A unique late-onset intraocular lens opacification 23 years after implantation: a clinical and laboratory case report.

We report an unusual, rare case of opacification of the hydrophilic acrylic intraocular lens (IOL) 23 years after the initial surgery with significant visual deterioration. Opacification of the hydrophilic acrylic IOL was primarily due to the formation of folds on the surface of the lens material, and less so due to calcium phosphate deposits. Calcification opacification can be attributed to recent events, as evidenced by deposits of dicalcium phosphate dihydrate (CaHPO42H2O) and octacalcium phosphate (Ca8H2(PO4)65H2O), both of which are transient calcium phosphate phases, converting hydrolytically to the thermodynamically most stable hydroxyapatite (Ca10(PO4)6(OH)2). To our knowledge, this case of hydrophilic acrylic IOL opacification is the only one that has been described so late, 23 years after cataract surgery.

Explantation of a sutureless scleral fixated Carlevale intraocular lens due to calcification: a clinical and laboratory report.

BACKGROUND: Hydrophilic intraocular lens opacification is a rare complication due to calcification. With current new surgical techniques, including lamellar endothelial keratoplasty and vitrectomies, this irreversible complication is becoming more common. In this case study, we present clinical and laboratory features of a case of Carlevale hydrophilic acrylic IOL calcification. CASE PRESENTATION: Observational case report of a single incident case. An 83-year-old man was referred to our ophthalmic department complaining of right eye vision blurring for six months. Slit-lamp biomicroscopy revealed IOL opacification. Deposits of calcium phosphate were found both on the IOL's surface and inside it, according to thorough investigation using optical, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectrometry. CONCLUSIONS: To the best of our knowledge, this is the first case to describe the laboratory evidence of Carlevale hydrophilic IOL calcification, suggesting possible explanation mechanisms based on underlying pathology and surgical technique. It reminds us that these findings suggest that physicians should be aware of possible hydrophilic IOL calcification.

Calcium Carbonate Mineralization of Microalgae.

Biological substrates catalyze the nucleation and growth of sparingly soluble salts however, the underlying mechanism is largely unknown. In the present study, the growth of calcium carbonate (CaCO3), on Acutodesmus obliquus (AO) microalgae was investigated. The test microalgae favored the growth of CaCO3 from solutions supersaturated with respect to calcite (7.94 < SRcalcite < 104.71). The precipitation of calcite on AO was not preceded by measurable induction times, and the rates of calcite crystal growth were higher for higher microalgae cell concentrations. The presence of the microalgae cultivation medium and illumination of the supersaturated solutions accelerated the precipitation of CaCO3, increasing the rate by 75% in comparison with the respective value in its absence. AO cultures, air dried at 25 °C yielded higher precipitation rates, in comparison with the respective rates in the presence of active AO cultures. At 70 °C, nucleation and growth were suppressed, due to the destruction of the molecular structure of the microalgae. The CaCO3 precipitation rates on calcite precipitated on air-dried AO culture, were doubled in comparison with the respective rates obtained with the respective quantities of each component of the composite substrate.

Decellularized tissue-engineered heart valves calcification: what do animal and clinical studies tell us?

Cardiovascular diseases are the first cause of death worldwide. Among different heart malfunctions, heart valve failure due to calcification is still a challenging problem. While drug-dependent treatment for the early stage calcification could slow down its progression, heart valve replacement is inevitable in the late stages. Currently, heart valve replacements involve mainly two types of substitutes: mechanical and biological heart valves. Despite their significant advantages in restoring the cardiac function, both types of valves suffered from serious drawbacks in the long term. On the one hand, the mechanical one showed non-physiological hemodynamics and the need for the chronic anticoagulation therapy. On the other hand, the biological one showed stenosis and/or regurgitation due to calcification. Nowadays, new promising heart valve substitutes have emerged, known as decellularized tissue-engineered heart valves (dTEHV). Decellularized tissues of different types have been widely tested in bioprosthetic and tissue-engineered valves because of their superior biomechanics, biocompatibility, and biomimetic material composition. Such advantages allow successful cell attachment, growth and function leading finally to a living regenerative valvular tissue in vivo. Yet, there are no comprehensive studies that are covering the performance of dTEHV scaffolds in terms of their efficiency for the calcification problem. In this review article, we sought to answer the question of whether decellularized heart valves calcify or not. Also, which factors make them calcify and which ones lower and/or prevent their calcification. In addition, the review discussed the possible mechanisms for dTEHV calcification in comparison to the calcification in the native and bioprosthetic heart valves. For this purpose, we did a retrospective study for all the published work of decellularized heart valves. Only animal and clinical studies were included in this review. Those animal and clinical studies were further subcategorized into 4 categories for each depending on the effect of decellularization on calcification. Due to the complex nature of calcification in heart valves, other in vitro and in silico studies were not included. Finally, we compared the different results and summed up all the solid findings of whether decellularized heart valves calcify or not. Based on our review, the selection of the proper heart valve tissue sources (no immunological provoking residues), decellularization technique (no damaged exposed residues of the decellularized tissues, no remnants of dead cells, no remnants of decellularizing agents) and implantation techniques (avoiding suturing during the surgical implantation) could provide a perfect anticalcification potential even without in vitro cell seeding or additional scaffold treatment.

A novel anticalcification treatment strategy for bioprosthetic valves and review of the literature.

BACKGROUND AND AIM OF THE STUDY: Glutaraldehyde (Glut) fixed bioprosthetic valves fail due to progressive dystrophic calcification. Many treatments have been proposed to eliminate calcification but none have been entirely successful. Calcitonin (CT) and sodium bisulfite (BSF) have recently been introduced as independent anticalcification reagents. It is postulated that their combined effect, along with the addition of the detergent Tween 80 and alcohol at 37°C, may efficiently minimize tissue calcification due to aldehyde adduct formation and elimination of lipids. MATERIAL AND METHODS: Three groups were created from porcine aortic leaflets: group I (Glut only), group II (Glut with 1% CT, 12.5% BSF, and 1.2% Tween 80 at 37°C), and group III (Glut with 1% CT, 10% BSF, 1.2% Tween 80, and 20% alcohol at 37°C). All tissues were implanted subdermally in three sets of eight (group I), six (group II), and five (group III) Wistar rats. After 4 months, the tissues were retrieved and lyophilized at -40°C at 100 mm Hg. The calcium was measured with a flat atomic absorption technique. RESULTS: The preimplantation calcium (Ca) concentration in mg Ca/gram of tissue was 1.79 ± 0.14 in group I, 1.65 ± 0.28 in group II, and 0.72 ± 0.79 in group III (P = ns). After 4 months, the Ca concentration was 277.55 ± 32.52, 103.54 ± 5.39 (P < .001) and 42.02 ± 15.63 (P < .001), respectively. There was also a significant difference (P < .001) between groups II and III. CONCLUSION: The combination of CT and BSF along with the detergent Tween 80 and alcohol at 37°C mitigates the calcification efficiently as compared to Glut treatment only.

Calcitonin as an anticalcification treatment for implantable biological tissues.

BACKGROUND AND AIM OF THE STUDY: Calcification remains the major role of failure of implantable biomedical material and in particular of bioprosthetic valves. Various treatments have been proposed to mitigate calcification of glutaraldehyde-fixed bioprosthetic valves but none have succeeded in inhibiting or mitigating efficiently the calcification process of the implantable biological tissues. Since the discovery of calcitonin (CT) and its therapeutic role in treating hypercalcemic patients, CT has never been tried as an anticalcification treatment for biomaterials. It is postulated, that tissue calcification may be efficiently minimized by forming adducts with aldehyde groups thus eliminating the places of the biological tissues onto the calcium cations could be deposited. MATERIAL AND METHODS: Fresh porcine aortic leaflets were cut radially in three parts. Three groups of tissue were created. Group I (glutaraldehyde only), Group II (glutaraldehyde with 1% CT) and Group III (glutaraldehyde with 10% CT). All tissues were then implanted subdermally in three sets of 8 (Group I) and 9 (Group II and Group III) male Wistar rats of 12 days old. 21 days later the rats were euthanized by inhalation of CO2. The tissues were retrieved and after rinsing with distilled water 3 times, were lyophilized at -40°C at high vacuum pressure of approximately 100mmHg for 16h. The calcium content was then measured with flat atomic absorption technique. RESULTS: The preimplantation values of Ca concentration as expressed in mg Ca/g of tissue were 1.79±0.14 in Group I, 4.78±0.0079 in Group II and 2.88±0.17 in Group III (p=ns). 21 days later the values of Ca concentration were 126.95±12.97 for Group I, 24.69±2.71 for Group II (p<0.05) and 27.16±2.95 for Group III (p<0.05). There was not significance difference between Groups II and III, even if Group II showed a less accumulation of Ca concentration (×5.16) than Group III (×9.43). CONCLUSION: An anticalcification treatment based on calcitonin as an additive to buffered glutaraldehyde, mitigates the calcification process of the implantable biological tissues, as compared to glutaraldehyde treatment only.

Physicochemical characterization of sterilized muds for pharmaceutics/cosmetics applications.

Clays and muds have been used for centuries as cosmetics or pharmaceutical products for various therapies. The suitability of muds and clays for health- and beauty-related applications depends on their physicochemical properties, mineralogical composition, particle characteristics and toxicity. In this work, the physicochemical characterization of 12 mud specimens from different natural spa resorts in Greece and one from Israel (Dead Sea) is presented. All specimens were sterilized at 121 °C for 20 min, because of their intended use. The Greek mud specimens were collected from various locations in Macedonia, Western Greece and Northeast Aegean. All muds were characterized concerning their mineralogical, chemical components as well as their morphological characteristics using appropriate methods [powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), nitrogen absorption specific surface area measurements (BET), scanning electron microscopy and energy dispersive X-ray spectroscopy]. The concentrations of F-, Cl-, NO3- and SO42- anions at equilibrium with the mud specimens were measured by ion chromatography. Total calcium concentration was measured using atomic absorption spectroscopy, and the concentration of total N, C, H and S in the solids was measured using elemental analysis. Moreover, total phenolic concentration (TPC) in distilled water equilibrated with the mud specimens was measured as an index for their antioxidant properties. Several muds were found to present high TPC. Several of the examined mud specimens were found to have the potential use as pharmaceuticals or cosmetics. Based on the physicochemical characteristics of the mud specimens examined, possible improvement in their use and applicability has been suggested.

Calcification of Hydrophilic Acrylic Intraocular Lenses With a Hydrophobic Surface: Laboratory Analysis of 6 Cases.

PURPOSE: To investigate the nature and characteristic features of deposits causing opacification of intraocular lenses (IOLs) based on the examination of clinical findings using scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDX) analysis. DESIGN: Retrospective, observational case series. METHODS: This is a multicenter study of 6 hydrophilic acrylic IOLs (Lentis LS-502-1; Oculentis GmbH, Berlin, Germany) with a hydrophobic surface that were explanted from 5 patients because of opacification. Three patients had an uncomplicated phacoemulsification. One patient underwent combined phacoemulsification and pars plana vitrectomy for retinal detachment and later silicone oil endotamponade owing to redetachment. The last patient had a pars plana vitrectomy and silicone oil instillation combined with phacoemulsification for tractive retinal detachment and diabetic retinopathy. The explanted lenses were submitted to our laboratory and were examined by SEM and EDX in order to identify the morphologic features and the composition of the deposits. RESULTS: SEM and EDX analyses confirmed the presence of calcific deposits in the interior of the opacified hydrophilic IOLs, with a pattern showing the formation of lumps on the surface. The lumps were due to subsurface formation of calcium phosphate crystalline deposits. The crystallite clusters seemed to diffuse from the IOL interior to the surface. CONCLUSIONS: We demonstrated the calcification pattern of the hydrophilic IOL (Lentis LS-502-1) with a hydrophobic surface. Although hydrophilic acrylic lenses have a hydrophobic surface, the development of calcification is a possible threat initiating from the hydrophilic subsurface of the IOLs.

Organized Silica Films Generated by Evaporation-Induced Self-Assembly as Hosts for Iron Oxide Nanoparticles.

In this work, we prepared oriented mesoporous thin films of silica on various solid substrates using the pluronic block copolymer P123 as a template. We attempted to insert guest iron oxide (FexOy) nanoparticles into these films by two different methods: (a) by co-precipitation-where iron precursors are introduced in the synthesis sol before deposition of the silica film-and subsequent oxide production during the film calcination step; (b) by preparing and calcining the silica films first then impregnating them with the iron precursor, obtaining the iron oxide nanoparticles by a second calcination step. We have examined the structural effects of the guest nanoparticles on the silica film structures using grazing incidence X-ray scattering (GISAXS), high-resolution transmission electron spectroscopy (HRTEM), spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), and Raman microscopy. Formation of nanoparticles by co-precipitation may induce substantial changes in the film structure leading, in our adopted process, to the appearance of lamellar ordering in the calcination stage. On the contrary, impregnation-based approaches perturb the film structures much more weakly, but are also less efficient in filling the pores with nanoparticles.

Detachment strength of human osteoblasts cultured on hydroxyapatite with various surface roughness. Contribution of integrin subunits.

Hydroxyapatite (HA) has been widely used as a bone substitute in dental, maxillofacial and orthopaedic surgery and as osteoconductive bone substitute or precoating of pedicle screws and cages in spine surgery. The aim of the present study was to investigate the osteoblastic adhesion strength on HA substrata with different surface topography and biochemistry (pre-adsorption of fibronectin) after blocking of specific integrin subunits with monoclonal antibodies. Stoichiometric HA was prepared by precipitation followed by ageing and characterized by SEM, EDX, powder XRD, Raman spectroscopy, TGA, and specific surface area analysis. Human bone marrow derived osteoblasts were cultured on HA disc-shaped substrata which were sintered and polished resulting in two surface roughness grades. For attachment evaluation, cells were incubated with monoclonal antibodies and seeded for 2 h on the substrata. Cell detachment strength was determined using a rotating disc device. Cell detachment strength was surface roughness, fibronectin preadsorption and intergin subunit sensitive.

Sand consolidation with calcium phosphate-polyelectrolyte composites.

A new method for the consolidation of loose sand formations has been developed. The method involves in situ precipitation of a composite calcium phosphate-polyelectrolyte salt that binds together with loose sand grains, thus resulting to their consolidation. Three different polyelectrolytes (PE) were tested, i.e., polyacrylic acid (PAA), polyallylamine hydrochloride (PAH), and polyethylenimine (PEI). The effect of PE tested on the thermodynamics and the kinetics of precipitation of calcium phosphate salts was investigated. Three types of experiments were done. Investigation of the adsorption of PE on either hydroxyapatite (Ca(5)(PO(4))(3)OH, HAP) crystals or on sand grains. Measurement of the kinetics of heterogeneous nucleation of HAP on the solid substrates and the mechanical properties of the obtained crystals in batch experiments of low and high supersaturation solutions, respectively. Evaluation of the consolidation in sand packs in order to investigate the effectiveness of the method. The crystallization rates, R(p), on HAP crystals in the presence of the PE tested were found in the order R(p)(PAA)>R(p)(PEI)>R(p)(PAH), while nucleation and crystal growth on silicate sand took place only in the absence of adsorbed PE. PAH favored strongly the consolidation process, whereas PEI and PAA resulted in the formation of poorly consolidated grain agglomerates.

Experimental investigation on mechanism of hydrophilic acrylic intraocular lens calcification.

PURPOSE: To construct a model simulating intraocular lens (IOL) opacification attributable to the formation of calcium phosphate deposits and to investigate the kinetics of deposit formation. DESIGN: Prospective laboratory investigation. SETTING: Department of Ophthalmology, Medical School and Department of Chemical Engineering, Laboratory of Inorganic and Analytical Chemistry, University of Patras, Greece. STUDY POPULATION: Three hydrophilic acrylic IOLs (26% water content) were placed inside a 10-mL double-walled thermostated reactor simulating the anterior chamber. Simulated aqueous humor was injected continuously into the reactor using a pump with variable speed. OBSERVATION PROCEDURES: The observation of IOLs was carried out in situ daily by optical microscopy. Scanning electron microscopy and energy-dispersive radiographic spectroscopy were used for the identification of the morphologic features and the composition of the deposits. RESULTS: The lenses were removed and inspected 5, 9, and 12 months after the initiation of the experiment. Investigation showed deposits of calcium phosphate crystallites in the interior of opacified IOLs. However, these deposits were not observed on the surface of the IOLs. CONCLUSIONS: In agreement with earlier reports by our group and in the literature, IOL opacification is the result of calcification. It is suggested that the surface hydroxyl groups of the polyacrylic polymeric components of the IOLs are capable of inducing surface nucleation and crystal growth of calcium phosphates. However, most important is the finding that the calcification of IOLs is initiated from their interior through the development of sufficiently high local supersaturation, realized through the diffusion of calcium and phosphate ions.

Adsorption of atrazine from aqueous electrolyte solutions on humic acid and silica.

The adsorption of, the still widely used, herbicide atrazine on model soil components, such as humic acid and humic acid-silica gel mixtures, was investigated in a series of batch experiments, under different experimental conditions (ionic strength, temperature, and pH). The investigation aimed at obtaining an estimate of the contribution of each of the soil components on the adsorption of atrazine from aqueous solutions. The kinetics of atrazine adsorption on humic acid showed two steps: a fast step, of a few hours duration, and a second slow step, which continued for weeks. The kinetics of adsorption data gave a satisfactory fit to the Elovich equation. Τhe adsorption of atrazine on the test substrates was found to be reversible in all cases. The atrazine uptake data on the test substrates were fitted best with the Freundlich adsorption isotherm. The ionic strength of the atrazine aqueous solutions did affect the amount of the atrazine adsorbed on the test substrates, suggesting that electrostatic forces between atrazine molecules and soil play a significant role in the adsorption process. An increase of temperature resulted in a decrease of atrazine adsorption on humic acid at low atrazine equilibrium concentrations. However, for higher levels of equilibrium concentrations (≥3 mg/L) the amount of atrazine adsorbed onto the test substrate increased as temperature increased. The calculated isosteric enthalpies of adsorption ranged between slightly exothermic at low atrazine uptake and slightly endothermic at high atrazine uptake, all values being in the range of physisorption.

Development of a new combined test setup for accelerated dynamic pH-controlled in vitro calcification of porcine heart valves.

Fifty years after their first implantation, bioprosthetic heart valves still suffer from tissue rupture and calcification. Since new bioprostheses exhibit a lower risk of calcification, fast and reliable in vitro methods need to be evaluated for testing the application of new anti-calcification techniques. This report describes a modification of the well-known in vitro dynamic calcification test method (Glasmacher et al, Leibniz University Hannover (LUH)), combined with the pH-controlled, constant solution supersaturation (CSS) method (University of Patras (UP)). The CSS method is based on monitoring the pH of the solution and the addition of calcium and phosphate ion solutions through the implementation of two syringe pumps. The pH and the activities of all ions in the solutions are thus kept constant, resulting in higher calcification rates compared to conventional in vitro methods in which solution supersaturation is allowed to decrease without any further control. To verify this hypothesis, five glutaraldehyde preserved porcine aortic valves were tested. Three of the valves were tested according to a free-drift methodology: the valves were immersed in a supersaturated calcification solution, with an initial total calcium times total phosphate product of (CaxP)=10.5 (mmol/L)2, renewed weekly. Two valves were tested by the new pH-controlled loop system, implementing the CSS methodology. All valves were tested for a 4-week period, loaded at 300 cycles per minute, resulting in a total of 12 million cycles at the end of the testing period. The degree of calcification was determined weekly by means of mux-ray, and by conventional, clinical and micro-computer tomography (CT, muCT). The results showed that the valves mineralizing at constant solution supersaturation in vitro yielded higher rates of calcification compared to the valves tested at conditions of decreasing solution supersaturation without any control, indicating the development of a new, accelerated, controllable in vitro calcification method.

Application of anodic stripping voltammetry for zinc, copper, and cadmium quantification in the aqueous humor: implications of pseudoexfoliation syndrome.

Anodic stripping voltammetric (ASV) procedure, using mercury film electrode, was optimized and applied to determine the concentrations of zinc, cadmium, and copper in the aqueous humor. Concentration levels as low as 1 ppb of the test metals was possible to be detected using short electrolysis times (120 s) and microquantities of aqueous humor (up to 35 µL). As a first application of the voltammetric analysis of trace metals in the aqueous humor, the role of the three selected trace elements in the pseudoexfoliation (PEX) syndrome was examined. Samples from aqueous humor were collected during cataract extraction from patients with and without PEX. The zinc and copper concentration levels in the aqueous humor did not show statistically significant difference in the study and control group. Cadmium was detected in a small number of samples, without however statistical differences between the two groups. ASV proved to be a highly precise and sensitive tool for the quantification of heavy metal ions in aqueous humor. Further studies may lead to useful conclusions for the role of zinc, copper, or cadmium in PEX syndrome.

Principles of demineralization: modern strategies for the isolation of organic frameworks. Part II. Decalcification.

This is the second paper on principles of demineralization. The initial paper is dedicated to the common definitions and the history of demineralization. In present work we review the principles and mechanisms of decalcification, i.e., removing the mineral Ca-containing compounds (phosphates and carbonates) from the organic matrix in its two main aspects: natural and artificial. Natural chemical erosion of biominerals (cavitation of biogenic calcareous substrata by bacteria, fungi, algae, foraminifera, sponges, polychaetes, and mollusks) is driven by production of mineral and organic acids, acidic polysaccharides, and enzymes (cabonic anhydrase, alkaline and phosphoprotein phosphataes, and H(+)-ATPase). Examples of artifical decalcification includes demineralization of bone, dentin and enamel, and skeletal formations of corals and crustacean. The mechanism and kinetics of Ca-containing biomineral dissolution is analyzed within the framework of (i) diffusion-reaction theory; (ii) surface-reaction controlled, morphology-based theories, and (iii) phenomenological surface coordination models. The application of surface complexation model for describing and predicting the effect of organic ligands on calcium and magnesium dissolution kinetics is also described. Use of the electron microscopy-based methods for observation and visualization of the decalcification phenomenon is discussed.

Opacification of hydrophilic acrylic intraocular lens attributable to calcification: investigation on mechanism.

PURPOSE: To identify the nature and to investigate the biochemical mechanisms leading to late opacification of implanted hydrophilic acrylic intraocular lenses (IOLs). DESIGN: Retrospective laboratory investigation. METHODS: setting: Department of Ophthalmology, Medical School, Department of Chemical Engineering, Laboratory of Inorganic and Analytical Chemistry, University of Patras and FORTH-ICEHT, Greece. study population: Thirty IOLs were explanted one to 12 years postimplantation attributable to gradual opacification of the lens material. observation procedures: Materials analysis was done using scanning electron microscopy (SEM) equipped with a microanalysis probe (EDS), confocal microscopy, x-ray diffraction (XRD), and Fourier transform infrared (FTIR) for the identification of the substances involved in the opacified lenses. RESULTS: SEM investigation showed plate-like as well as prismatic nanoparticle deposits of calcium phosphate crystallites on the surface and in the interior of opacified IOLs. The plate-like deposits exhibited morphology and particle size typical for octacalcium phosphate (OCP), while the respective characteristics of the prismatic nanocrystals were typical of hydroxyapatite (HAP). EDS analysis confirmed the chemical composition of the deposits. Aqueous humor analysis showed that the humor is supersaturated with respect to both OCP and HAP, favoring the formation of the thermodynamically more stable HAP, while the formation and kinetic stabilization of other transient phases is also very likely. In vitro experiments using polyacrylic materials confirmed the clinical findings. CONCLUSIONS: Hydrophilic acrylic IOLs' opacification may be attributed to the deposition of calcium phosphate crystallites. HAP is the predominant crystalline phase of these crystallites. Surface hydroxyl groups of the polyacrylic materials facilitate surface nucleation and growth.

Principles of demineralization: modern strategies for the isolation of organic frameworks. Part I. Common definitions and history.

In contrast to biomineralization phenomena, that are among the most widely studied topics in modern material and earth science and biomedicine, much less is systematized on modern view of demineralization. Biomineralized structures and tissues are composites, containing a biologically produced organic matrix and nano- or microscale amorphous or crystalline minerals. Demineralization is the process of removing the inorganic part, or the biominerals, that takes place in nature via either physiological or pathological pathways in organisms. In vitro demineralization processes, used to obtain mechanistic information, consist in the isolation of the mineral phase of the composite biomaterials from the organic matrix. Physiological and pathological demineralization include, for example, bone resorption mediated by osteoclasts. Bioerosion, a more general term for the process of deterioration of the composite biomaterials represents chemical deterioration of the organic and mineral phase followed by biological attack of the composite by microorganisms and enzymes. Bioerosional organisms are represented by endolithic cyanobacteria, fungi, algae, plants, sponges, phoronids and polychaetes, mollusks, fish and echinoids. In the history of demineralization studies, the driving force was based on problems of human health, mostly dental caries. In this paper we summarize and integrate a number of events, discoveries, milestone papers and books on different aspect of demineralization during the last 400 years. Overall, demineralization is a rapidly growing and challenging aspect of various scientific disciplines such as astrobiology, paleoclimatology, geomedicine, archaeology, geobiology, dentistry, histology, biotechnology, and others to mention just a few.

Heterogeneous nucleation and growth of calcium carbonate on calcite and quartz.

The precipitation of calcium carbonate as a binding salt for the consolidation of loose sand formations is a promising approach. The heterogeneous nucleation and growth of calcite were investigated in supersaturated solutions. The ionic activities in the solutions tested were selected so that they included both supersaturations in which crystal growth took place only following the introduction of seed particles and supersaturations in which precipitation occurred spontaneously past the lapse of induction times. In the latter case the supersaturation conditions were sufficiently low to allow the measurement of induction times preceding the onset of precipitation. The stability domain of the calcium carbonate system was established at pH 8.50, 25 degrees C, measuring the induction times in the range between 30 min and 2 h. The rates of precipitation following the destabilization of the solutions were measured from the pH and/or concentration-time profiles. The induction times were inversely proportional and rates proportional to the solution supersaturation as expected. The high-order dependence of the rates of precipitation on the solution supersaturation suggested a polynuclear growth mechanism. Fitting of the induction time-supersaturation data according to this model yielded a value of 64 mJ/m2 for the surface energy of the calcite nucleus. In the concentration domain corresponding to stable supersaturated solutions, seeded growth experiments at constant supersaturation showed a second-order dependence on the rates of crystal growth of calcite seed crystals. Inoculation of the stable supersaturated solutions with quartz seed crystals failed to induce nucleation. Raising supersaturation to reach the unstable domain showed interesting features: calcite seed crystals yielded crystal growth kinetics compatible with the polynuclear growth model, without any induction time. The presence of quartz seed crystals reduced the induction times and resulted in nucleation in the bulk solution. The kinetic data in the latter case were consistent with the polynuclear growth model and the surface energy for the newly forming embryo was calculated equal to 31.1 mJ/m2, because of the dominantly heterogeneous nature of the process.