FT-Raman spectroscopy of lichens on dolomitic rocks: an assessment of metal oxalate formation

The FT-Raman spectra of five epilithic lichen taxa growing on dolomite and magnesium-rich carbonate rocks have been analysed and interpreted for the key molecular marker bands associated with calcium oxalate monohydrate (whewellite), calcium oxalate dihydrate (weddelite) and magnesium oxalate dihydrate. From the results, it can be concluded that the biomineral product of lichen biodeterioration involves the calcareous part of the substratum only; no trace of magnesium oxalate has been found in the Raman spectra. Two of the species, Lecanora sulfurea and Aspicilia calcarea, produce calcium oxalate monohydrate exclusively, but Dirina massiliensis f. sorediata, D. massiliensis f. massiliensis and Tephromela atra produce significant quantities of the dihydrate. An explanation is advanced for the exclusive accumulation of calcium oxalate into the lichen thallus despite the significant presence of magnesium ions.     

Diphenyl carbazone as an internal indicator in volumetric analysis

Summary A method for the volumetric determination of calcium using diphenyl carbazone as indicator has been described. Calcium is precipitated by excess sodium oxalate, the excess oxalate being determined by standard lead nitrate. A study of the possible interferences of barium and magnesium in the above determination is undertaken and it is shown that the above procedure is applicable to the determination of calcium in the presence of magnesium and barium.Sincere thanks of the authors are due to Professor G. B. Singh for providing the necessary facilities during the course of the above investigation.     

Thermal, UV, FTIR, and XRD studies of urinary stones

Various crystals are seen in human urine. Oxalate, Phosphate, Uric acid, and Urate crystals are generally seen in urinary calculi. Calcium stones are most common, comprising 75 % of all urinary calculi. They may be pure calcium oxalate or calcium phosphate or a mixture of both. Many stones are not homogeneous. Low calcium intake increases the intestinal absorption of calcium, thus decreasing the amount of calcium available in the intestinal tract to form insoluble complexes with Oxalate. Consequently, a higher amount of oxalate is available for intestinal absorption and as a result, urinary oxalate excretion increases. Mineral water consumption did not reduce urinary oxalate excretion. High urinary excretion and concentration of magnesium decrease both the nucleation and growth rates of calcium oxalate crystals in urine, because of the higher solubility of magnesium oxalate compared with calcium oxalate. Analytical results show calcium oxalate to be one of the major inorganic components of renal stones and found to be present in almost all kidney and bladder stones. About 39.5 % of the total composition of the calculi is found to contain purely calcium oxalate and also hydroxyl apatite. The ten samples are a mixture of calcium oxalate and phosphate stones. Four samples are calcium oxalate as major composition and the remaining are calcium phosphate as major composition. These kidney stones are taken photographically and size of the stone are measured using optical microscopy. These qualitative analyses are also confirmed by UV, FTIR, DSC, and XRD analysis.     

A rapid complexometric scheme for analysis of iron, aluminium, calcium and magnesium in slags

A simple and rapid complexometric method has been developed for the simultaneous determination of iron, aluminium, calcium and magnesium in a single solution in slags. Phosphorous and small amounts of chromium (1.5 mg) and vanadium (1 mg) do not interfere in the titration. Titanium and manganese are suitably masked with lactic acid and tetra sodium pyrophosphate, respectively. In a suitable aliquot, iron is titrated at pH 2 with EDTA, using sulphosalicylic acid as indicator. To this solution, excess disodium 1,2-cyclohexane diamine tetra acetic acid (DCTA) is added and aluminium is titrated by titrating the excess DCTA with standard copper sulphate solution at pH 3.5, using 1-(2-pyridylazo)-2-naphthol (PAN) as an indicator. A known excess of EDTA is added, the pH is raised to 10 and calcium and magnesium are jointly titrated by titrating the excess EDTA with copper sulphate solution, using PAN indicator. The Ca-EDTA complex is demasked with ammonium oxalate at pH 5 and the released EDTA equivalent to calcium is titrated with copper sulphate solution at pH 10 with PAN indicator. Results of analysis compare favourably with certified values and values obtained by standard methods for BCS and other slags. A set of five samples can be analysed for iron, aluminium, calcium and magnesium in four hours as compared to three days by the classical conventional method.     

Thermal studies on beryllium,magnesium and calcium hafnyl oxalates

Beryllium hafnyl oxalate tetrahydrate, magnesium hafnyl oxalate tetrahydrate and calcium hafnyl oxalate tetrahydrate abbreviated as BHO, MHO and CHO, respectively, have been prepared in an aqueous medium and characterized by elemental analysis, magnetic susceptibility measurements and infrared spectral data. The thermal behaviour of these compounds in non-isothermal conditions have been investigated by employing TG, DTG and DSC techniques. The intermediates obtained at the end of various thermal decomposition steps were identified on the basis of elemental analysis and infrared spectral studies. The graphical method of Coats and Redfern has been employed to evaluate the kinetic parameters such as apparent activation energy and order of reaction. Heat of reaction for different decomposition steps have been calculated from the DSC curves.     

Compleximetric determination of calcium in impure calcium carbonate and limestone

Calcium is determined in impure calcium carbonate and limestone samples by titrating with 0.01 M disodium EGTA at pH 12 in the presence of at least 0.6 mg of magnesium and a maximum of 500 μg of iron(III), using a pH 12.5 sodium hydroxide-potassium cyanide-sodium sulfide buffer and Calcon indicator. The results of such titrations are compared with those obtained by titrating at pH 10 the calcium perchlorate solutions derived from calcium oxalate, and with those of a modified LEWIS AND MELNICK method. The results for magnesium (% MgO) obtained by difference are in fair agreement. Magnesium can be titrated compleximetrically as magnesium perchlorate, but the reagent blank must be determined.     

The use of thermal analysis in determination of some urinary calculi of calcium oxalate

The human urinary calculi are mainly constituted by calcium oxalate, magnesium ammonium phosphate hexahydrate, and uric acid. The ions or molecules are easily characterized by wet chemical methods. The difficulties appear in the differentiation of the hydrates of calcium oxalate (monohydrate COM or Whewellite, and dihydrate COD or Weddelite). A high level of COD in the urinary stones leads, often, inflammation, sharp pain and blood in urine. In the worse cases, they must be extracted by surgical way. The identification of the main components of urinary calculi, the knowledge of the true number of water molecules bounded to the calcium oxalate, and the determination of each hydrate in the mixture, are the interests of this memory. The thermal analysis (simultaneous DTA-TG) was applied on thirty-three urinary calculi. The determination of the calcium oxalate hydrates was confirmed by calorimetry (DSC). This revised version was published online in July 2006 with corrections to the Cover Date.     

Value of the urinary stone promoters/inhibitors ratios in the estimation of the risk of urolithiasis

An imbalance between urinary-promoting and -inhibiting factors has been suggested as more important in urinary stone formation than a disturbance of any single substance. To investigate the value of promoter/inhibitor ratios for estimation of the risk of urolithiasis, urinary citrate/calcium, magnesium/calcium oxalate, and oxalate/citrate x glycosaminoglycans ratios were determined in 30 children with urolithiasis, 36 children with isolated hematuria, and 15 healthy control children. The cutoff points between normal children and children with urolithiasis, accuracy, specificity, and sensitivity for each ratio were determined and compared with those of the 24-h urine calcium and oxalate excretion and urine saturation calculated with the computer program EQUIL 2. The neural network application (aiNET Artificial Neural Network, version 1.25) was used for the determination of the cutoff points for the classification of normal children and the urolithiasis group. The best test for differentiating stone formers from non-stone formers proved the aiNET determined cutoff values of oxalate/citrate x glycosaminoglycans ratio. The method showed 97.78% accuracy, 100% sensitivity, and 93.33% specificity. Two cutoff points between normal and urolithiasis groups were found showing that the children with urolithiasis had ratio values either above 34.00 or less than 10.16. Increased oxalate excretion was linked to the first cutoff value (34.00), and decreased glycosaminoglycans excretion was typical of the second cutoff value (10.16).     

Simultaneous determination of calcium and magnesium by derivative spectrophotometry in pharmaceutical products

First- and second-derivative spectrophotometric methods for the simultaneous determination of calcium and magnesium in their mixtures are described. The methods are based on the colored complexes formed by calcium and magnesium with bromopyrogallol red in presence of Tween 80 as a surfactant. The zero-crossing method has been utilized to measure the first- and second-derivative value of the derivative spectrum. Calcium (0.8-4.8microgml(-1)) is determined in the presence of magnesium (0.5-3.5microgml(-1)) at the pH 10 and vice versa at zero-crossing wavelengths of 544.5 and 570nm in the first-derivative procedure and 574 and 531nm in the second-derivative procedure, respectively. The detection limits achieved were 0.0575microgml(-1) of calcium and 0.03microgml(-1) of magnesium. The relative standard deviations were in all instances less than 2%. The proposed method has been applied to the simultaneous determination of calcium and magnesium in different samples: commercial multivitamin, human serum and drinking water where excellent agreement between reported and obtained results was achieved.     

Phytate Dephosphorylation Products Also Act as Potent Inhibitors of Calcium Oxalate Crystallization

Phytate has been classified as an anti-nutrient, but there are no adverse effects from the consumption of a balanced diet with 1 to 2 g of daily phytate (inositol-hexaphosphate, InsP6) as a calcium magnesium salt, the form naturally present in grains. Furthermore, recent research has shown that phytate consumption may prevent pathological calcifications, such as kidney stones and cardiovascular calcifications. However, many endogenous and exogenous enzymes can hydrolyze phytate to lower inositol phosphates (InsPs) that also have biological activity. We performed a controlled hydrolysis of phytate and identified the products (InsPs) using tandem mass spectrometry (MS/MS). The total level of all InsPs was measured using a non-specific methodology. In addition, we evaluated the effects of the InsP6 hydrolysates on calcium oxalate crystallization using scanning electron microscopy and measuring the time needed for the induction of crystallization. Our results indicate that InsP6 and its hydrolysis products functioned as effective inhibitors of calcium oxalate crystallization. Thus, even though InsP6 is hydrolyzed after consumption, the enzymatic products also have the potential to reduce pathological calcifications. Finally, although it is useful to measure the overall level of InsPs in biological fluids, such as urine, there is a need to develop simple analytical methods to quantify the level of individual InsPs.     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

Rapid visual compleximetric titration of calcium in natural waters

Visual compleximetric methods for the titration of calcium in the presence of magnesium have been based either on masking the magnesium or using an indirect indicator procedure, e.g., the system Zn-EGTA-Zincon. In the proposed method these two approaches are combined. Zn-EGTA complex is added to the mixture and the zinc liberated in the calcium replacement reaction is titrated with EGTA after the magnesium has been masked with fluoride ion.     

无机钙材料在石灰岩文物表面防护中的应用

由于碳酸盐矿物的质地特点,石灰岩文物在露天环境中极易发生表面溶蚀,其上赋存文化信息的文字、纹饰和符号等雕刻痕迹也随之湮灭,对其文物价值造成了严重减损。从耐候性和兼容性角度考虑,无机保护材料显然更适合于石灰岩文物的表面防护处理。近年来,基于草酸钙、磷灰石和碳酸钙等钙基材料的石灰岩文物表面防护研究逐渐兴起并开始走向应用。本文就上述钙基保护材料的特点、防护膜制备和应用实践等做了归纳和评述,以期为石灰岩文物保护研究提供参考和借鉴。     

FT-Raman spectroscopic study of calcium-rich and magnesium-rich carbonate minerals

Calcium and magnesium carbonates are important minerals found in sedimentary environments. Although sandstones are the most common rock colonized by endolith organisms, the production of calcium and magnesium carbonates is important in survival strategies of organisms and as a source for the removal of oxalate ions. Extremophile organisms in some situations may convert or destroy carbonates of calcium and magnesium, which gives important information about the conditions under which these organisms can survive. The identification on the surface of Mars of 'White Rock' formations, in Juventae Chasma or Sabaea Terra, as possibly carbonate rocks makes the study of these minerals a prerequisite of remote Martian exploration. Here, we show the protocol for the identification by Raman spectroscopy of different calcium and magnesium carbonates and we present a database of relevance in the search for life, extinct or extant, on Mars; this will be useful for the assessment of data obtained from remote, miniaturized Raman spectrometers now proposed for Mars exploration.     

石质文物表面生物矿化保护材料的仿生制备

许多濒危石质文物急需进行保护处理. 但是, 调查表明已经使用过的表面防护材料很难令人满意, 探索新的石质文物保护材料已是当务之急. 本工作以石质文物表面天然生成的生物矿化膜为仿生合成目标, 依据生物矿化的原理, 以硫酸软骨素作为有机模板, 草酸钙的亚稳过饱和溶液作为无机前驱物, 室温下在石材表面仿生合成了主要成分为一水草酸钙的无机表面保护材料. 其制备工艺用正交试验进行了优化; 结构和形貌用X射线衍射分析仪和原子力显微镜进行了表征; 通过憎水性、耐污性和耐酸性试验进行了合成膜的保护性能测试, 效果良好. 本方法为开拓新的石质文物保护材料提供了思路.     

Characterization of hot particles in surface soil around the Chernobyl NPP

An ICP-AES method for the analysis of trace amounts of lanthanides and yttrium in sodium or magnesium diuranate samples (yellow cake) and other beneficiation product generated during the uranium extraction process (hydrometallurgy) from its ores is described. Most of the matrix elements are removed by an initial oxalate precipitation of lanthanides using calcium as carrier. A solvent extraction procedure using a mixture of mono 2-ethylhexyl dihydrogen phosphate (H₂MEHP) and bis (2-ethylhexyl) hydrogen phosphate (HDEHP) is used for the removal of calcium, iron and the occluded uranium. A combination of oxalate precipitation and solvent extraction procedure is applied for the selective separation and preconcentration of traces of lanthanides from yellow cake and iron cake samples. The solvent extraction procedure is directly applied for the separation of lanthanides from the uranium leach liquor and lime cake. The accuracy of the method is checked by analyzing synthetic mixture containing known amounts of traces of lanthanides and also by comparing with another standard separation procedure like ion exchange method, and the recovery was better than 95%. The method is rapid, simple, accurate and suitable for the separation of lanthanides from uranium, iron and calcium rich materials. The precision of the method is characterized by an RSD of 2 to 4%.     

氧化镁标准物质的研制

介绍氧化镁标准物质的研制过程，氯化镁轻重结晶提纯，与草酸铵反应制得草酸镁，将草酸镁煅烧制备成氧化镁标准物质，采用称量滴定法进行定值，实验结果表明，该标准物质定值结果准确，均匀性，稳定性良好，满足实际工作的需要。     

Procedure for determination of trace ions in boric acid by matrix volatilization-ion chromatography

A method for determination of anions and cations in boric acid is proposed by matrix volatilization. The boric acid matrix was eliminated as trimethyl borate ester in a vapour phase matrix elimination (VPME) system using a mixture of glycerol-methanol. In this VPME system, in situ reagent purification, sample decomposition and digest evaporation were achieved in a single step. Trace anions were separated on anion-exchange column (IonPac AS17) by an isocratic elution with 15 mM sodium hydroxide and the cations on a cation-exchange column (IonPac CS12) by 20 mM hydrochloric acid as eluents. Method detection limits (3sigma) for most ions ranged from 0.3 to 8 ng/g (ppb). Recovery experiments combined with comparison of data obtained by other methods were employed to verify the accuracy of the proposed method. Application of the method to determine trace levels of anions like acetate, oxalate, sulfate, phosphate and cations such as lithium, sodium, potassium, magnesium and calcium in two highly pure grades of boric acid using ion chromatography is demonstrated.     

Influence of PSSS additive and temperature on morphology and phase structures of calcium oxalate

Calcium oxalate (CaOx) particles with different morphologies and phase structures were prepared by a facile precipitation reaction of sodium oxalate with calcium chloride in the absence and presence of poly(sodium 4-styrene-sulfonate) (PSSS) at different temperatures. The as-prepared products were characterized with scanning electron microscopy and X-ray diffraction. The influence of experimental conditions including pH, temperature, and concentration of PSSS and CaC2O4 on the morphologies and phase structures of the prepared calcium oxalate particles were investigated. It was found that variations in the concentration of PSSS and CaC2O4, temperature, and pH significantly influenced the crystal structure, morphology, and particle size of the samples. Various crystal morphologies of calcium oxalate, such as plate, leaf-shaped, bipyramid, and cylinder could be fabricated, depending on the experimental conditions. Higher PSSS concentration and reaction temperature favored the formation of metastable calcium oxalate dihydrate (COD) crystals and stable calcium oxalate monohydrate (COM), respectively. Especially, cylinder-shaped CaC2O4 particles were obtained at 80 degrees C in the presence of PSSS for the first time. This research may provide new insight into understanding and potentially regulating the formation of kidney stones and the control of morphology and phase structures of calcium oxalate particles.     

Selective preconcentration of rare earth elements by substoichiometric precipitation of calcium oxalate and its application to the neutron activation analysis of biological material

A preconcentration method for trace amounts of rare earth elements (REs) based on the substoichiometric precipitation of calcium oxalate was developed. RE(III) was quantitatively coprecipitated with calcium oxalate which had been precipitated from the calcium of a macrocomponent in a biological sample by addition of a substoichiometric amount of oxalate. In this way high selectivity for RE(III) from other elements was achieved. The method was applied to the neutron activation analysis of a biological sample (NBS SRM 1572 Citrus Leaves), and Sc, La, Ce, Pf, Nd, Sm, Eu, Th, Dy, Ho, Yb and Lu were determined with a relative standard deviation of less than 5%.