Effect of O2, Ni0 coatings, and iron oxide phases on pentachlorophenol dechlorination by zero-valent iron.

This study explores the zero-valent iron (ZVI) dechlorination of pentachlorophenol (PCP) and its dependence on the dissolved oxygen (O2), presence/formation of iron oxides, and presence of nickel metal on the ZVI surface. Compared to the anoxic system, PCP dechlorination was slower in the presence of O2, which is a potential competitive electron acceptor. Despite O2 presence, Ni0 deposited on the ZVI surfaces catalyzed the hydrogenation reactions and enhanced the PCP dechlorination by Ni-coated ZVI bimetal (Nic/Fe). The presence of O2 led to the formation of passivating oxides (maghemite, hematite, lepidocrocite, ferrihydrite) on the ZVI and Nic/Fe bimetallic surfaces. These passive oxides resulted in greater PCP incorporation (sorption, co-precipitation, and/or physical entrapment with the oxides) and decreased PCP dechlorination in the oxic systems compared to the anoxic systems. As received ZVI comprised of a wustite film, and in the presence of O2, only ≈ 17% PCP dechlorination observed after 25 days of exposure with tetrachlorophenol being detected as the end product. Wustite remained as the predominant oxide on as received ZVI during the 25 days of reaction with PCP under oxic and anoxic conditions. ZVI acid-pretreatment resulted in the replacement of wustite with magnetite and enhanced PCP degradation (e.g. ≈ 52% of the initial PCP dechlorinated after 25 days under oxic condition) with accumulation of mixtures of tetra-, tri-, and dichlorophenols. When the acid-washed ZVI was rinsed in NiSO4/H2SO4 solution, Ni0 deposited on the ZVI surface and all the wustite were replaced with magnetite. After 25 days of exposure to the Nic/Fe, ≈ 78% and 97% PCP dechlorination occurred under oxic and anoxic conditions, respectively, producing predominantly phenol. Wustite and magnetite are respectively electrically insulating and conducting oxides and influenced the dechlorination and H2 production. In conclusion, this study clearly demonstrates that the dissolved oxygen present in the aqueous solution decreases the PCP dechlorination and increases the PCP incorporation when using ZVI and Nic/Fe bimetallic systems. The findings provide novel insights towards deciphering and optimizing the performance of complex ZVI and bimetallic systems for PCP dechlorination in the presence of O2.

Pentachlorophenol dechlorination with zero valent iron: a Raman and GCMS study of the complex role of surficial iron oxides.

The dechlorination of chlorinated organic pollutants by zero valent iron (ZVI) is an important water treatment process with a complex dependence on many variables. This complexity means that there are reported inconsistencies in terms of dechlorination with ZVI and the effect of ZVI acid treatment, which are significant and are as yet unexplained. This study aims to decipher some of this complexity by combining Raman spectroscopy with gas chromatography-mass spectrometry (GC-MS) to investigate the influence of the mineralogy of the iron oxide phases on the surface of ZVI on the reductive dechlorination of pentachlorophenol (PCP). Two electrolytic iron samples (ZVI-T and ZVI-H) were found to have quite different PCP dechlorination reactivity in batch reactors under anoxic conditions. Raman analysis of the "as-received" ZVI-T indicated the iron was mainly covered with the ferrous oxide (FeO) wustite, which is non-conducting and led to a low rate of PCP dechlorination. In contrast, the dominant oxide on the "as-received" ZVI-H was magnetite which is conducting and, compared to ZVI-T, the ZVI-H rate of PCP dechlorination was four times faster. Treating the ZVI-H sample with 1 N H2SO4 made small change to the composition of the oxide layers and also minute change to the rate of PCP dechlorination. However, treating the ZVI-T sample with H2SO4 led to the loss of wustite so that magnetite became the dominant oxide and the rate of PCP dechlorination increased to that of the ZVI-H material. In conclusion, this study clearly shows that iron oxide mineralogy can be a contributing factor to apparent inconsistencies in the literature related to ZVI performance towards dechlorination and the effect of acid treatment on ZVI reactivity.

Calcium phosphates in Ca(2+)-fortified milk: phase identification and quantification by Raman spectroscopy.

Calcium phosphate nanoclusters (CPNs) are important for the structure, function, and nutrient density of many dairy products. Phosphorylated amino acids in caseins stabilize calcium phosphate as nanoclusters which are amorphous to X-ray diffraction and exist within casein micelles, and these CPNs play a key role in micelle stability. Addition of calcium to milk results in further calcium phosphate removal from the serum, and there is uncertainty about the nature of the material formed and its stability. In this work we investigate both the solution and colloidal phases in CaCl2 enriched bovine milk to identify, quantify, and determine the solubility of the calcium phosphate material formed in response to calcium addition to milk. The P-O stretching bands are quite distinct in the Raman spectra of the main synthetic calcium phosphate mineral phases, including the amorphous calcium phosphate phase. In response to adding between 5 and 40 mM CaCl2 to milk, the serum phosphate concentration decreased asymptotically from 7.5 ± 0.2 to 0.54 ± 0.05 mM. Using Raman spectroscopy with a combination of internal and external standards, it was possible to show that the calcium phosphate material formed after Ca(2+) addition to milk was the same as amorphous calcium phosphate nanoclusters present in the absence of added calcium. The use of an internal standard allowed a quantitative analysis of the spectra which demonstrated that the amorphous calcium phosphate formed accounted for all of the calcium and phosphate that was removed from solution in response to calcium addition.

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.

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 BE's 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.

Short range order at the amorphous TiO(2)-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.

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.

Experimental and theoretical investigations into the counter-intuitive shift in the antisymmetric ν(Si-O) vibrational modes upon deuteration of solvated silicic acid (H4SiO4).

The IR and Raman spectra of fully deuterated silicic acid (D(4)SiO(4)) have been obtained for the first time in solution and contrasted with the analogous spectra of H(4)SiO(4). The IR spectra feature antisymmetric ν(SiO) stretching modes at 939 and 951 cm(-1) for H(4)SiO(4) and D(4)SiO(4) respectively. The observed increase in frequency of the ν(SiO) modes upon deuteration is contrary to the expected effect of increasing the reduced mass. Broader and weaker bands due to δ(SiOX), X = H or D, deformations occur in the IR spectra at ∼1100 and 800 cm(-1), respectively. The symmetric ν(SiO) modes in the Raman occur at 787 and 764 cm(-1) for H(4)SiO(4) and D(4)SiO(4), respectively, and exhibit the expected decrease in frequency upon deuteration. To analyse these phenomena, RB3LYP/6-31+G(d) calculations were initially performed on gaseous H(4)SiO(4) and D(4)SiO(4). Significant coupling between antisymmetric ν(SiO) and δ(SiOH) deformations, calculated to be of comparable frequency, is noted in gaseous H(4)SiO(4). The calculated frequencies of the δ(SiOD) modes in gaseous D(4)SiO(4) occur ∼200 cm(-1) lower than those of ν(SiO) vibrations and the modes are not coupled. However, the predicted gas phase frequencies of δ(SiOX) modes are ∼200 cm(-1) lower than those observed for the solvated H(D)(4)SiO(4), and the observed reverse isotope shift of the antisymmetric ν(SiO) is not reproduced. Inclusion of a highly disordered 28 water solvation shell is found to significantly stiffen δ(SiOX) modes, leading to a significant blue-shift of 200-300 cm(-1) relative to analogous gas-phase frequencies and providing an accurate description of the bending modes. This frequency shift decouples the ν(SiO) and δ(SiOH) modes in H(4)SiO(4) but leads to coupling in solvated D(4)SiO(4) which is responsible for the observed reverse isotope shift of the antisymmetric ν(SiO) modes.

Insights into H(4)SiO(4) surface chemistry on ferrihydrite suspensions from ATR-IR, Diffuse Layer Modeling and the adsorption enhancing effects of carbonate.

Silicic acid (H(4)SiO(4)) adsorbs at the ferrihydrite-water interface as monomeric or oligomeric surface silicate complexes.ATR-IR spectra were used to determine the proportions of monomeric and oligomeric surface silicate as a function of pH and Si surface concentrations (Γ(Si)) for H(4)SiO(4) in ferrihydrite suspensions.At each pH the proportion of adsorbed silicate present as monomers decreased as Γ(Si) increased while at a given Γ(Si) the proportion of adsorbed silicate present as monomers was higher at higher pH. ATR-IR spectra for ferrihydrite suspensions in combination with the adsorption isotherm data were used to calibrate the Diffuse Layer Model (DLM) to describe H(4)SiO(4) adsorption as monomers and oligomers on ferrihydrite surface sites (≡FeOH). Using a set of reactions that were consistent with the ATR-IR spectra the DLM could accurately describe the H(4)SiO(4) adsorption isotherms, the distribution of surface monomeric and oligomeric silicates, and the decrease in surface potential with Γ(Si).The reactions included the formation of monomeric complexes (≡FeH((3-n))SiO(4)((-n))) and trimeric silicate complexes formed between two surface sites(≡Fe(2)H((6-n))Si(3)O(10)((-n))). This oligomer stoichiometry is consistent with previous studies suggesting the surface silicate oligomer is formed by a solution H(4)SiO(4) bridging two adjacent adsorbed monomers to form a linear trimer. This study also showed that carbonate can enhance H(4)SiO(4) adsorption between pH 9 and 11. The data were consistent with formation of an outer-sphere complex between a solution H(3)SiO(4)(-) and a protonated adsorbed carbonate species which is analogous to the mechanism by which carbonate enhances the goethite adsorption of sulfate.

Silicic acid adsorption and oligomerization at the ferrihydrite-water interface: interpretation of ATR-IR spectra based on a model surface structure.

Oxide surfaces can promote specific lateral interactions between adsorbed species that become concentrated in specific orientations at an interface. In this article, in situ attenuated total reflectance (ATR) IR spectra were collected over time (from 0 to approximately 100 h) as the iron oxide ferrihydrite reacted with H(4)SiO(4) (between 0.007 and 1.65 mM) and at a pH of 4, 7, or 10. Under all conditions, the first product formed was a monomeric surface species with distinct bands at 945 and 880 cm(-1), and a bidentate (2)C complex with SiO(4) sharing corners with two edge-linked Fe octahedra was proposed. Once a certain surface concentration (Gamma(Si)) of monomers was reached, a condensed oligomeric surface species with Si-O-Si linkages was observed on the surface with bands at 1005, 917, and 827 cm(-1) and one or more bands at >1050 cm(-1). This species was observed as a minor surface component at Gamma(Si) that was up to 10 times lower than the calculated density of (2)C adsorption sites on ferrihydrite and became the dominant surface species at higher Gamma(Si). This formation of a specific oligomer is rationalized on the basis of a recent model for the ferrihydrite surface, with the arrangement of (2)C adsorption sites on the (021) ferrihydrite face causing adjacent Si monomers to be held in an orientation that is conducive to the formation of a condensed Si species upon insertion of a solution H(4)SiO(4). Therefore, this model predicts that the ferrihydrite surface may act as a template for oligomerization in one dimension forming segments of pyroxene-like structures. The ATR-IR spectra and changes in the surface species' composition with time are consistent with such a model.

Cadmium(II) speciation in complex aquatic systems: a study with ferrihydrite, bacteria, and an organic ligand.

Understanding the chemical interactions that occur in complex natural systems is fundamental to their management In this work the distribution of cadmium in the presence of phthalic acid (H2Lp), ferrihydrite, and bacteria cells (Comamonas spp., heat killed) was measured and modeled for systems with incrementally increasing complexity. In binary systems, cadmium adsorption onto bacteria or ferrihydrite was accurately predicted using the nonelectrostatic four site model (NFSM) and the diffuse layer model (DLM), respectively. Phthalic acid (0.6 mM) enhanced Cd2+ adsorption onto ferrihydrite (due to surface ternary complex formation) butinhibited Cd2 adsorption onto bacteria to the same extent as predicted by Cd-phthalate solution complex formation constants, implying no significant surface ternary interaction occurred in this system. In Cd-ferrihydrite-bacteria systems, Cd2+ adsorption was up to 10% lower than that predicted by additive adsorption onto the pure phases which suggests that an interaction between ferrihydrite and the bacteria is occupying or masking adsorption sites. By adding a generic reaction to the model for the interaction between ferrihydrite and the bacteria, the adsorption of Cd2+ onto Comamonas spp.-ferrihydrite was accurately predicted and Cd2+ distribution and speciation in systems containing ferrihydrite, Comamonas spp., and H2Lp could be predicted.

Copper(II) and cadmium(II) sorption onto ferrihydrite in the presence of phthalic acid: some properties of the ternary complex.

Copper, cadmium, and phthalic acid (H2Lp) adsorption by ferrihydrite was examined for binary and ternary systems. In binary systems adsorption was well reproduced using the diffuse layer model (DLM), and H2Lp adsorption was analogous to that of inorganic diprotic acids in terms of the relationship between the adsorption constants and acidity constants. In ternary systems H2Lp caused both the enhancement (due to ternary complexformation) and inhibition (due to solution complex formation) of Cu2+ and Cd2+ sorption depending on the conditions. The DLM could only describe the effect of H2Lp on metal ion sorption by including ternary complexes of the form [triple bond]FeOHMLp (0), where [triple bond]FeOH is a surface site and M is Cu or Cd. The relationship between binary metal adsorption constants and the ternary complex adsorption constants from this and previous studies suggest several properties of ternary complexes. First, ternary complex structures on both ferrihydrite and goethite are either the same or similar. Second, those cations having large adsorption constants also have large equilibrium constants for ternary complex formation. Third, ligands forming stronger solution complexes with cations will also form stronger surface ternary complexes though, because of the strong solution complex, they will not necessarily enhance cation adsorption.