Kidney stones consisting predominantly of whewellite (calcium oxalate monohydrate, COM) are often found attached to hydroxylapatite (HA) plaques that form in the soft tissue of kidneys, cause lesions and become exposed to urine. Although the processes of stone formation are not entirely known, it is an established view that so-called Randall’s plaques serve as substrates for COM crystal nucleation and growth from correspondingly supersaturated urine. However, the results presented here suggest an additional mineral replacement process is involved. In an experimental approach, HA was reacted in 0.25 mM, 0.5 mM and 1.0 mM oxalate solutions with pH ranging from 4.5 to 7.5, simulating normal to harsh conditions encountered in urine. Extremely acidic solutions induce dissolution of HA crystals coupled with re-precipitation of the released Ca2+ ions as COM on the HA surface. When, instead, bone was used as a substrate, being more similar to the pathological plaque (aggregated HA nanocrystals within an organic matrix), the HA-COM mineral-replacement reaction is induced even under much milder fluid conditions, commonly found in urine. Hence, a process of COM partly replacing and encrusting Randall’s plaque may take place in the urinary tract of idiopathic stone formers, representing a potential starting event for nephrolithiasis.

Vivid blue inclusions in white whewellite or weddellite, occurring within the medulla of four lichen species growing on copper-bearing rocks, have been identified as the hydrated copper oxalate, moolooite, CuC2O4. nH2O (n ∼ 0.4–0.7), by infrared spectroscopy and X-ray powder diffraction. The mineral is believed to have been formed by reaction between oxalic acid secreted by the lichen and ground or surface water containing copper.

The crystal structure of whewellite [Ca(C2O4)·H2O] and the dehydration mechanism of caoxite [Ca(C2O4)·3H2O] have been studied by means of differential thermal analysis, X-ray diffraction (powder and single-crystal) analysis and infrared analysis. The first and second analyses confirmed the direct transformation of caoxite into whewellite without an intermediate weddellite [Ca(C2O4)·2H2O] stage. Infrared spectra obtained from caoxite, weddellite and whewellite emphasize the similarity of the O–H-stretching band and O–C–O-stretching band in whewellite and caoxite and the unique bands of weddellite. The structure refinement at low temperature (123 K) reveals that all the hydrogen atoms of whewellite form hydrogen bonds and the two water molecules prop up the crystal structure by the hydrogen bonds that cause a strong anisotropy of the displacement parameter.

Comparing the structural features of whewellite with those of weddellite and caoxite suggests that caoxite and whewellite have a sheet structure consisting of Ca2+ ions and oxalate ions although weddellite does not. It is additionally confirmed that the sheets of caoxite are corrugated by hydrogen bonds but whewellite has flat sheets. The corrugated sheets of caoxite would be flattened by dehydration so the direct transformation of caoxite into whewellite would not occur via weddellite. Essential for this transformation is the dehydration of interlayered water molecules in caoxite leading to the building of the crystal structure of whewellite on its intralayered water molecules. The difference in conformation of water molecules between those two crystal structures may explain the more common occurrence of whewellite than of caoxite in nature.

The factors influencing the predominance of one of the two mineral forms of calcium oxalate (CO), the monohydrated whewellite (COM) and the di-hydrated weddellite (COD), forming the pruina of the upper cortex of lichens, have been investigated through a simple, sensitive histochemical assay: toluidine blue O (TBO), a metachromatic staining test. The differential reactivity of 43 thalli of 17 pruinose foliose species, supplemented by X-ray diffraction analysis and observations with polarizing and scanning electron microscopy, suggests that the histochemical reactivity of hyphal walls and cementing substances of the upper cortex are related to the density of anionic charges. These factors are probably due to the occurrence of polyuronic acid substances that strongly affects the mineralization of CO. Di-hydrated wedellite is always associated with TBO metachromatic reactivity, and COM with orthochromatic reactivity. When the material has an ambiguous ortho/metachromatic reactivity, COD and COM may occur together. This study presents the first experimental evidence that in lichens CO biomineralization is at least partially biologically controlled.