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。     

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。     

The Determination of Trace Elements by Solid State Luminescence

Abstract

Phosphor luminescence, resulting from the incorporation of trace metal ions into a solid state crystal lattice, has been applied to the quantitative determination of lead and bismuth. The relative fluorescence intensity is linear for 15 to 100 ng of bismuth per spot on calcium carbonate. Lead(II), preconcentrated by co-precipitation with calcium oxalate, can be determined at the ng per ml level by measurement of luminescence after ignition of oxalate to oxide; results are reproducible and the calibration curve is linear up to 15 μg of lead per 100 mg of calcium oxalate precipitate.     

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.     

Thermal analysis of monument patina containing hydrated calcium oxalates

This work describes the thermal transformation of patina samples formed on the surface of dolomitic rocks used to build the Romanesque Torme's Church (Burgos, Spain). Analyses were performed using a combination of high-temperature XRD, simultaneous TG/DTA and gas mass spectrometry. The XRD analysis revealed the presence of hydrated calcium oxalates. The following three steps were proposed for the thermal transformation of the raw material: dehydration of weddellite/whewellite to form calcium oxalate, transformation of calcium oxalate to calcium carbonate, and formation of calcium oxide produced via decomposition of the calcite. DTA/TG and mass spectrometry analyses confirmed this mechanism. In addition, a high proportion of organic compounds was detected and was possibly formed via degradation of products applied for the building's conservation by the action of microorganisms attack. Mass spectrometry analysis revealed CO (and CO₂) gas evolved during the transformation of CaC₂O₄ to CaCO₃. The CO₂ gas also appears at 765 °C due to the decomposition of calcium carbonate, and it appears over a large range of temperatures due to the decomposition of organic compounds. The TG analyses performed in a CO₂ atmosphere were used to determine the percentages of Ca and Mg contained in dolomite, and the calcium carbonate formed by oxalate decomposition. DRIFTS and mass spectrometry results revealed the presence of several aliphatic and/or aromatic compounds containing CO groups.     

Thermal treatment of whewellite—a thermal analysis and Raman spectroscopic study

Thermal transformations of natural calcium oxalate monohydrate known in mineralogy as whewellite have been undertaken using a combination of thermal analysis and Raman microscopy with the use of a thermal stage. High resolution thermogravimetry shows that three mass loss steps occur at 162, 479 and 684 °C.Evolved gas mass spectrometry shows that water is evolved in the first step and carbon dioxide in the second and third mass loss steps. The changes in the molecular structure of whewellite can be followed by the use of the in situ Raman spectroscopy of whewellite at the elevated temperatures. The whewellite is stable up to around 161 °C, above which temperature the anhydrous calcium oxalate is formed. At 479 °C, the oxalate transforms to calcium carbonate with loss of carbon dioxide. Above 684 °C, calcium oxide is formed.     

Quantitative calibration of a TPD-MS system for CO and CO2 using calcium carbonate and calcium oxalate

A method is described for calibrating quantitatively a temperature-programmed decomposition, mass-spectrometric (TPD-MS) system by monitoring the gases evolved during the thermal decomposition of a chemical within the TPD reactor. A method for calibrating for evolved CO and CO₂ is described using the thermal decompositions of calcium carbonate and calcium oxalate. The method takes into account the production of CO⁺ ions from CO₂⁺ ions and secondary reactions in the thermal decomposition of calcium oxalate.     

Thermal study of unaltered and altered dolomitic rock samples from ancient monuments

In this study, the decomposition behaviour of unaltered and altered dolomitic rock samples used in Cultural Heritage buildings was studied by simultaneous TG–DTA experiments at different atmospheres, X-ray diffraction in a high-temperature chamber, and evolved gas analysis. The components of dolomite rock samples and hydrated calcium oxalate formed during the alteration processes of the rocks were characterized, and the decomposition mechanisms of these components were determined. The TG–DTA experiments carried out at CO₂ atmosphere were used to determine the carbonate compounds in the rock samples. The TG–DTA study characterized the presence of organic compounds formed during the biological degradation of the rock samples, possibly responsible of the hydrated calcium oxalate formation.     

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.     

Investigation on the drying and decomposition of sodium oxalate

The drying of sodium oxalate at various temperatures was investigated by the micro-determination of the residual water in the heated sample and of the carbon monoxide produced by thermal decomposition. Sodium oxalate heated for 2hr above 200 degrees and cooled contains less than 20 ppm of water, and may be used as a standard for titrimetry. The decomposition of sodium oxalate into sodium carbonate and carbon monoxide was investigated by non-aqueous titrimetric micro-determination of carbon monoxide. The decomposition begins at 290 degrees and heating between 200 degrees and 250 degrees is recommended for the dehydration of sodium oxalate. The decomposition is complete between 750 degrees and 800 degrees within 20 min and the sodium carbonate obtained begins to decompose at above 810 degrees .     

Sur la thermogravimétrie des précipités analytiques: Dosage du calcium

With the object of determining the best conditions of temperature to be used by the analyst for weighing to constant weight precipitates containing calcium, the authors made a detailed study of the curves of pyrolysis which they have recorded by means of the Chevenard thermobalance. The following were studied : oxalate, carbonate, oxide, precipitated sulphate and gypsum, fluoride, iodate, arsenate, molybdate, tungstate, nickel-hexanitrite, tartrate, 8-hydroxyquinolate, and picrolonate. They suggest a rapid method for the analysis of the sulphate and carbonate of calcium in gypsum, a. new gravimetric determination by electrolysis of nickel-hexanitrite of calcium-potassium, of which the structural formula has been established. Finally, they recommend, in the case of precipitation of calcium as the tartrate, weighing as carbonate rather than oxide.     

Photodissolution of ferrihydrite in the presence of oxalic acid: an in situ ATR-FTIR/DFT study

The photodissolution of the iron oxyhydroxide, ferrihydrite, in the presence of oxalic acid was investigated with vibrational spectroscopy, density functional theory (DFT) calculations, and batch geochemical techniques that determined the composition of the solution phase during the dissolution process. Specifically, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR- FTIR) was used to determine the structure of the adsorbed layer during the dissolution process at a solution pH of 4.5. DFT based computations were used to interpret the vibrational data associated with the surface monolayer in order to help determine the structure of the adsorbed complexes. Results showed that at pH 4.5, oxalate adsorbed on ferrihydrite adopted a mononuclear bidentate (MNBD) binding geometry. Photodissolution at pH 4.5 exhibited an induction period where the rate of Fe(II) release was limited by a low concentration of adsorbed oxalate due to the site-blocking of carbonate that was intrinsic to the surface of the ferrihydrite starting material. Oxalate displaced this initial carbonate over time, and the dissolution rate showed a corresponding increase. Irradiation of oxalate/ferrihydrite at pH 4.5 also ultimately led to the appearance of carbonate reaction product (distinct from carbonate intrinsic to the starting material) on the surface.     

A novel approach to Ca-Sr separation in the determination of90Sr using inorganic exchangers: An application to environmental samples

A procedure for⁹⁰Sr determination in calcium rich samples is presented. It is based on the precipitation of calcium oxalate in homogeneous solution and under controlled conditions to minimize the coprecipitation of strontium. The latter is subsequently separated as carbonate and radiochemical purification is completed by ion exchange chromatography on two inorganic exchangers: PRTD (partially reduced tin dioxide) and CUCR (copper chromate). The procedure was applied to environmental samples such as ashed sediment, fish and vegetable and results are reported.     

Thermal decomposition of calcium oxalate: beyond appearances

The goal of this study is twofold: to take a fresh look at the decomposition of calcium oxalate and to warn users of thermogravimetric analysis against the hasty interpretation of results obtained. Since the pioneer work of Duval 70 years ago, the scientific community has agreed unanimously as to the decomposition of anhydrous calcium oxalate (CaC₂O₄) into calcium carbonate (CaCO₃) and CO gas, and that of the calcium carbonate into calcium oxide (CaO), and CO₂ gas. We will demonstrate how these reactions, simple in appearance, in fact result from a succession of reactive phenomena involving numerous constituents both solid (CaCO₃, free carbon) and gaseous (CO₂ and CO) produced by intermediary reactions. The mass losses evaluated in the two distinct domains correspond closely to the molar masses of CO and CO₂, respectively. The simple mathematical calculation of that mass loss has simply concealed the existence of other reactions, and, most particularly the Boudouard reaction and that of solid phases between CaCO₃ and C. It just goes to show that appearances can be deceiving.

     

Analysis of calcium, oxalate, and citrate interaction in idiopathic calcium urolithiasis in children

The majority of urinary stones in children are composed of calcium oxalate. To investigate the interaction between urinary calcium, oxalate, and citrate as major risk factors for calcium stones formation, their 24-h urinary excretion was determined in 30 children with urolithiasis and 15 normal healthy children. The cutoff points between children with urolithiasis and healthy children, accuracy, sensitivity, and specificity for each risk factor alone as well as for all three taken together were determined. OneR and J4.8 classifiers as parts of the larger data mining software Weka, based on machine learning algorithms, were used for the determination of the cutoff points for differentiation of the children. The decision tree based on J4.8 classifier analysis of all three risk factors together proved to be the best for differentiating stone formers from normal children. In comparison to the accuracy of the differentiation after calcium and oxalate of 80% and 75.6%, respectively, the decision tree showed an accuracy of 97.8%. Even when its stability was tested by the leave-one-out cross-validation procedure, the accuracy remained at a very acceptable percentage of 93.2% correctly classified patients. J4.8 classifier analysis gave a look inside urinary calcium, oxalate, and citrate interaction. Urinary calcium excretion was shown as the most informative in discrimination of the children with urolithiasis from healthy children. However, it was shown that oxalate and citrate excretions might influence the stone formation in a subpopulation of the stone formers. In patients with low urinary calcium, a major role in lithogenesis belongs to oxalate, in some of them alone and in others in conjunction with citrate. Decreased urinary citrate excretion in the presence of increased oxalate excretion may lead to stone formation.     

Etude de la Reactivite Entre L'orthophosphate Tricalcique Apatitique et L'oxalate de Calcium

Several difficulties arise when studying the mineral component of calcified tissues: This material is complex due to the large number of atomic components, its heterogeneous composition, and varying factors. It is linked strongly to the organic component, and today no available technique allows a complete separation of these two components without alteration of one of them. In the present work the interaction of apatitic calcium phosphate with calcium oxalate has been studied. By heating stoechiometric amounts of these two solids, it was found that the presence of CO 3 2 m and CaO produced by calcium oxalate induces a decrease in P 2 O 7 4 m arising from HPO 4 2 m content of apatitic calcium phosphate. L'étude physico-chimique de la partie minérale des tissus calcifiés est extrêmement étendue et complexe. Fortement liée à des composés organiques, des difficultés de séparation, d'identification et d'étude du comportement de ces matériaux ont été signalées par de nombreux auteurs. En vue d'identifier l'effet des ions carbonate CO 3 2 m et du CaO sur la détermination de la teneur des ions (HPO 4 2 m ) des apatites synthétiques, les interactions entre le phosphate tricalcique apatitique et l'oxalate de calcium ont été étudiées. Il a été constaté que les ions CO 3 2 m produits par le carbonate de calcium issu de l'oxalate de calcium, conduisent à une diminution relative de la teneur des ions P 2 O 7 4 m (provenant des ions HPO 4 2 m ) dans le mélange équimolaire de phosphate apatitique et d'oxalate de calcium, dans le domaine de températures 400-520°;C. Au-delà de 520°;C la seconde diminution de la teneur des ions P 2 O 7 4 m est attribuée aux interactions des ions P 2 O 7 4 m et du CaO.     

Pyrolysis of Nickel Zirconyl Oxalate

Nickel zirconyl oxalate hexahydrate (NiZrOx) is δ prepared and characterised by I.R. spectral and chemical analysis. Its thermal decomposition has been investigated by employing TG, DTG, DTA and chemical analysis. End product was identified by X-ray diffraction studies. The decomposition proceeds through four steps i) dehydration of NiZrOx in two steps, ii) partial decomposition of oxalate to give an oxalate carbonate intermediate, iii) decomposition of oxalate to give a non-stoichiometric carbonate and iv) decomposition of this non-stoichiometric carbonate to give the end product a mixture of NiO+ZrO₂. On the basis of the results obtained, a tentative scheme for the decomposition of NiZrOx is proposed.     

Determination of 41Ca in biological-shield concrete by low-energy X-ray spectrometry

An X-ray spectrometric method has been developed for the determination of 41Ca in the biological-shield concrete of nuclear reactors. The concrete sample was first decomposed with nitric, hydrofluoric, and perchloric acids. Calcium was then separated from other radionuclides by ion-exchange chromatography and recovered as an oxalate precipitate. X-rays at 3.3 keV from 41Ca in the calcium oxalate pellet were measured. The detection efficiency of the X-ray measurement at 3.3 keV was calculated from those obtained by measuring 55Fe standard pellets at 5.9 keV using mass-absorption coefficients of the calcium oxalate pellet at each X-ray energy. A lower limit of determination of 8 Bq g(-1) was obtained for a sample weight of 1 g.     

Enthalpies of reaction of calcium chloride and sodium oxalate in aqueous solution of Tween 80

The heats of mixing of dilute calcium chloride and sodium oxalate solutions in water and aqueous solutions of a nonionogenic surfactant, namely, polyoxyethylene (20) sorbitan monooleate (Tween 80) containing 1–5 wt % of the dissolved substance were measured at 298.15 K. The heats of dilution of calcium chloride solutions were determined, and the enthalpies of precipitation of calcium oxalate in water and surfactant solutions were calculated. The surfactant concentration was found to have almost no effect on the enthalpies of the processes under study; rather, it modifies the shape of the resultant deposit by preventing the agglomeration of calcium oxalate particles.     

用草酸钙共沉淀法分离富集骨中稀土元素

采用草酸钾作沉淀剂 ,在 pH2时将骨中钙部分沉淀 ,通过草酸钙载体共沉淀富集骨中稀土元素。用分光光度法、同位素示踪法和中子活化法检验模拟样品中稀土元素富集效果。结果显示 ,当每 g钙的沉淀量为48mg时 ,微克量和纳克量的稀土元素共沉淀率达到90 %以上。方法简单、可靠 ,且避免了钙、磷和钠等宏量元素的干扰 ,可对0.5～5g骨样中的稀土元素进行有效的分离富集。