes. Fourier transform infrared spectra of TiO(2)-adsorbed OFX were invariable over a wide concentration and pH range and were similar to measured spectra of dissolved species wherein the carboxylate group is deprotonated. A charge distribution surface complexation model constrained by spectroscopic observations was developed to describe macroscopic adsorption trends. A tridentate mode of adsorption involving bridging bidentate inner-sphere coordination of the deprotonated carboxylate group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring resulted in successful predictions of observed adsorption trends. In NaClO(4) electrolyte, spectroscopic data and model fitting suggested that OFX ion pairing with ClO(4)(-) enhanced adsorption under acidic conditions. Moreover, comparison of OFX adsorption data with the pH trend in the kinetics of OFX degradation by visible light (λ400 nm) photocatalysis suggested that adsorbed OFX-ClO(4)(-) ion pairs inhibit photodegradation.

Liu and co-workers [Phys. Rev. B 82, 161415 (2010)] discussed the long-standing debate regarding whether H${}_{2}$O molecules on the defect-free (110) surface of rutile (\ensuremath{\alpha}-TiO${}_{2}$) sorb associatively, or there is dissociation of some or all first-layer water to produce hydroxyl surface sites. They conducted static density functional theory (DFT) and DFT molecular dynamics (DFT-MD) investigations using a range of cell configurations and functionals. We have reproduced their static DFT calculations of the influence of crystal slab thickness on water sorption energies. However, we disagree with several assertions made by these authors: (a) that second-layer water structuring and hydrogen bonding to surface oxygens and adsorbed water molecules are ``weak''; (b) that translational diffusion of water molecules in direct contact with the surface approaches that of bulk liquid water; and (c) that there is no dissociation of adsorbed water at this surface in contact with liquid water. These assertions directly contradict our published work, which compared synchrotron x-ray crystal truncation rod, second harmonic generation, quasielastic neutron scattering, surface charge titration, and classical MD simulations of rutile (110) single-crystal surfaces and (110)-dominated powders in contact with bulk water, and (110)-dominated rutile nanoparticles with several monolayers of adsorbed water.

The adsorption of Y 3+ and Nd 3+ onto rutile has been evaluated over a wide range of pH (3–11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 °C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd 3+ first adsorbing at slightly lower pH values. The adsorption of both Y 3+ and Nd 3+ commences at pH values below the pH znpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y 3+ adsorption onto the (1 1 0) rutile surface ( Zhang et al., 2004b ). The MD simulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y 3+ and Nd 3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y 3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y 3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y 3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs) should aid in elucidating a fundamental understating of ion-adsorption reactions.

A stirred hydrogen-electrode concentration cell was used to follow hydrogen ion adsorption by the rutile surface in NaCl media (0.01–1.0 m) between 25 and 250°C. The pH of zero net surface charge (pHzpc) decreases to 200°C and then appears to increase. Away from the pHzpc, negative surface charge is screened more efficiently by Na+ ions than positive charge is by Cl− ions and this effect increases with temperature. Thus, Na+ moves closer to the rutile surface with increasing temperature relative to Cl−. Finally, [ pHzpc − 1 2pK w ] is approximately constant (− 1.1 ± 0.2) for this rutile sample to 250°C and is also equivalent to the equilibrium constant for an isocoulombic form of the “IpKa” surface ionization model. Thus, the constancy of [ pHzpc − 1 2pK w ] may also be useful for extrapolating rutile pHzpc values to higher temperatures and pressures than those studied here, and may also apply to many other oxide surfaces as well.

Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner-sphere cation binding is relatively more favorable.

Titration calorimetry was used to determine the protonation and ionization enthalpies of peat-derived and aquatic humic and fulvic acids from pH 3.6 to 10.4 and for 0.001-0.1 M ionic strength [NaCl and tetraethylammonium chloride (TEACl)]. Protonation and ionization enthalpies were not completely equivalent, and protonation enthalpies were concluded to more accurately reflect the enthalpies associated with proton binding and release. Below pH 7, protonation enthalpies were similar to simple carboxylic acids (6 to -5 kJ/mol), and no ionic strength effects were apparent. Above pH 9, enthalpies were similar to those of simple phenolic acids (-20 to -36 kJ/mol), and less exothermic values were observed at I=0.1 M.

Peat-derived humic and fulvic acids, isolated using widely accepted techniques, were investigated for their ability to reduce gold (III) chloride and dissolve elemental gold. Au(III)-chloride (1–20 mg 1 −1 ) was reduced to elemental colloidal Au by both humic and fulvic acids (1–20 mg 1 −1 ) under all conditions studied. The growth rate and mean size of the colloidal Au formed was monitored using UV-visible spectroscopy. Larger colloids were formed in the presence of humic (∼60-nm mean diameter) than fulvic acid (∼20-nm mean diameter). Otherwise, colloidal growth rates were similar for humic and fulvic acids. Colloidal Au formation was completed in ∼8 days at pH 4 and slowed to > 14 days at pH > 7. Cupric ion (2 · 10 −5 -2 · 10 −3 M) accelerated colloidal Au development from 2 to 20 times while equal concentrations of Ca 2+ had no effect. About 10 mg 1 −1 humic and fulvic acids were necessary to completely reduce 10 mg 1 −1 Au (III)-chloride which is equivalent to a reduction capacity of ∼15 meq e − /g humic substance. IR spectroscopy and acid titration results suggest that humic substance oxidation included the addition of phenolic, alcohol and ketone groups which helps to account for the appreciable reduction capacity observed. Ten mg 1 −1 solutions of these same humic substances did not dissolve elemental Au to levels > 1 μ g 1 −1 over periods up to 150 days. Consequently, it is concluded that humic and fulvic acids function primarily as reductants of oxidized Au species rather than as dissolution and complexation agents for elemental Au. This implies that other components of natural organic matter are primarily responsible for the dissolution and complexation of elemental Au in surficial environments.

Specific studies detailing the effects of amines, used as pH control agents for corrosion inhibition in power plants, on the surface charge of iron oxides provide data to assess the mechanism of how these amines impact deposition rate. The current study was undertaken in order to determine accurately the dissociation constants of the relevant amines at Pressurized Water Reactor (PWR) operating conditions and to investigate the effect of sorption of two of these amines (morpholine and dimethylamine) by magnetite. The acid-dissociation equilibria of morpholine (MOR), dimethylamine (DMA) and ethanolamine (ETA) were measured potentiometrically with a hydrogen-electrode concentration cell (HECC) from 0 to 290 °C in sodium trifluoromethanesulfonate (NaTr) solutions at ionic strengths up to 1 mol⋅kg−1. Magnetite surface titrations were performed at an ionic strength of 0.03 mol⋅kg−1 (NaTr medium) in the presence or absence of morpholine and dimethylamine buffers over a wide range of pH and total amine concentrations at 150–250 °C.