Morphology and composition of calcium oxalate monohydrate phytoliths in the bark of Betula ermanii (stone birch): Case study from Sakhalin Island.

The morphology of calcium oxalate monohydrate precipitates (COM, Ca(C2O4)·H2O, P21/c, whewellite) occurring as crystals or intergrowths, as well as distribution of crystal-bearing idioblasts, have been studied for the first time in the bark of stone birch Betula ermanii from Sakhalin Island sampled in an area affected by mud volcanism and an unaffected typical forest environment taken for reference. The study addresses several issues (i) number and size of phytoliths and their distribution in different cell types; (ii) density of calcification in specific cells; (iii) habits of single crystals, twins, and complex intergrowths, as well as frequency of different morphologies and their relations. The trends of time-dependent morphological changes in separately analyzed crystals and intergrowths record the evolution of COM morphology from nuclei to mature grains. Of special interest are the nucleation sites and features of organic and inorganic seeds and nuclei for COM phytoliths. The precipitation process and crystal habits are mainly controlled by supersaturation, and it is thus important to constrain the Ca distribution patterns in different bark tissues. The B. ermanii samples were analyzed by several methods: scanning electron microscopy (SEM) for the distribution patterns and micromorphology of COM precipitates and bulk Ca content in bark; electron probe microanalysis (EPMA) for the mineral chemistry of COM precipitates; inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) for trace elements in bulk bark and wood. RESEARCH HIGHLIGHTS: The distribution and morphology of whewellite precipitates in the analyzed B. ermanii bark samples indicate that the aqueous solution was most strongly supersaturated with respect to the Ca(C2O4)·H2O solid phase at the parenchyma-sclerenchyma boundary, where most of the COM spherulites are localized and often coexist with large single crystals and contact COM twins.

Biofilm Medium Chemistry and Calcium Oxalate Morphogenesis.

The present study is focused on the effect of biofilm medium chemistry on oxalate crystallization and contributes to the study of the patterns of microbial biomineralization and the development of nature-like technologies, using the metabolism of microscopic fungi. Calcium oxalates (weddellite and whewellite in different ratios) were synthesized by chemical precipitation in a weakly acidic environment (pH = 4-6), as is typical for the stationary phase of micromycetes growth, with a ratio of Ca2+/C2O42- = 4.0-5.5, at room temperature. Additives, which are common for biofilms on the surface of stone in an urban environment (citric, malic, succinic and fumaric acids; and K+, Mg2+, Fe3+, Sr2+, SO42+, PO43+ and CO32+ ions), were added to the solutions. The resulting precipitates were studied via X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS). It was revealed that organic acids, excreted by micromicetes, and some environmental ions, as well as their combinations, significantly affect the weddellite/whewellite ratio and the morphology of their phases (including the appearance of tetragonal prism faces of weddellite). The strongest unique effect leading to intensive crystallization of weddellite was only caused by the presence of citric acid additive in the medium. Minor changes in the composition of the additive components can lead to significant changes in the weddellite/whewellite ratio. The effect of the combination of additives on this ratio does not obey the law of additivity. The content of weddellite in the systems containing a representative set of both organic acids and environmental ions is ~20 wt%, which is in good agreement with natural systems.

Characterization of Calcium Oxalate Hydrates and the Transformation Process.

Calcium oxalate can be found in humans as kidney stones and in cultural heritage as films in two crystallographic species, dihydrate (COD/weddellite) and/or monohydrate (COM/whewellite). Due to its instability, COD is transformed into COM. Studying this crystalline conversion provides information about the origin of the monohydrated species, which will help in the assessment of prevention measurements to avoid their formation. In the present study, the synthesis of calcium oxalate hydrate microcrystals has been carefully performed to avoid mixture of phases in the final products; the long and short range order structure of both species have been studied by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS), respectively. This structural information was considered in the density functional theory (DFT) computational study performed to assign the characteristic vibrational IR and Raman frequencies found. This detailed characterization allows an unambiguous assignment of the vibrations, thus providing the appropriate parameters required to monitor and characterize the transformation process.

Radiation effect on cathodoluminescence and thermoluminescence emission of Ca-rich oxalates from the human body.

The radiation effect of luminescence emission of Ca-rich oxalate biogenic materials (gallbladder and renal calculi) and a commercial standard sample (CaC2 O4 ·H2 O) is reported. The samples were characterized by environmental scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric and differential thermal analyses, display complex cathodoluminescence (CL) and thermoluminescence (TL) glow emissions. CL spectra (in the UV-infrared range) displayed non-well defined peaks, and exhibited emission at: (i) higher energies (300-490 nm) mainly associated with non-bridging oxygen hole centers, oxygen-deficient centers and peroxy intrinsic defects, regardless of the sample; and (ii) higher, narrow and sharp wavebands, in the red region, probably induced by the presence of traces of Sm3+ (4 G5/2 →6 H9/2 transition) and/or Tb3+ (5 D4 →7 F3 transition) only for mineral-like materials in the human body. The UV-blue TL emission showed low-intensity maxima in which it was possible to distinguish at least four groups of components in each sample.

[Crystalluria in ethylene glycol intoxication]. / La cristallurie dans l'intoxication à l'éthylène glycol.

When seen, some habits of calcium oxalate monohydrate crystals (whewellite) are so typical of ethylene glycol intoxication that they may be helpful for its diagnosis when circumstances are not clearly established.

Phase transformation of calcium oxalate dihydrate-monohydrate: effects of relative humidity and new spectroscopic data.

New data on vibrational properties of calcium oxalates and their controversial transformation mechanism are presented. We have focused on whewellite (CaC2O4·H2O) and weddellite [CaC2O4·(2+x) H2O], the most common phases of calcium oxalate; these compounds occur in many organisms, in kidney stones and in particular kinds of films found on the surface of many works of art. Low temperature experiments carried out by Fourier transform infrared spectroscopy have highlighted both the high structural order in the crystalline state of whewellite and the disordered distribution of the zeolitic water molecules in weddellite. The synthesised nanocrystals of weddellite have been kept under different hygrometric conditions in order to study, by X-ray powder diffraction, the role of "external" water molecules on their stability. Moreover, in order to identify the different kinds of water molecules, a re-investigation, supported by quantum chemical calculations, of the observed vibrational spectra (IR and Raman) of whewellite has been conducted.

Characterization of biominerals in species of Canna (Cannaceae)

Plant biominerals are not always well characterized, although this information is important for plant physiology and can be useful for taxonomic purposes. In this work, fresh plant material of seven wild neotropical species of genus Canna, C. ascendens, C. coccinea, C. indica, C. glauca, C. plurituberosa, C. variegatifolia and C. fuchsina sp. ined., taken from different habitats, were studied to characterize the biominerals in their internal tissues. For the first time, samples from primary and secondary veins of leaves were investigated by means of infrared spectroscopy, complemented with X-ray powder diffractometry and scanning electron microscopy. The spectroscopic results, supported by X-ray powder diffractometry, suggest that the calcium oxalate is present in the form of whewellite (CaC2O4×H2O) in all the investigated samples. It is interesting to emphasize that all IR spectra obtained were strongly similar in all species studied, thus indicating an identical chemical composition in terms of the biominerals found. In this sense, the results suggest that the species of Canna show similar ability to produce biogenic silica and produce an identical type of calcium oxalate within their tissues. These results can be an additional trait to support the relationship among the families of Zingiberales. Rev. Biol. Trop. 58 (4): 1507-1515. Epub 2010 December 01.

Los biominerales de las plantas no siempre han sido bien caracterizados aunque esta información es importante en fisiología vegetal y puede ser de utilidad para fines taxonómicos. En este trabajo se estudió material vegetal fresco de siete especies silvestres neotropicales: Canna, C. ascendens, C. coccinea, C. indica, C. glauca, C. plurituberosa, C. variegatifolia and C. fuchsina sp. ined., provenientes de diferentes localidades, con el fin de caracterizar los biominerales presentes en sus tejidos foliares internos. Por vez primera, muestras de venas primarias (ejes foliares) y secundarias de hojas de estas especies se investigaron por medio de espectroscopia de infarrojo, complementada con estudios por difracción de rayos X de polvos y microscopía electrónica de barrido. Los resultados indicaron la presencia de ópalo (sílice biogénica) y oxalato de calcio en los tejidos vegetales analizados. Además, se determinó que el oxalato de calcio está presente en forma de whewellita (CaC2O4×H2O), información nueva para el género. Tanto el ópalo como la whewellita están presentes en todas las especies analizadas, que representan aproximadamente un tercio de las especies silvestres del género. La capacidad de biomineralizar SiO2 en forma de ópalo en especies de Canna de diversos ambientes resulta también un rasgo altamente sugerente para futuros estudios.