Two-line ferrihydrite is an important adsorbent of many toxics in natural and anthropogenic systems; however, the specific structural sites responsible for the high adsorption capacity are not well understood. A combination of chemical and spectroscopic techniques have been employed in this study to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59Fe-NTA solutions, while the second population of sites, referred to as non-labile, exhibited a much slower rate of isotopic exchange. Adsorbed arsenate reduced the degree of exchange by labile sites, indicating that the anion blocked or greatly inhibited the rate of exchange of these sites. Mössbauer spectra were collected from a variety of samples including 56Fe-ferrihydrite samples with 57Fe in labile sites, samples containing 57Fe throughout the structure, and samples with 57Fe in non-labile sites. The spectra showed characteristic broad doublets signifying poor structural order. Refined fits of the spectra indicated that labile sites have larger quadrupole splitting, hence more local distortion, than non-labile sites. In all cases, the spectra demonstrated some degree of asymmetry, indicating a distribution of Fe environments in ferrihydrite. Overall spectral findings, combined with recent EXAFS results (Waychunas et al., 1993), indicate that labile sites likely are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population of surface sites. Mössbauer spectra of samples containing adsorbed arsenate indicated that the anion may slightly decrease the distortion of labile sites and stabilized the structure as a whole by bidentate bonding.

The atomic structure of dioctahedral 2:1 phyllosilicate edge surfaces was calculated using pseudopotential planewave density functional theory. Bulk structures of pyrophyllite and ferripyrophyllite were optimized using periodic boundary conditions, after which crystal chemical methods were used to obtain initial terminations for ideal (110)- and (010)-type edge surfaces. The edge surfaces were protonated using various schemes to neutralize the surface charge, and total minimized energies were compared to identify which schemes are the most energetically favorable. The calculations show that significant surface relaxation should occur on the (110)-type faces, as well as in response to different protonation schemes on both surface types. This result is consistent with atomic force microscopy observations of phyllosilicate dissolution behavior. Bond-valence methods incorporating bond lengths from calculated structures can be used to predict intrinsic acidity constants for surface functional groups on (110)- and (010)-type edge surfaces. However, the occurrence of surface relaxation poses problems for applying current bond-valence methods. An alternative method is proposed that considers bond relaxation, and accounts for the energetics of various protonation schemes on phyllosilicate edges.

The morphology, dehydroxylation, and dissolution properties of single- and multi-metal (Cr, Zn, Cd, and Pb)-substituted goethites prepared using hydrothermal methods are reported. The crystal morphology varied with the nature and the number of metals present in the system. The presence of Cr produced broader crystals while Zn, Cd, and Pb produced narrower crystals than pure goethite. The presence of multiple metals retards the crystal growth of the mineral. Metal substitution caused changes in the unit-cell parameters and the infrared (IR) spectra of the samples. The IR spectra were also sensitive to the morphology of the crystals. The separation of γO and δOH bending frequencies increased with increase in area and aspect ratio of the (100) crystal face. The dissolution-kinetics studies (1 M HCl, 40ºC) of single-metal-substituted goethite provided the following dissolution rate order: Zn- > Pb(II)- ≥ Pb(IV)- > unsubstituted > Cd- > Cr-goethite. More complex results were obtained for the multi-metal-substituted samples. In the di-metal-substituted goethites, incorporation of Cr suppressed the dissolution rate of Zn-substituted goethite by 85% and Cd suppressed the dissolution rate of Zn-substituted goethite by 53%. Similarly, incorporated Cr and Cd suppressed the dissolution rate of Pb(II)-substituted goethite by 50%. The dissolution rates of multi-metal-substituted goethite were linearly related to the steric strains derived from the lattice parameters of the mineral. Dissolution studies also showed that Cr, Zn, Cd, and Pb(IV) were distributed homogeneously throughout goethite crystals while Pb(II) was enriched in the near-surface regions of the crystals. Incorporation of Cr and Pb(II) increased, while Zn and Pb(IV) decreased the dehydroxylation temperature of single-metal-substituted goethites. Incorporation of Zn suppressed the effect of Cr on the dehydroxylation temperature in multi-metal-substituted goethites.

The dissolution kinetics of sepiolite in hydrochloric acid and nitric acid were studied in a batch reactor. The effects of reaction temperature, acid concentration, particle size and solid-to-liquid ratio on the dissolution process were investigated. Experimental studies were carried out in the ranges of 25–75°C for reaction temperature, 0.25–1.00 mol/L for acid concentration, 0.00755–0.05020 cm for average particle size and 2.5 to 12.5 g of solid/100 mL of acid for solid-to-liquid ratio. It was determined that the dissolution process is controlled by resistance of the diffusion through the product layer. The activation energies of the process were determined to be 40.8 and 38.3 kJ/mol for hydrochloric and nitric acid, respectively. The apparent rate constants were expressed as a function of reaction temperature, acid concentration, particle radius and solid-to-liquid ratio: kαe−4910(1/T)Cr−0.6 (s/l)−1 and kαe−4606(1/T)Cr−0.5 (s/1)−1 for hydrochloric and nitric acid, respectively; k is the apparent rate constant in min−1; T, the reaction temperature (K); C, the acid concentration (mol/L); r, the initial particle radius (cm); s/l, the solid-to-liquid ratio (g of solid/100 mL of acid).

Extensive use of cement and concrete is envisaged in the construction of geological disposal facilities for radioactive wastes. The hyperalkaline porefluids typical of groundwaters that have reacted with these materials have the potential to react chemically with other engineered barrier components such as bentonite, potentially degrading their performance. Analcime, NaAlSi2O6.H2O, has been identified from previous modelling and experimental studies as a potential alteration product of bentonite.

Laboratory experiments to investigate the stability of analcime under hyperalkaline porefluid conditions have been performed. Experiments used both batch and fluidized bed equipment at 25, 50, 70 and 90°C in K-based pH buffer solutions, both under- and over-saturated with respect to analcime. Results from dissolution experiments demonstrate that release of Na was greatly enhanced (by up to a factor of thirty) over that for Si and Al, particularly at pH 10 and 11. However, enhanced release of both Na and Al occurred in the batch experiments at pH 12–13. Near stoichiometric dissolution was observed in fluidized bed experiments under steady-state conditions at 70°C. Sodium was removed from the analcime structure by ion exchange for K, without involving dissolution and re-precipitation of the analcime framework. Scanning electron microscopy of reacted analcime grains showed that some grains had pronounced cracks parallel to original cleavage traces. These cracks were a result of volume decrease due to the substitution of K for Na ions and water molecules in the analcime structure to form leucite, KAlSi2O6.

Synthesis of the dissolution data shows that the rate of dissolution increased with increasing temperature in the range 25–70°C and with pH at each temperature. Absolute rates of dissolution ranged from 10−10 mol m−2 s−1 at pH 9.5 at 25°C to 10−7 mol m−2 s−1 a pH 12 at 70 and 90°C. The rate of dissolution at any temperature was pH-dependent, such that the rate could be described by k (aH+)n, where k is the rate constant and n is −0.3 at 25°C, −0.4 at 50°C, −0.6 at 70°C and −0.7 at 90°C. Attempts to measure the growth rate of analcime in supersaturated solutions at 70 and 90°C were unsuccessful, although a limiting rate at 70°C, pH 10 was calculated to be 4 × 10−11 mol m−2 s−1, roughly 100× less than the rate of dissolution under the same conditions.

These results imply that any trace amounts of analcime in bentonite will be converted to leucite by reaction with cement fluids with a high K/Na ratio. In some instances, leucite may thus incorporate K+ in preference to other phases (e.g. illite, K-feldspar) during alteration of bentonite by cement porefluids.

A survey of the surface-area-normalized dissolution rates of major phosphate bearing minerals shows these rates to vary by >8 orders of magnitude with a general dissolution-rate trend sturvite > britholite ∼ fluoroapatite > variscite > monazite ∼ rhabdophane. This trend reflects the relative strength of the metal-oxygen bonds holding together the phosphate tetrahedra in the mineral structure. Due to the high surface-area-normalized reactivity of fluoroapatite, and the high surface area of natural variscite and rhabdophane, it seems likely that these minerals buffer the concentration of P and the rare-earth elements in many natural waters. As such, the solubility of these minerals plays a significant role in the global phosphorus cycle, and may potentially provide clues for future sustainable phosphorus use.

In this work, differential scanning calorimetry (DSC) was used to characterize and analyze the precipitation/dissolution kinetics of second phase particles during the cooling/reheating process in a vanadium microalloyed steel. The results indicated that three obvious exothermic peaks were detected on the cooling DSC curve. Furthermore, three corresponding endothermic peaks were also detected on the heating DSC curve. Combined with thermodynamic calculation and transmission electron microscopy analysis, these three exothermic peaks along cooling DSC curve were defined as the precipitation reaction of V(CN), the reaction of austenite transformation into ferrite and the precipitation reaction of VC, respectively. Meanwhile, three corresponding reverse reactions for cooling were also defined along the reheating DSC curve. The linear regression result revealed that the precipitation activation energies for V(CN) and VC were identified as 311.2 kJ/mol and 167.6 kJ/mol, respectively. The dissolution activation energies for VC and V(CN) were identified as 255.4 kJ/mol and 592.6 kJ/mol, respectively.