Calcification within breast cancer is a diagnostically significant radiological feature that generally consists of hydroxylapatite. Samples from 30 cases of breast carcinoma with calcification were investigated using optical microscopy, energy-dispersive X-ray analysis, transmission-electron microscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, synchrotron radiation X-ray diffraction and X-ray fluorescence. Under optical microscopy, the calcifications were found to consist of either irregular aggregates with widths > 200 μm or spherical aggregates similar to psammoma bodies with an average diameter of 30 μm. Transmission-electron microscopy showed that short columnar or dumbbell-shaped crystals with widths of 10–15 nm and lengths of 20–50 nm were the most common morphology; spherical aggregates (~1 μm in diameter) with amorphous coatings of fibrous nanocrystals were also observed. Results indicated that hydroxylapatite was the dominant mineral phase in the calcifications, and both CO32– and cation substitutions (Na, Mg, Zn, Fe, Sr, Cu and Mn) were present in the hydroxylapatite structure. Fourier-transform infrared spectra show peaks at 872 and 880 cm–1 indicating that CO32– substituted both the OH– (A type) and PO43– (B type) sites of hydroxylapatite, making it an A and B mixed type. The ratio of B- to A-type substitution was estimated in the range of 1.1–18.7 from the ratio of peak intensities (I872/I880), accompanied with CO32– contents from 1.1% to 14.5%. Trace arsenic, detected in situ by synchrotron radiation X-ray fluorescence was found to be distributed uniformly in the calcifications in the form of AsO43– substituting for PO43–. It is therefore proposed that identifying these trace elements in breast cancer calcifications may be promising for future clinical diagnostics.

Allophane-like materials occur in the weathered zones of the phosphate-rich veins hosted in Silurian metasediments of the Catalonian Coastal Ranges. These metasediments also host sulphide and phosphate sedimentary mineralizations. Mineralogical and geochemical investigations of the allophanic samples indicate that they comprise Si-rich allophane, with a molar SiO2/Al2O3 ratio ranging between 1.19 and 2.23, with amorphous Al-(Ca) phosphate and hydroxylapatite as major minerals, and minor goethite and quartz. It is assumed that allophane, amorphous Al-(Ca) phosphate and hydroxylapatite come from the reaction of acid solutions, released during the weathering of sulphide interbedded in black shales, with phosphate-rich veins and volcano- sedimentary host rocks. Silica-alumina gels were deposited in fissures and cavities left by a previous dissolution of the phosphate-rich veins. Later the phosphate minerals filled the conchoidal microfractures and shrinkage microcracks of the allophane.

Hydrothermal conversion of single crystals of calcite, CaCO3, dolomite, CaMg(CO3)2, and magnesite, MgCO3, was carried out in ammonium phosphate buffer solution. While calcite easily forms a pseudomorph of hydroxylapatite, Ca5(PO4)3OH, it takes several weeks to convert magnesite into pseudomorphic dittmarite, (NH4)Mg(PO4)·H2O. The conversion of dolomite, as the compositional intermediate, also proceeded slowly, but yielded a biphasic pseudomorph composed of whitlockite, Ca9Mg(PO4)6O(PO3OH), and dittmarite. To our knowledge, this is the first description of a biphasic pseudomorph with chemically and structurally different phases. Near the surface, the two phases formed a porous layered structure, while towards the core of the single crystal a fine-grained mixture of both minerals precipitated. The initially sequential pattern of precipitation of Ca-rich whitlockite followed by Mg-rich dittmarite can be explained by dissolved Mg ions being adsorbed onto the dolomite surface or incorporated into hydrated magnesium complexes, retarding crystallization of dittmarite. Surface adsorbed Mg ions impeding further dissolution of dolomite also partly accounts for the observed lower reaction rates of dolomite and magnesite, as compared to calcite. An additional factor decreasing the reaction rates of dolomite and magnesite is a considerable increase in molar volume upon conversion, which restricts the formation of porosity and, hence, ion transport to the reaction front.

Brachiopods are a phylum of shell-forming sessile marine invertebrates which have existed since the early Cambrian. Two very different biomaterial design strategies for their shells evolved early in their history. Both strategies use hybrid fibre composites, however, one is based on mineral fibres embedded in ~2 wt.% of organic biopolymer sheaths and the inorganic fibres are calcite single crystals. In the second strategy the fibres are biopolymers and are reinforced with Ca-phosphate nanoparticles to form a fibrous nanocomposite. Here the organic component (chitin) dominates. The Ca-phosphate nanoparticle-reinforcement strategy is not unlike that in vertebrate bone, however, the microscale structure is laminated with alternating laminae which have a different degree of mineralization.

The calcitic shells feature an outer compact layer of calcite micro- and nanoparticles protecting the inner fibrous layer from the outside. Transmission electron microscopy of the fibrous layer reveals intercrystalline and intracrystalline biopolymers. The calcitic shell material is stiff with nano-indentation E-moduli of 63±8 GPa and relatively hard (Vickers microhardness up to 400 HV 0.0005/10 and nanohardness 4±0.5 GPa). Compared to inorganic calcite the microhardness is doubled and the nanohardness increases by 60%. We attribute this increased hardness to intracrystalline biopolymers. The nano-indentation E-moduli of the chitinophosphatic shells range from 3 to 55 GPa as a result of the varying degree of mineralization between their laminae, and similarly their nanohardness varies between 0.1 and 3 GPa. For brachiopods burrowing inside the sediment, the alternation of non-mineralized laminae with thin, more strongly mineralized laminae provides abrasion-resistance, hardness and longitudinal stiffness while it preserves the flexibility provided by the organic component for bending movements.

Changes in the lability and local environment of Cd sorbed onto calcite, hydroxylapatite and humic acid have been investigated as a function of time (30 min–9 months) using a combination of X-ray adsorption spectroscopy (XAS) and isotopic dilution techniques with Cd concentrations between 1 and 1000 mmol kg –1. Enhanced X-ray absorption fine structure (EXAFS) shows that precipitation of Cd carbonate was initially observed on calcite. Ageing of a 10 mmol kg–1 sample showed replacement of Cd in the fourth shell with Ca, indicating diffusion between the two phases had occurred. This diffusion appeared to be ongoing for a 10 mmol kg–1 sample even after 9 months of reaction. Only 20% of the Cd in a sample with 10 mmol kg–1 Cd remained labile after 6 months of reaction, suggesting a high degree of incorporation into the solid phase, in agreement with the XAS results. The XAS results for hydroxylapatite indicated that Cd is not fixed in the mineral lattice and Cd lability in a sample loaded with 10 mmol kg–1 Cd was ∼55% after 6 months of reaction. This indicates that a relatively high proportion of the Cd sorbed to hydroxylapatite remained as kinetically active surface species. Little change was observed in the local environment of Cd adsorbed on flocculated Ca-humate samples as a function of time and ∼75% of the Cd remained radio-labile after 6 months of reaction regardless of initial Cd loading. High lability is expected because incorporation into a solid matrix or surface precipitation of a Cd phase is less likely than with the mineral phases.

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.

Mechanisms for the incorporation of carbonate into minerals of the apatite group have been explored in both the geological and medical literature. An important problem with respect to biological apatite, which requires further clarification, is the hydroxyl content of the carbonatedapatite of bone. Recent studies reveal bone apatite to contain only ∼20 mol.% of the hydroxyl content of stoichiometric hydroxylapatite, with negligible chloride or fluoride. We investigated the hypothesis that the development of vacancies in the hydroxyl channel sites is a charge-balancingmechanism for the substitution of carbonate ions into hydroxylapatite. Raman spectroscopic analyses of synthetic carbonated apatites (containing 1 to >15 wt.% carbonate) show that their hydroxyl ion concentration correlates inversely with carbonate concentration. The specific relationshipbetween carbonate and hydroxyl concentration in these samples closely follows the theoretical relationship defined by type-B substitution of carbonate for phosphate in the apatite structure. However, the 6–8 wt.% carbonate concentration in bone apatite falls far short of accounting forall of the hydroxyl depletion that occurs in bone apatite. Some of the additional hydroxyl depletion in bone apatite might result from substitution of Na+ for Ca2+, but further mechanism(s), perhaps (HPO4)2– substitution, must also play a significantrole.

The removal of phosphorus from wastewaters is becoming very common, to meet water quality targets, and avoid environmental problems related to eutrophication. At the same time, agricultural application of P-rich sewage biosolids is diminishing for reasons of logistics and of public pressure. As a result P from wastewaters is ultimately disposed of in landfills. Over the long term, phosphate ore reserves will become depleted. Recycling of P from wastewaters may thus be a realistic prospect if scientific and technical issues can be resolved. At the centre of the scientific problems lie considerations about optimizing phosphate precipitation as Ca phosphates. A number of Ca phosphate minerals exist, although by far the most common of these is hydroxylapatite. Precipitation kinetic considerations, however, suggest that other Ca phosphates (such as brushite, octacalcium phosphate, whitlockite, monetite or amorphous Ca phosphate) may initially precipitate, and later recrystallize into the most stable hydroxylapatite. This article reviews the complex precipitation mineralogy, chemistry and kinetics of Ca phosphates.

The mineral in bones and teeth is an impure form of hydroxylapatite (HAP), the principal impurity being 2—5 wt.% carbonate. This mineral dissolves during remodelling of bone and also in dental caries as a result of the action of acids produced by osteoclasts and by bacteria, respectively. In enamel, demineralization proceeds with preferential loss of carbonate relative to phosphate. Surprisingly, in the early stages, the demineralization is subsurface. In order to facilitate the understanding of physical chemical aspects of these processes, we have undertaken studies of demineralization in model systems. We give three examples here. The first two used scanning microradiography in which the specimen is stepped across a 10—30 μm diameter X-ray beam. Intensity measurements allow calculation of the mineral mass per unit area in the X-ray path through the specimen. In the first experiment, porous HAP sections were separated from a reservoir of acidic buffer by a column initially filled with water (the diffusion length) and scanned with the X-ray beam perpendicular to the axis of the diffusion length. The rate of total loss of mineral along each profile was calculated from the scans. The rate of demineralization fell as the diffusion length increased. We believe the explanation is that the rate-controlling step is the diffusion of dissolved HAP away from the solid to the buffer reservoir. In the second experiment, demineralizing solution and water were pumped alternately, for equal lengths of time, past blocks of porous HAP or enamel. The X-ray beam was perpendicular to the exposed surface. As the rate of switching between solutions decreased, the mean rate of demineralization also fell. We propose that this effect is due to retention of acid in the pores of the HAP during the time when water flows, allowing further demineralization to take place during this time. The third study used X-ray microtomography, a form of 3D microscopy, to study the loss of mineral in compacted carbonate apatite powders. The powders were packed in six 10 mm internal diameter acrylic cylinders to a depth of 4 mm (after pressing). One end was covered with a porous polyethylene disc and each tube placed in acidic buffer for 70 days. Periodic examination by microtomography showed the development of subsurface demineralization. Infrared spectroscopy of the dissected-out surface layers showed preferential loss of carbonate over phosphate by comparison with deeper layers. Rietveld analysis of X-ray powder diffraction data showed changes in the crystallographic structures of the apatites between the initial and dissected-out apatite.

Ancient ivory, from the Chengdu Jinsha and Guanghan Sanxingdui sites in China, has been buried for several thousand years. In order to determine the degradation mechanisms and to provide a scientific basis for protecting them, these ancient ivory samples have been compared with modern ivory using infrared spectroscopy in the frequency range 400–4000 cm–1. By combining chemical analysis data we compare the crystallinity and crystal chemistry of the apatite component, as well as the structural characteristics of the ivory. These investigations showed that the ancient ivory consists almost entirely of hydroxyl-carbonate apatite as the predominant phase. Compared with the modern ivory, the PO43– and CO32– bands are stronger, the PO4RF values are obviously greater, and an extra OH– band at 3569 cm–1 is observed in the ancient ivory. These results indicate that there is a greater degree of apatite crystallinity in the ancient ivory and also imply that there has been incorporation and recrystallization of CO32– in the apatite during burial. Positive correlations have been found between the apatite crystallinity, CO32– and OH– ion contents, and burial time. The organic matter in ancient ivory has been lost or decomposed as the organic bands (e.g. at 1238 cm–1 and 1337 cm–1) have disappeared. This may be the main reason that ancient ivory is easily dewatered and readily friable after being unearthed.

Arsenic(V) removal from aqueous solution following addition of either a mixture of synthetic hydroxylapatite and baryte or bone-char is discussed. Arsenic concentrations of 4, 10 and 100 mg/l were investigated and additions of 0.2—10 g/l of solid (hydroxylapatite, baryte or bone-char) were tested, at an initial pH of either 5 or 7. Although the mixture of hydroxylapatite and baryte had a small influence on arsenic concentrations, bone-char was found to be a very effective sorbing agent for arsenic(V). Packed-column studies to investigate the bone-char capacity, followed by leaching tests were carried out. The capacity of bone-char was found to be superior to that of granular activated carbon. The experiments presented here indicate that the mechanism involved is adsorption rather than co-precipitation.

A CO-bearing member of the hydroxylapatite–hydroxylellestadite series occurs as a Si-rich part of a hydroxylapatite–hydroxylellestadite series mineral (hydroxylapatitess) in a skarn xenolith from Tadano, Fukushima Prefecture, Japan. Hydroxylapatitess is composed of Si-poor and Si-rich parts. The Si-poor part is F-rich hydroxylapatite. The infrared spectrum of the Si-rich part demonstrates the presence of B-type CO3. A representative analysis of the Si-rich part yielded the empirical formula Ca4.989[(PO4)1.315 (SiO4)0.848 (SO4)0.368(CO2.943)0.480]∑3.011(OH0.629 Cl0.264 F0.107)∑1.000 on the basis of 8 cations, assuming Si = S + C. There is a very strong inverse correlation between Si and P in both the Si-poor and Si-rich parts. These data indicate that the substitution mechanism (SO4,CO3)2– + (SiO4)4– = 2(PO4)3– probably occurs in hydroxylapatite ss. Therefore, it was concluded that the Si-rich part corresponds to a CO3-bearing hydroxylapatite–hydroxylellestadite series mineral with CO3 partially replacing SO4. Most of the Si-rich part shows CO3 > SO4 and its composition approaches Ca5(SiO4)1.5(CO3,SO4)1.5(OH,Cl,F).