Evaluation of Manganese(II) and Manganese(VII) Speciation in Water Samples by Ion Pair High-performance Liquid Chromatography-inductively Coupled Plasma Mass Spectrometry

The speciation of Mn(II) and Mn(VII) is reported by ion pair chromatography. To optimize the separation, sample pH, ion pair reagent, Mn(II) complexing agent, and composition of mobile phase were characterized. The separation of Mn(II) and Mn(VII) was performed using ethylenediamine tetraacetic acid to complex Mn(II), tetrabutylammonium hydroxide as an ion pair reagent, and a C8 column. The separation of the manganese species was demonstrated by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC ICP-MS). The conversion of Mn(VII) to Mn(II) occurred during the separation and influenced the quantification; hence, the factors affecting this process including the storage time, manganese species ratio, and sample matrix composition were evaluated and suitable calibration was demonstrated. The method was validated by characterization of the selectivity, specificity, linearity, limits of detection and quantification, repeatability, and intermediate precision. The detection limit for Mn(II) was 0.22 µg?L^?1, while for Mn(VII), the value was 1.55 µg?L^?1.     

Weathering Phenomena on Naturally Weathered Potash-Lime-Silica-Glass with Medieval Composition Studied by Secondary Electron Microscopy and Energy Dispersive Microanalysis

 Samples of two model glasses with chemical compositions similar to medieval stained glass were exposed to the natural environment at 23 test sites for a period of 6 months, 1 and 2 years within an exposure programme of the “Working Group of Effects on Materials, Including Historic and Cultural Monuments” of the Economic Commission for Europe of the United Nations. During the exposure the environmental data were measured and collected at each test site in order to enable a correlation between the pollutant load in the ambient atmosphere and the weathering phenomena of the glass samples. After the exposure, which was performed in a sheltered as well as in an unsheltered mode for gaining information about the influence of dry and wet deposition of air pollutants, the glass samples were analysed in the scanning electron microscope with energy dispersive microanalysis (SEM/EDX). Model glass M1 – a potassium rich glass – was covered to a high amount with crystalline weathering products (above all syngenite), whereas glass M3 – a glass with a higher Ca and Si content – turned out to be more stable against weathering. This glass was covered with gypsum and arcanite crystals but in total to a less extent than glass M1. Received March 30, 1998. Revision February 8, 2000.     

在超声分子束条件下Mn2(CO)10的多光子电离解离

近年来，人们对具有金属－金属键的Mn2（CO）10分子的光解离电离动力学的研究十分关注．这一方面是由于其独特的分子结构可以获得丰富的光化学及其化学性质方面的信息；另一方面从其结构和光活性之间的关系，有助于了解双核金属有机化合物在催化反应中所起的作用．Leutwyler和Even[1]曾在超声分子来条件下，用脉冲染料激光实现了Mn2（CO）10的多光子电离解离（MPID）过程，获得Mni＋（i＝1，2，3）金属碎片离子．Lichin等人[2]曾用511nm和483nm激光引起Mn2（CO）10的气相多光子解离和电离，测得产物中除了Mn＋，Mn2＋和MnCO＋离子…     

Cobalt absorption bands for the differentiation of historical Na and Ca/K rich glass

The main purpose of this publication is to define sensing parameters by means of optical spectroscopy to study and characterize ancient glass. Because during different times different flux agents were used, a chemical individuation of these elements provides a first dating classification. Normally, X‐ray‐based chemical methods are applied to this kind of investigation. On the basis of the Ligand‐field theory, the absorption band positions of a transition metal ion undergo a change when the ion is placed in different chemical environments. A total of 25 cobalt coloured Roman, post‐medieval and industrial glasses were analyzed by means of SEM–energy dispersive X‐ray spectroscopy to group them according to their chemical composition. Optical spectroscopy was applied to build a method to study glass with this low‐cost and non‐destructive technique. It is proved that the cobalt absorption band situated around 535.5 nm for sodium‐rich glasses (Roman and industrial material) is shifted towards 526.5 nm for calcium–potassium‐rich glasses (post‐medieval window glass). This feature was employed as a marker in the case study of the Renaissance window of the Church Wardens from the Church of Our Lady in Bruges, Belgium to distinguish the post‐medieval material from the 19th and 20th century restoration material. Copyright © 2011 John Wiley & Sons, Ltd.     

Identification and Classification of Iridescent Glass Artifacts with XRF and SEM/EDX

 Art Nouveau (Tiffany, Loetz) and modern (Jack Ink, Strini Art Glass) iridescent glass fragments were characterized using energy dispersive X-ray fluorescence analysis (EDXRF) and energy dispersive X-ray microanalysis in a scanning electron microscope (SEM/EDX) in combination with factor analysis in order to obtain clustring. A character istic of Tiffany glass fragments is leaded bulk glass, whereas in the case of Loetz K-Ca-Si bulk glass could be determined. Modern glass fragments show a high amount of Na (7 wt% in the bulk of Jack Ink) and 0.6–1.5 wt% Sr in the bulk of Strini Art Glass. The contents of Si and Ca are similar to Loetz glass. Furthermore, the differences in the structure of the glass artifacts could be determined. The cross-sections of Tiffany show a layered structure of the bulk without a specific surface layer whereas the cross-sections of Loetz glass reveal a homogeneous bulk material with one or two homogeneous surface layers in the BE-image. In the case of the Jack Ink a homogeneous bulk glass and an inhomogeneous multilayered surface could be determined. Strini Art Glass show a homogeneous bulk glass and a homogeneous surface layer in the backscattered electron image.     

Statistical evaluation of potash-lime-silica glass weathering

Two potash-lime-silica model glasses with compositions similar to those of medieval stained glass were exposed at 26 test sites all over Europe and in North America for 3–6 years. The objectives of this large-scale field exposure programme were: (a) a qualitative analysis of the weathering products formed on the surface of the samples in the (environmental) scanning electron microscope in combination with energy dispersive X-ray microanalysis (ESEM/EDX or SEM/EDX, respectively); (b) a statistical evaluation of the weathering phenomena by applying a multiple linear regression (MLR) analysis to find correlations between the degree of weathering, which was measured in terms of surface coverage with reaction products, and environmental parameters such as the concentration (c) of the acidifying gases SO₂, NO₂ and O₃, the temperature (T) and the relative humidity (RH); and (c) the calculation of a time-dependence function of the weathering process of these glasses. Mainly sulfates of calcium and potassium such as gypsum (CaSO₄·2 H₂O), arcanite (K₂SO₄) and syngenite (CaSO₄·K₂SO₄·H₂O) could be identified in the SEM and ESEM. Carbonates, nitrates and many particles deposited on the glass surface were found as well. MLR calculations exhibit significant dependencies of the degree of weathering on T, RH, c(NO_x), c(SO₂) and c(O₃). Applying a time-dependence function of the general form y=a·t^b (t=time) results in a value of approximately 0.42 for the exponent b, which comes close to values expected from various studies in the literature.     

Colourants and opacifiers in seventh and eighth century glass investigated by spectroscopic techniques

Glass fragments dating from the seventh and eighth century AD were excavated in the Crypta Balbi in Rome. They were studied to detect agents involved in colour development and opacification. Reflectance spectra recorded on powdered samples revealed the contribution of Fe(II), Fe(III), Mn(III), Cu(II), and Co(II) ions in determining colour hues. The effect of the Mn/Fe atomic ratio on glass colour is discussed. It is apparent that medieval glassmakers in Italy could obtain a wide range of colours by exploiting the presence of iron and manganese as contaminants of sand and flux and controlling the amount of oxygen let into the furnace. X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray analysis were used to study opaque fragments. The presence of calcium antimonate was detected in white, blue, and blue-green fragments, and elemental copper was detected in a red glass.     

Feasibility of ETV-ICP-OES for Characterization of Archaeological Glasses

In the present study the possibilities of electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES) for characterization of archaeological glasses were investigated. The objects of our research were fragments of a colorless late antique Roman flat window glass (fifth century A.D.) and colored medieval glass bracelets (eleventh–twelfth century A.D.) excavated in the region of Pernik (West Bulgaria).

The finely ground glass samples were analyzed directly and CHF₃ was used as evaporation and transport modifier. Dried aqueous standard solutions and certified reference materials with different matrix (glass, fly ash, and stream sediment) were used as calibration standards. No matrix effects were observed by the optimized conditions. Measurements were performed using common calibration curves obtained with all appropriate calibration standards and major, minor, and trace element concentrations were determined. ETV-ICP-OES analytical data were used to establish the type of glass, the fluxing agents, the typical coloring and decoloring elements, and the recipe norm.     

Scanning electron microscopy and energy dispersive analysis: applications in the field of cultural heritage

Scanning electron microscopy has been extensively used for the material characterization of objects of artistic and archaeological importance, especially in combination with energy dispersive X-ray microanalysis (SEM/EDX). The advantages and limitations of SEM/EDX are presented in a few case studies: analysis of pigments in cross-sections of paint layers, quantitative analysis of archaeological glass from the Roman period excavated in Ephesos/Turkey, and investigations on glasses with medieval composition concerning their weathering stability and degradation phenomena.     

High resolution gas chromatography/mass spectrometric characterization of urinary metabolites of N,N-diethyl-m-toluamide (DEET) in man

Studies of the pharmacology and toxicology of the popular insect repellant, N,N-diethyl-m-toluamide (DEET), have largely been done in animal models using radioactive tracing without the structural elucidation of its metabolites. This paper describes a high resolution gas chromatography/mass spectrometry (GC/MS) technique and reports the results of the preliminary characterization of the metabolites of DEET in the urine of a 30-year-old man who had been exposed to DEET contained in a commercial product. The metabolites were extracted and separated with an OV-101 glass capillary column, 30 m × 0.3 mm, and mass spectrometric elucidations were carried out with both Electron Impact (EI) and Chemical Ionization-Methane (MCI) modes. Oxidation of the benzylic moiety and hydroxylation of the sidechain of DEET molecules appeared to be the predominate routes of metabolism in man. The artifacts were also proposed.     

电致化学发光法测定Mn2+含量的研究

在H3 PO4溶液中,利用Ag+存在条件下,Mn2+可以被电化学氧化成KMnO4,KMnO4进而与酸性邻苯二酚或碱性鲁米诺等发生反应,得到较好的化学发光信号,构建了一种间接测定水溶液中Mn2+含量的方法.研究了Ag+对Mn2+电化学氧化的影响.Mn2+电化学氧化过程中,当Ag+浓度为1.5×10-5 mol/L,H3 PO4浓度为0.01 mol/L,电解2 min后,发光强度达到最大.探讨了不同pH条件下的化学发光强度与Mn2+浓度的关系及选择性.在酸性介质中,邻苯二酚的发光强度与Mn2+在1.82×10-7~7.27×10-5mol/L的浓度范围内呈现良好的线性关系;常见的金属离子等对Mn2+测定干扰小.将本方法用于地表水及饮用水中Mn2+的测定,与标准方法相比,结果令人满意.     

Hydrolysis of Nb(V) and Ta(V) in aqueous KCl at 25°C. Part II: Construction of a thermodynamic model for Ta(V)

In this work the hydrolysis of Ta(V) in 3.0M KCl has been studied by measuring the H₃O⁺ ion concentration with a glass electrode. The experimental work consisted of automatically controlled potentiometric titrations. The results were treated using graphical and numerical methods and, as a result, the hydrolysis process can be considered as a homonuclear protolysis. Finally, the results obtained were compared with other data found in the literature and a hydrolysis model for Ta(V) was built by means of the modified Bromley theory.     

高效液相色谱光度法测定痕量铜、锌、铁、锰的磺化四苯基卟啉配合物

本文用磺化四苯基卟啉作柱前衍生试剂,研究了试剂与铜(Ⅱ)、锌(Ⅱ)、铁(Ⅲ)及锰(Ⅱ)的络合反应。在ODS柱上,用乙腈-水(40:60,V/V)作流动相,溴化四丁基铵作离子对试剂,在420nm波长处进行光度检测。提出了离子对反相高效液相色谱快速分离及测定痕量铜、锌、铁及锰的新方法。检测下限为(×10^-3ppm):Mn 3.6、Fe 1.8 、Zn 0.93、Cu 0.70。应用于植物样品中痕量铜、锌、铁及锰的测定,分析结果与标准参考值相符。     

PHBV/Sol-gel Bioglass多孔材料在模拟生理溶液中的化学反应研究

3-羟基丁酸-co-3-羟基戊酸共聚物(PHBV)/生物活性玻璃(SGBG)是一种用于骨和软骨组织工程支架的新型多孔复合材料,本文探讨了PHBV/SGBG在模拟生理溶液中的一系列化学反应,以及多孔材料在模拟生理溶液中浸泡后的成分和结构变化.研究结果表明,在SBF溶液中浸泡后,SGBG与SBF溶液的离子交换反应和PHBV的降解反应使SBF溶液的离子浓度发生变化,并在PHBV/SGBG表面形成了结晶态类骨碳酸羟基磷灰石.     

Surface,thermal and mechanical characteristics of polymeric solids

Surface molecular motions of amorphous polymeric solids have been directly measured on the basis of lateral force microscopic (LFM) and scanning viscoelasticity microscopic (SVM) measurements. SVM measurement revealed that the molecular motion at the surface of the monodisperse polystyrene (PS) film with Mn less than ca.30k was fairly activated compared with that in a bulk region, mainly due to the surface segregation of chain end groups. Temperature dependent LFM and SVM measurement revealed that the surface glass transition temperature, Tg of the monodisperse PS film was lower than the bulk one, even though Mn was fairly large as 140k and also, that the time-temperature superposition was applicable to the surface relaxation process. The chain end group segregation at the air/PS interface was verified from the dynamic secondary ion mass spectroscopic (DSIMS) depth profiling of the proton and deuterium ion for the end-labeled deutrated-PS (dPS) film. These results suggest that the surface Tg is depressed due to an increase in free volume near surface region, being induced by the preferential surface localization of chain end groups.     

Trace analysis of glasses by magnetically enhanced rf GDMS

A radiofrequency (rf) glow discharge ion source coupled to a commercial double-focusing mass spectrometer was used for the direct trace element analysis of glass samples. By utilizing an additional ring-shaped magnet located behind the flat sample in an rf glow discharge ion source compared with a configuration without a magnet, the sputtering and ionization efficiency of glass samples was enhanced and the detection power for trace elements was improved. The detection limits for elements determined by rf glow discharge mass spectrometry at low mass resolution (m/Δm = 300) are 10–100 ng/g. Possible interferences of atomic ions of analyte and molecular ions which limited the determination of some elements (e.g. Ti, Mn, Fe, Ni, Co, Cu, Zn) could be resolved at the mass resolution of m/Δm = 3000. The detection limits for these elements were found to be about 100 ng/g. Relative sensitivity factors (RSFs) for all elements of interest with respect to Sr (internal standard element) were determined in the range of 0.2–3.     

现场紫外-可见吸收光谱研究电解二氧化锰的还原过程

应用现场紫外 可见吸收光谱研究碱性溶液中电解MnO2(EMD)放电机理.结果表明,对EMD电极的放电还原,包括两个单电子过程,其第1电子还原又分为3步:①还原MnO2颗粒表面和阳离子空位附近的Mn4+离子,②还原斜方锰矿中的Mn4+离子,③还原软锰矿中的Mn4+离子.第2电子还原是将溶解的Mn3+还原成Mn2+,进一步转化成Mn(OH)2和Mn3O4.     

锂离子交换剂制备及交换反应动力学

通过XRD分析、Li＋抽出率βLi及Mn2＋溶出率γMn的计算，考察了不同焙烧温度及抽锂剂对前驱体锂锰氧化物LiMn2O4结构及稳定性的影响.结果表明, 750 ℃下焙烧2 h，并使用过硫酸铵(NH4)2S2O8作抽锂剂，制备的Li＋交换剂MnO2(Li)对Li＋的交换容量αLi较大.另外，通过Li＋在固液两相间分配系数的测定及交换反应动力学实验，对离子交换反应机理进行了研究，并建立了有限浴条件下MnO2(Li)离子交换反应动力学模型.结果表明,该离子交换过程近似符合颗粒扩散控制；交换反应主要发生在交换剂颗粒外层；提出的动力学模型与实验结果符合较好.     

Synthesis and crystal structure of aquachlorobis(1,10-phenanthroline)manganese(II) nitrobenzoate trihydrate

The title compound has been prepared and its crystal structure determined by X-ray diffraction methods. The complex salt consists of Mn(II) complex cations, benzoate anions and lattice water molecules. Mn(II) assumes a distorted octahedral geometry defined by two 1,10-phenanthroline (phen) ligands, a Cl^? ion and a water molecule. A comparison of bond distances and bond angles suggests electrostatic interaction between Mn(II) and coordinated N atoms. The nitrobenzoate anion does not coordinate to the Mn atom but links with the complex cation via O?H···O hydrogen bonds. Aromatic stacking occurs between phen rings and between phen and benzoate.     

Syntheses,crystal structures and magnetic properties of heteronuclear bimetallic compounds of [Cu(pdc)2][M(H2O)5]·2H2O [M=Ni(II), Co(II), Mn(II); pdc=2,6-pyridinedicarboxylato]

The complexes [M(H₂O)₅][Cu(pdc)₂]·2H₂O [M=Ni(II) 1, Co(II) 2, Mn(II) 3; pcd=2,6-pyridinedicarboxylato] are prepared and their crystal structures, magnetic susceptibilities and UV-Visible properties reported. In all cases, the Cu(II) ion occupies the chelating site in the pdc ligand, while the M(II) occurs as a pentaaqua ion bridged to the [Cu(pdc)₂] moiety through a carboxylate as demonstrated by both UV-Visible spectroscopy and X-ray diffraction. Single crystal X-ray diffraction shows the three complexes to be isostructural. Weak antiferromagnetic interactions between the metal ions are observed in 1 and 3, while the magnetic behavior of 2 is dominated by single ion anisotropy.