Yantao Song

Ionic strength effects on silicic acid (H4SiO4) sorption and oligomerization on an iron oxide surface: an interesting interplay between electrostatic and chemical forces.

The effect of ionic strength on reactions at aqueous interfaces can provide insights into the nature of the chemistry involved. The adsorption of H(4)SiO(4) on iron oxides at low surface silicate concentration (Γ(Si)) forms monomeric silicate complexes with Fe-O-Si linkages, but as Γ(Si) increases silicate oligomers with Si-O-Si linkages become increasingly prevalent. In this paper, the effect of ionic strength (I) on both Γ(Si) and the extent of silicate oligomerization on the ferrihydrite surface is determined at pH 4, 7, and 10, where the surface is, respectively, positive, nearly neutral, and negatively charged. At pH 4, an increase in ionic strength causes Γ(Si) to decrease at a given H(4)SiO(4) solution concentration, while the proportion of oligomers on the surface at a given Γ(Si) increases. At pH 10, the opposite is observed; Γ(Si) increases as I increases, while the proportion of surface oligomers at a given Γ(Si) decreases. Ionic strength has only a small effect on the surface chemistry of H(4)SiO(4) at pH 7, but at low Γ(Si) this effect is in the direction observed at pH 4 while at high Γ(Si) the effect is in the direction observed at pH 10. The pH where the surface has zero charge decreases from ≈8 to 6 as Γ(Si) increases so that the surface potential (Ψ) is positive at pH 4 for all Γ(Si) and at pH 7 with low Γ(Si). Likewise, Ψ < 0 at pH 10 for all Γ(Si) and at pH 7 with high Γ(Si). The diffuse layer model is used to unravel the complex and subtle interactions between surface potential (Ψ) and chemical parameters that influence interfacial silicate chemistry. This analysis reveals that the decrease in the absolute value of Ψ as I increases causes Γ(Si) to decrease or increase where Ψ is, respectively, positive or negative. Therefore, at a given Γ(Si), the solution H(4)SiO(4) concentration changes with I, and because oligomerization has a higher H(4)SiO(4) stoichiometry coefficient than monomer adsorption, this results in the observed dependence of the extent of silicate oligomerization on I.

Arsenate–Ferrihydrite Systems from Minutes to Months: A Macroscopic and IR Spectroscopic Study of an Elusive Equilibrium

Sorption by ferrihydrite is an important control on As(V) concentrations in many oxic aquatic systems. There are significant discrepancies in reported sorption constants (log(KAs)), which presents a problem for quantifying and understanding this important system. A review of reported ferrihydrite-As(V) sorption studies indicated a positive correlation between reaction time used in the experiments and the log(KAs) values derived from the data. In this paper, we study the kinetics of As(V) sorption over ≈3000 h in nine systems with varying pH and As(V)/Fe. Ferrihydrite was stable in all systems containing As(V), and the [As(V)] in solution decreased linearly as a function of log(t) (termed Elovich kinetics) over the full 3000 h in most systems. A stable [As(V)] was only observed in systems with low As(V)/Fe and low pH. Apparent As(V) sorption constants were derived from the data at specific time intervals using the diffuse layer model and equations describing log(KAs) values as a function of time provide a way to describe this elusive equilibrium. IR spectra support the hypothesis that slow interparticle diffusion is responsible for the slow approach to equilibrium. This work resolves discrepancies in previous studies of As(V)-ferrihydrite and provides equations to allow for system appropriate log(KAs) values to be used.

Short range order at the amorphous TiO2–water interface probed by silicic acid adsorption and interfacial oligomerization: An ATR-IR and 29Si MAS-NMR study

Adsorption and oligomerization of H(4)SiO(4) at the amorphous TiO(2)-aqueous interface were studied using in situ Attenuated Total Reflectance Infrared (ATR-IR) and ex situ solid state (29)Si nuclear magnetic resonance (NMR). The ATR-IR spectra indicate that a monomeric silicate species is present at low silicate surface concentration (Γ(Si)). Above a threshold Γ(Si) linear silicate oligomers are formed and these oligomers dominate the surface at high Γ(Si). Interestingly the ATR-IR spectra of H(4)SiO(4) on the TiO(2) surface are very similar to those previously observed on the poorly ordered iron oxide phase ferrihydrite. The (29)Si NMR spectrum of silicate on the TiO(2) surface shows the presence of Si in three states with chemical shifts corresponding to isolated monomers (Q(0)), the ends of linear oligomers (Q(1)) and the middle of linear oligomers (Q(2)). The ratio of the area of the Q(1) and Q(2) peaks was ≈2:1 which is consistent with the proposed formation of linear silicate trimers by insertion of a solution H(4)SiO(4) between adjacent suitably orientated adsorbed silicate monomers. A structural interpretation indicates that the observed interfacial silicate oligomerization behavior is a general phenomenon whereby bidentate silicate monomers on oxide surfaces are disposed towards forming linear oligomers by condensation reactions involving their two terminal Si-OH groups. The high surface curvature of nanometer sized spheres inhibits the formation of interfacial silicates with a higher degree of polymerization.

The influence of surface structure on H4SiO4 oligomerization on rutile and amorphous TiO2 surfaces: an ATR-IR and synchrotron XPS study.

Silicic acid (H(4)SiO(4)) is ubiquitous in natural aquatic systems. Applications of TiO(2) in these systems will be influenced by H(4)SiO(4) sorption and oligomerization reactions on the TiO(2) surface, and this can affect many aspects of TiO(2) reactivity. The spatial arrangement of sorption sites on a metal oxide surface can promote specific lateral interactions, such as oligomerization, between sorbed species. In this work we explore the relationship between surface structure and interfacial H(4)SiO(4) oligomerization by quantifying the extent of H(4)SiO(4) sorption and oligomerization on three TiO(2) phases; a rutile phase having well-developed (110) faces (R180), a rutile phase with poorly developed (110) faces (R60), and an amorphous TiO(2) (TiO(2(am))). The in situ ATR-IR spectra measured over time as 0.2 mM H(4)SiO(4) reacted with TiO(2) were quite different on the three TiO(2) phases. The percentage of the surface H(4)SiO(4) that was present as oligomers increased over time on all phases, but after 20 h almost all H(4)SiO(4) on the R180 surface was oligomeric, while the H(4)SiO(4) on TiO(2(am)) was predominantly monomeric. The extent of H(4)SiO(4) oligomerization on R60 was intermediate. When the TiO(2) phases reacted with 1.5 mM H(4)SiO(4) the ATR-IR spectra showed oligomeric silicates dominating the surface of all three TiO(2) phases; however, after 20 h the percentage of the surface H(4)SiO(4) present as three-dimensional polymers was ∼30, 10, and 0% on R180, R60, and TiO(2(am)) respectively. The Si 2s photoelectron peak binding energy (BE) and the H(4)SiO(4) surface coverage (Γ(Si)) were measured by XPS over a range of Γ(Si). For any given Γ(Si) the Si 2s BEs were in the order R180 > R60 > TiO(2(am)). A higher Si 2s BE indicates a greater degree of silicate polymerization. The ATR-IR and XPS results support the existing model for interfacial H(4)SiO(4) oligomerization where linear trimeric silicates are formed by insertion of a solution H(4)SiO(4) between suitably orientated adjacent bidentate sorbed monomers. The TiO(2(am)) has previously been shown to consist of ∼2 nm diameter particles with a highly disordered surface. When compared to the TiO(2(am)) surface, the regular arrangement of TiO(6) octahedra on the rutile (110) face means that sorbed H(4)SiO(4) monomers on adjacent rows of singly coordinated oxygen atoms are oriented so as to favor linear trimer formation. Higher silicate polymers can form between adjacent trimers, and this is favored on the rutile (110) surfaces compared to the TiO(2(am)). This is also expected on the basis of the arrangement of surface sites on the rutile (110) surface and because the high surface curvature inherent in a ∼2 nm spherical TiO(2(am)) particle would increase the spatial separation of adjacent trimers.

Accurate and in situ monitoring of bacterial concentration using a real time all-fibre spectroscopic device

Accurate in situ monitoring of bacterial transport is important for increased understanding and improvement of bioremediation processes where microorganisms convert toxic compounds to more benign compounds. Bioremediation methods have become the preferred mechanism for the rehabilitation of hard to reach contaminated environments. In this study, we have used fluorescence spectroscopy to monitor the movement of fluorescently labelled bacteria (Rhodococcus erythropolis and Pseudomonas putida) within a bench-top column filled with a porous medium. In situ fluorescence measurements made using a fibre optic based instrument (‘optrode’) were compared to ex situ measurements made using a plate reader. In situ monitoring using this fibre optic based instrument is a promising alternative to ex situ measurements as the initial flow of bacteria is reliably observed. However, a greater understanding of the effect of the porous medium on fluorescence measurements is required to develop an accurate calibration for bacterial concentration based in situ measurements.

Modeling Cd2 + sorption onto ferrihydrite in the presence of phthalic acid

Cadmium sorption by ferrihydrite in the presence of phthalic acid was examined over a range of pH (4.0 approximately 8.5) conditions and sorbate/sorbent ratios. The presence of phthalic acid enhanced Cd(2+) sorption by forming ternary complexes on ferrihydrite surface, especially at low pH, but for high pH and high total organic ligand/Fe(mmol/mol) ratios, it decreased Cd(2+) sorption onto ferrihydrite by forming soluble complexes with the phthalate in solution. In binary systems, Cd(2+) and phthalic acid sorption by ferrihydrite was well reproduced using the diffuse layer model with sorption constants derived from the experimental data. Prediction using the optimised binary sorption constants for Cd(2+) sorption onto ferrihydrite in the presence of phthalic was poor and achieving a good fit required the inclusion of two additional ternary complexes.