Search Results (6)

The simple salt approximation (SSA) for lattice energies is used to rationalize the composition of Tutton salts with the formula A₂M(SO₄)₂(H₂O)₆, where A is a monovalent cation, usually K⁺, and M is a divalent cation, usually a transition metal cation such as Cu²⁺. These salts have become increasingly advantageous due to their heat exchange and optical properties, as well as providing vehicles for the study of the Jahn–Teller effect. The SSA suggests that the solubility of a double salt will be about the same as, or slightly lower than, that of the constituent simple salts when the simple salts have similar solubilities. This generalization has been used to rationalize the stability of the double salts synthesized and reported herein using standard procedures (mixing of simple salt constituents followed by slow evaporation). As expected, the hexa-coordination of water was obtained only with small divalent cations. Of particular interest is the absence of Tutton salts containing small alkali metal cations, specifically Li⁺ and Na⁺, an observation that is seemingly inconsistent with the large lattice energies that these ions should confer on the double salts and the similar solubilities of their salts to those of the transition metal sulfate. Although analytical data appeared to provide evidence for Tutton salts when M = Li⁺, the PXRD patterns of the synthesized compounds clearly showed mixtures of the simple-salt-starting reagents. We conclude that inability to synthesize a Tutton salt using small alkali metal cations is predominantly due to the lower-than-expected lattice energies of these compounds and consequent greater solubilities than their simple salt constituents. Moreover, we can attribute this instability to the extensive hydrogen-bonding present in the Tutton structure, which produces long monovalent sulfate distances and weaker-than-supposed lattice energies. However, it is also true that both the heat of hydration of the Li⁺ ion and its entropy of hydration also conspire to provide greater solubility. Full article

The environment model for the description of the location of carbonate ions in apatites predicts that approximately half of the carbonate occupies the apatite channel. This model relies on the influence of entities surrounding the carbonate on its IR spectrum and can be used to determine how various substituents affect the location and structure of that ion. Careful deconvolution (peak-fitting) of the asymmetric carbonate IR region was used to determine the percentage of A-type (channel) ions, A′-type (channel with either a Ca²⁺ vacancy or substitution of Na⁺ for Ca²⁺) ions, and B-type (substitution for phosphate) ions. In our previous applications of this model, we have looked at the effect of alkali metal ions, such as sodium, lithium, and potassium, the ammonium ion, and the rare earth europium ion. In the present work, we explore the incorporation of the first-row transition metal ions and find that they have little effect on the location of the carbonate ion. Like the un-substituted carbonated apatite, these apatites contain about half of the carbonate in the channel, at least in derivatives that contain up to half a mole of the metal ion per mole of apatite. Attempts to incorporate greater amounts of metal ions by aqueous ion-combination reactions generally lead to lower-resolution XRD patterns and IR spectra that produce greater uncertainties in the peak-fitting modeling. Full article

In this first exploration of europium-doped carbonated apatites the location of carbonate was determined using the environment model for the analysis of IR and NMR spectra. Europium-doped carbonated apatites, containing Eu/(Eu + Ca) mole ratios of about 10%, were prepared by aqueous one-step and addition syntheses. The IR and NMR spectra of the carbonate in the samples are described using the environment model: A-type carbonate is assigned to channels containing only calcium ions (A = Ca6) or to channels containing one Na⁺ or a vacancy (A’ = Ca5Na or Ca5). The presence of the channel Eu³⁺ and the use of triammonium phosphate in the synthesis produce considerable A-type carbonate. For the apatites reported here, the carbonate is distributed in approximately a 60 to 40 ratio for channel occupancy versus replacement of phosphate. The europium is assumed to have replaced calcium ions in the Ca(II) (channel) location and the stoichiometry of the products is used to propose that, contrary to much of the Eu(III) substitution literature, the charge-balance mechanism is likely to involve the substitution of two europium ions for three calcium ion with the concomitant formation of a calcium vacancy. The environment model is also used in the correlation of the a-axial lattice parameter with the percent A-type carbonate. Full article

The identification and characterization of lead-bearing and associated minerals in scales on lead pipes are essential to understanding and predicting the mobilization of lead into drinking water. Despite its long-recognized usefulness in the unambiguous identification of crystalline and amorphous solids, distinguishing between polymorphic phases, and rapid and non-destructive analysis on the micrometer spatial scale, the Raman spectroscopy (RS) technique has been applied only occasionally in the analysis of scales in lead service lines (LSLs). This article illustrates multiple applications of RS not just for the identification of phases, but also compositional and structural characterization of scale materials in harvested lead pipes and experimental pipe-loop/recirculation systems. RS is shown to be a sensitive monitor of these characteristics through analyses on cross-sections of lead pipes, raw interior pipe walls, particulates captured in filters, and scrapings from pipes. RS proves to be especially sensitive to the state of crystallinity of scale phases (important to their solubility) and to the specific chemistry of phases precipitated upon the introduction of orthophosphate to the water system. It can be used effectively alone as well as in conjunction with more standard analytical techniques. By means of fiber-optic probes, RS has potential for in situ, real-time analysis within water-filled pipes. Full article

Parasitic weeds of the family Orobanchaceae attach to the roots of host plants via haustoria capable of drawing nutrients from host vascular tissue. The connection of the haustorium to the host marks a shift in parasite metabolism from autotrophy to at least partial heterotrophy, depending on the level of parasite dependence. Species within the family Orobanchaceae span the spectrum of host nutrient dependency, yet the diversity of parasitic plant metabolism remains poorly understood, particularly during the key metabolic shift surrounding haustorial attachment. Comparative profiling of major metabolites in the obligate holoparasite Phelipanche aegyptiaca and the facultative hemiparasite Triphysaria versicolor before and after attachment to the hosts revealed several metabolic shifts implicating remodeling of energy and amino acid metabolism. After attachment, both parasites showed metabolite profiles that were different from their respective hosts. In P. aegyptiaca, prominent changes in metabolite profiles were also associated with transitioning between different tissue types before and after attachment, with aspartate levels increasing significantly after the attachment. Based on the results from ¹⁵N labeling experiments, asparagine and/or aspartate-rich proteins were enriched in host-derived nitrogen in T. versicolor. These results point to the importance of aspartate and/or asparagine in the early stages of attachment in these plant parasites and provide a rationale for targeting aspartate-family amino acid biosynthesis for disrupting the growth of parasitic weeds. Full article

The recent definitive deuterium solid state NMR spectroscopic evidence for structural water in fluor- and hydroxylapatites has prompted our study of the conditions necessary for the removal and reincorporation of this important structural feature of apatites. Thermal gravimetric analysis of 20 synthetic carbonated calcium hydroxylapatite (CCaApOH) samples and nine carbonated calcium fluorapatite (CCaApF) samples has been used to determine the amount of structural and adsorbed water in each sample. No correlation between the weight percent and number of moles of structural water and the weight percent carbonate in CCaApOH and CCaApF has been found. In contrast, there appears to be a relationship between the amount of adsorbed water and the carbonate concentration in the fluorapatites prepared with a two hour digestion time, as well as in the hydroxylapatites prepared with one hour digestion periods, presumably due to the effect of carbonate on crystallite size. Structural water can be removed from the apatite lattice, primarily above 200 °C, but heating to over 550 °C is required for complete removal. This water can be partly reincorporated through an apparently kinetically-controlled process that is enhanced by an increase in time and/or temperature. We speculate that the incorporation of structural water occurs at the beginning of the formation of the apatite structure, approximately coincident with the incorporation of carbonate. We also speculate that water is both removed and reincorporated by proton transfers from water molecules to hydroxide ions. Full article