Juyoung Ha

Adsorption of organic matter at mineral/water interfaces: 7. ATR-FTIR and quantum chemical study of lactate interactions with hematite nanoparticles.

The interaction of the l-lactate ion ( l-CH3CH(OH)COO(-), lact(-1)) with hematite (alpha-Fe2O3) nanoparticles (average diameter 11 nm) in the presence of bulk water at pH 5 and 25 degrees C was examined using a combination of (1) macroscopic uptake measurements, (2) in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, and (3) density functional theory modeling at the B3LYP/6-31+G* level. Uptake measurements indicate that increasing [ lact(-1)]aq results in an increase in lact(-1) uptake and a concomitant increase in Fe(III) release as a result of the dissolution of the hematite nanoparticles. The ATR-FTIR spectra of aqueous lact(-1) and lact(-1) adsorbed onto hematite nanoparticles at coverages ranging from 0.52 to 5.21 micromol/m2 showed significant differences in peak positions and shapes of carboxyl group stretches. On the basis of Gaussian fits of the spectra, we conclude that lact(-1) is present as both outer-sphere and inner-sphere complexes on the hematite nanoparticles. No significant dependence of the extent of lact(-1) adsorption on background electrolyte concentration was found, suggesting that the dominant adsorption mode for lact(-1) is inner sphere under these conditions. On the basis of quantum chemical modeling, we suggest that inner-sphere complexes of lact(-1) adsorbed on hematite nanoparticles occur dominantly as monodentate, mononuclear complexes with the hydroxyl functional group pointing away from the Fe(III) center.

Interaction of Aqueous Zn(II) with Hematite Nanoparticles and Microparticles. Part 1. EXAFS Study of Zn(II) Adsorption and Precipitation

Sorption of Zn(II)(aq) on hematite (alpha-Fe2O3) nanoparticles (average diameter 10.5 nm) and microparticles (average diameter 550 nm) has been examined over a range of total Zn(II)(aq) concentrations (0.4-7.6 mM) using Zn K-edge EXAFS spectroscopy and selective chemical extractions. When ZnCl2 aqueous solutions were reacted with hematite nanoparticles (HN) at pH 5.5, Zn(II) formed a mixture of four- and six-coordinated surface complexes [Zn(O,OH)4 and Zn(O,OH)6] with an average Zn-O distance of 2.04+/-0.02 A at low sorption densities (Gamma<or=1.1 micromol/m2). On the basis of EXAFS-derived Zn-Fe3+ distances of (3.10-3.12)+/-0.02 A, we conclude that both Zn(O,OH)6 and Zn(O,OH)4 adsorb on octahedral Fe3+(O,OH)6 or pentahedral Fe3+(O,OH)5 surface sites on HN as inner-sphere, mononuclear, bidentate, edge-sharing adsorption complexes at these low sorption densities. It is possible that polynuclear Zn complexes are also present because of the similarity of Zn and Fe backscattering. At higher Zn(II) sorption densities on hematite nanoparticles (Gamma>or=3.38 micromol/m2), we observed the formation of Zn(O,OH)6 surface complexes, with an average Zn-O distance of 2.09+/-0.02 A, a Zn-Zn distance of 3.16+/-0.02 A, and a linear multiple-scattering feature at 6.12+/-0.06 A. Formation of a Zn(OH)2(am) precipitate for the higher sorption density samples (Gamma>or=3.38 micromol/m2) is suggested on the basis of comparison of the EXAFS spectra of the sorption samples with that of synthetic Zn(OH)2am. In contrast, EXAFS spectra of Zn(II) sorbed on hematite microparticles (HM) under similar experimental conditions showed no evidence of surface precipitates even at the same total [Zn(II)(aq)] that resulted in precipitate formation in the nanoparticle system. Instead, Zn(O,OH)6 octahedra (d(Zn-O)=2.10+/-0.02 A) were found to sorb dominantly in an inner-sphere, bidentate, edge-sharing fashion on Fe3+(O,OH)6 octahedra at hematite microparticle surfaces, based on an EXAFS-derived Zn-Fe3+ distance of 3.44+/-0.02 A. CaCl2 selective extraction experiments showed that 10-15% of the sorbed Zn(II) was released from Zn/HN sorption samples, and about 40% was released from a Zn/HM sorption sample. These fractions of Zn(II) are interpreted as weakly bound, outer-sphere adsorption complexes. The combined EXAFS and selective chemical extraction results indicate that (1) both Zn(O,OH)4 and Zn(O,OH)6 adsorption complexes are present in the Zn/HN system, whereas dominantly Zn(O,OH)6 adsorption complexes are present in the Zn/HM system; (2) a higher proportion of outer-sphere Zn(II) surface complexes is present in the Zn/HM system; and (3) Zn-containing precipitates similar to Zn(OH)2(am) form in the nanoparticle system but not in the microparticle system, suggesting a difference in reactivity of the hematite nanoparticles vs microparticles with respect to Zn(II)(aq).

Effect of polymers on the nanostructure and on the carbonation of calcium silicate hydrates: a scanning transmission X-ray microscopy study

This study investigated the effects of organic polymers (polyethylene glycol and hexadecyltrimethylammonium) on structures of calcium silicate hydrates (C–S–H) which is the major product of Portland cement hydration. Increased surface areas and expansion of layers were observed for all organic polymer modified C–S–H. The results from attenuated total reflectance–Fourier transform infrared (ATR–FTIR) spectroscopic measurements also suggest lowered water contents in the layered structures for the C–S–H samples that are modified by organic polymers. Scanning transmission X-ray microscopy (STXM) results further supports this observation. We also observed difference in the extent of C–S–H carbonation due to the presence of organic polymers. No calcite formed in the presence of HDTMA whereas formation of calcite was observed with C–S–H sample modified with PEG. We suggest that the difference in the carbonation reaction is possibly due to the ease of penetration and diffusion of the CO2. This observation suggests that CO2 reaction strongly depends on the presence of organic polymers and the types of organic polymers incorporated within the C–S–H structure. This is the first comprehensive study using STXM to quantitatively characterize the level of heterogeneity in cementitious materials at high spatial and spectral resolutions. The results from BET, XRD, ATR–FTIR, and STXM measurements are consistent and suggest that C–S–H layer structures are significantly modified due to the presence of organic polymers, and that the chemical composition and structural differences among the organic polymers determine the extent of the changes in the C–S–H nanostructures as well as the extent of carbonation reaction.

Interaction of Zn(II) with hematite nanoparticles and microparticles: Part 2. ATR-FTIR and EXAFS study of the aqueous Zn(II)/oxalate/hematite ternary system.

Sorption of Zn(II) to hematite nanoparticles (HN) (av diam=10.5 nm) and microparticles (HM) (av diam=550 nm) was studied in the presence of oxalate anions (Ox2-(aq)) in aqueous solutions as a function of total Zn(II)(aq) to total Ox2-(aq) concentration ratio (R=[Zn(II)(aq)]tot/[Ox2-(aq)]tot) at pH 5.5. Zn(II) uptake is similar in extent for both the Zn(II)/Ox/HN and Zn(II)/Ox/HM ternary systems and the Zn(II)/HN binary system at [Zn(II)(aq)](tot)<4 mM, whereas it is 50-100% higher for the Zn(II)/Ox/HN system than for the Zn(II)/Ox/HM ternary and the Zn(II)/HN and Zn(II)/HM binary systems at [Zn(II)(aq)]tot>4 mM. In contrast, Zn(II) uptake for the Zn(II)/HM binary system is a factor of 2 greater than that for the Zn(II)/Ox/HM and Zn(II)/Ox/HN ternary systems and the Zn(II)/HN binary system at [Zn(II)(aq)]tot<4 mM. In the Zn(II)/Ox/HM ternary system at both R values examined (0.16 and 0.68), attenuated total reflectance Fourier transform infrared (ATR-FTIR) results are consistent with the presence of inner-sphere oxalate complexes and outer-sphere ZnOx(aq) complexes, and/or type A ternary complexes. In addition, extended X-ray absorption fine structure (EXAFS) spectroscopic results suggest that type A ternary surface complexes (i.e., >O2-Zn-Ox) are present. In the Zn(II)/Ox/HN ternary system at R=0.15, ATR-FTIR results indicate the presence of inner-sphere oxalate and outer-sphere ZnOx(aq) complexes; the EXAFS results provide no evidence for inner-sphere Zn(II) complexes or type A ternary complexes. In contrast, ATR-FTIR results for the Zn/Ox/HN sample with R = 0.68 are consistent with a ZnOx(s)-like surface precipitate and possibly type B ternary surface complexes (i.e., >O2-Ox-Zn). EXAFS results are also consistent with the presence of ZnOx(s)-like precipitates. We ascribe the observed increase of Zn(II)(aq) uptake in the Zn(II)/Ox/HN ternary system at [Zn(II)(aq)]tot>or=4 mM relative to the Zn(II)/Ox/HM ternary system to formation of a ZnOx(s)-like precipitate at the hematite nanoparticle/water interface.

Role of Adsorption Phenomena in Cubic Tricalcium Aluminate Dissolution

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C3A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C3A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C3A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C3A, reducing its zeta potential to negative values at pH >12. The S and Ca K-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO42- on the partially dissolved C3A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C3A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C3A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C3A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.

Scanning Transmission X-Ray Microscopic Study of Carbonated Calcium Silicate Hydrate

Calcium silicate hydrate (C-S-H) is the main hydration product of portland cement. Studying the structural and chemical decomposition of C-S-H after carbonation is critical for determining the durability and serviceability of concrete. Recent studies showed that the mechanical properties are likely to be enhanced when mineral admixtures and polymers are introduced. So far, no molecular-level studies have been conducted on carbonated C-S-H material to clarify these effects. In this research, scanning transmission X-ray microscopy (STXM) is used to study C-S-H modified with two organic polymers (hexadecyltrimethyl-ammonium and polyethylene glycol 200) and exposed to different reaction times with CO2. STXM uses light in the soft X-ray region where a number of atomic resonances are present. By tuning the X-ray energies to a certain absorption edge, elemental and chemical identification was performed. The energy of the X-rays was tuned to the C K-edge, Ca L2,3-edge, and Si K-edge. Detailed images were also recorded with a lateral resolution of 30 nm. Structural, elemental, and chemical heterogeneities were spatially identified. Significant differences were found in carbon spectra in the atmospheric and 48-h continuous CO2-carbonated C-S-H samples, suggesting that carbon-containing precipitates formed within a C-S-H matrix differ depending on the extent of carbonation. Si K-edge spectra suggest increased polymerization of silicates depending on the duration of CO2 exposure. This study found that the degree of silicate polymerization and the coordination environment for carbon-containing mineral phases vary with the CO2 exposure level.

Phase Changes of Monosulfoaluminate in NaCl Aqueous Solution

Monosulfoaluminate (Ca4Al2(SO4)(OH)12∙6H2O) plays an important role in anion binding in Portland cement by exchanging its original interlayer ions (SO42− and OH−) with chloride ions. In this study, scanning transmission X-ray microscope (STXM), X-ray absorption near edge structure (XANES) spectroscopy, and X-ray diffraction (XRD) were used to investigate the phase change of monosulfoaluminate due to its interaction with chloride ions. Pure monosulfoaluminate was synthesized and its powder samples were suspended in 0, 0.1, 1, 3, and 5 M NaCl solutions for seven days. At low chloride concentrations, a partial dissolution of monosulfoaluminate formed ettringite, while, with increasing chloride content, the dissolution process was suppressed. As the NaCl concentration increased, the dominant mechanism of the phase change became ion exchange, resulting in direct phase transformation from monosulfoaluminate to Kuzel’s salt or Friedel’s salt. The phase assemblages of the NaCl-reacted samples were explored using thermodynamic calculations and least-square linear combination (LC) fitting of measured XANES spectra. A comprehensive description of the phase change and its dominant mechanism are discussed.

Ca L2,3-edge near edge X-ray absorption fine structure of tricalcium aluminate, gypsum, and calcium (sulfo)aluminate hydrates

Abstract Tricalcium aluminate (cement clinker phase), gypsum, katoite, ettringite, and calcium monosulfoaluminate hydrate (abbreviated as kuzelite) are the major minerals in the hydration reaction of tricalcium aluminate in the presence of gypsum and have critical impacts on the kinetics and thermodynamics of early-age cement hydration mechanisms. Here, spectroscopic analysis of these minerals is conducted using scanning transmission X-ray microscopy (STXM). Their Ca L2,3-edge near edge X-ray absorption fine structure (NEXAFS) spectra are measured and correlated to the known Ca coordination environments. The results indicate that these minerals have unique Ca environments that can be differentiated from one another based on the intensities and positions of the absorption peaks at 346.5–348.5 and 350.5–351.5 eV. It is concluded that Ca in tricalcium aluminate (cubic and orthorhombic polymorphs) and katoite is in cubic-like coordination with negative 10Dq, whereas Ca is in an octahedral-like coordination with positive 10Dq in ettringite, gypsum, and kuzelite. For tricalcium aluminate, the Ca atoms in both polymorphs are in similar chemical environments with slightly more distortion in the orthorhombic polymorph. As a common issue in STXM experiments, absorption saturation of NEXAFS spectra is also investigated. It is demonstrated that the optical density difference between pre- and post-edge absorption levels provides a reliable indication of the sample thickness in the systems studied. The present work provides a reference for the STXM study of the calcium (sulfo)aluminate reactions in cement hydration and natural aqueous environments, and in the former case, provides a more complete understanding of a system that may serve as a low-C alternative to Portland cement.

Characterization of Class F Fly Ash Using STXM

Chemical and physical characterization of fly ash particles were conducted using scanning transmission X-ray microscopy STXM. Compositional and spatial investigation and correlation among the main elemental constituents of fly ash Al, Si, and Fe were conducted based on microscopic and NEXAFS spectral analysis. Homogeneous oxidation and coordination state of Al and Fe were observed whereas Si shows spatial variation in its chemical state. We also identified that Si and Al are spatially correlated at nanometer scale in which high concentration of Si and Al was concurrently and consistently observed within the 30u2009nm resolution whereas Fe distribution did not show any specific correlation to Al and Si. Results of this study indicate that fly ash chemical composition has heterogeneous distribution depending on the elements which would determine and result in the differences in the reactivity.

Synchrotron X-ray studies of heavy metal mineral-microbe interactions

The availability of analytical methods that utilize the very intense and bright X-rays from synchrotron radiation sources has fundamentally changed the way in which geoscientists, environmental scientists and soil scientists study complex environmental samples and decipher the chemical and biological processes that impact the speciation, transport and potential bioavailability of environmental toxins (Brown et al. , 2006). Such samples are often mixtures of crystalline and amorphous phases in particle-sizes ranging from cm to nm, adsorbed metal ions and organic molecules, natural organic matter, microbial organisms, algae, plant materials and aqueous solutions. The processes that affect the chemical forms and environmental fate of contaminants in such mixtures range from surface adsorption, desorption, precipitation and dissolution reactions, often involving a combination of hydrolysis, ligand exchange and electron transfer, to biological interactions in which microbial organisms, algae or plants interact with mineral surfaces and environmental contaminants. These processes can result in: (1) the formation of biominerals, which can effectively sequester contaminants; (2) oxidation-reduction reactions of redox-sensitive contaminants, which can transform such contaminants into more (or less) toxic forms; and (3) mineral dissolution reactions, which can release heavy metal and metalloid contaminants. Determining the effects of these processes on environmental contaminants and characterizing the types and speciation of contaminants present in complex environmental samples are challenging tasks that require a variety of analytical methods. Such methods must be element-selective, sensitive enough to detect elemental concentrations at the ppm level, have spatial resolutions comparable to the spatial scales of elemental and structural heterogenieties of the samples, and be capable of providing molecular-scale structural and compositional information so that contaminant speciation can be defined quantitatively. Because many of the chemical and biological processes of interest in this context occur at environmental interfaces (e.g. mineral/water or mineral/microbe interfaces), it is also essential that some of the …