Characterization of the patina formed on a low tin bronze exposed to aqueous hydrogen sulfide

The dark gray corrosion layer (patina) formed on the surface of a polished low tin bronze alloy following exposure to a deoxygenated and saturated aqueous solutions of H₂S has been characterized by X‐ray photoelectron spectroscopy, scanning electron microscopy‐energy dispersive spectroscopy and X‐ray diffraction. The system represents a model for bronze corrosion in reducing conditions where sulfate‐reducing bacteria in soils or deoxygenated seawater may generate H₂S during respiration. The initial surface was dominated by metallic copper together with Sn, Pb and Zn oxides and hydroxides. Surface enrichment of Pb and Zn was noted because of a smearing effect during polishing. At least some of the lead was crystalline. In contrast, the corrosion layer formed by H₂S(aq) exposure was dominated by polycrystalline Cu₂S (low and high chalcocite) and smaller concentrations of CuSO₄ · nH₂O. This surface was enriched with Zn as Zn(OH)₂. Lead was present as redeposited PbS (galena) crystallites in at least two different morphologies. Unlike bronzes exposed to oxidizing conditions, which develop protective SnO₂ layers, the H₂S(aq)‐exposed surface was considerably depleted in Sn. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrothermal synthesis of potassium molybdenum oxide bronzes: structure-inheriting solid-state route to blue bronze and dissolution/deposition route to red bronze

The hydrothermal syntheses of the alkali metal molybdenum bronzes from starting solids (H_xMoO₃) with structural affinities to the desired products were investigated. Single-phase potassium blue and red bronzes were prepared by the hydrothermal treatments at around 430 K, and characterized by powder X-ray diffraction, IR spectroscopy, and SEM. The formation processes of these two bronzes during the hydrothermal treatments were found to differ. The blue bronze was formed by a structure-inheriting solid-state route from H_xMoO₃ with x<0.3, whereas the red bronze was formed for x>0.3 through a solution dissolution/deposition route via the formation of MoO₃+MoO₂.     

A study for the characterization of binding media from medieval polychrome sculptures by gas chromatography-mass spectrometry

Summary Binding media in samples taken from XIIth–XIIIth century polychrome sculptures in the Baptistery of Parma (Italy) were characterized by gas chromatography-mass spectrometry, after hydrolysis and derivatization procedures. The use of SE-52 capillary columns and the application of selected ion monitoring (SIM) allowed an increasing in the sensitivity and the ability to differentiate between animal glues, casein, egg and drying oils as components of the binders of paint and ground layers. Small amounts of material were enough for a satisfactory characterization.     

Characterization of a heavily corroded bronze statue from Pharaonic Egypt

The current study aims to characterize a heavily corroded bronze statue from Pharaonic Egypt, in terms of the morphology and mechanism of corrosion. The characterization was carried out by a combination of methods, including the scanning electron microscope equipped with energy dispersive X-ray spectroscopy (SEM–EDS), USB digital microscope, X-ray micro-diffraction, and Raman micro-spectroscopy. Insights into the morphology and corrosion mechanisms of two corrosion stages are presented. Specifically, the metallic-wall layer was first converted into grayish-brown corrosion mottled with green and gray spots in the central part, in which a greenish-white corrosion phase was formed in the second stage. The EDS analysis of the greenish-white phase revealed the predominance of tin, copper, oxygen, and carbon and a low chlorine content. The greenish-white phase consisted of four corrosion products: romarchite, cassiterite, malachite, and a small amount of atacamite. The morphology developed upon corrosion was attributed to the selective dissolution and depletion of copper in the central layer, internal oxidation of tin, and conversion of cuprite into malachite. Moreover, the usual bronze corrosion products were formed as a superficial layer on the statue.     

铯钨青铜的合成及其对甘油脱水制丙烯醛的催化性能

以仲钨酸铵、硝酸铯为原料,乙二胺四乙酸(EDTA)为模板剂和还原剂,采用水热法合成了铯钨青铜,考察了EDTA用量、水热前驱液浓度、铯钨比等条件对水热产物组成及形貌的影响,并以所得产物为催化剂在固定床反应器中进行甘油脱水制丙烯醛的反应研究,发现铯含量对催化性能有较大影响,在Cs/W摩尔比为0. 2∶1时催化性能最好,甘油转化率达到81. 3%,丙烯醛的选择性达到92. 9%。     

Application of chemical and chemometric analytical techniques to the study of ancient ceramics from Dougga (Tunisia)

In the present paper chemical characterization has been carried out on 67 shards of archaeological pottery from Dougga (North Tunisia). The analysed shards, dated to the Byzantine period (VI–VII century A.D.), belong to the three ceramic classes African Red Slip Ware, Dougga Ware and African cooking Ware. Fourteen elements have been determined by both atomic emission spectroscopy with flame as source (AES) and by using an inductively coupled plasma source (ICP-OES). The data acquired have been treated by statistical techniques in order to define grouping for the examined shards. Both unsupervised and supervised methods have been employed in order to define groups of different pottery shards. As a comparison, some samples (control group) coming from Southern Tunisia have been examined. All the statistical methods employed have evidenced how the control group, as concerns the chemical composition, is clearly distinguishable from Ain Wassel samples which are highly homogeneous. In fact because of the compositional homogeneity of the Northern Tunisia productions, it is quite difficult to establish a good classification and distribution of the samples in well defined cluster. Nevertheless supervised analysis has evidenced how, among the three classes, the African cooking Ware is the more distinguishable one confirming the archaeologists' hypothesis that Dougga Ware is an imitation of African Red Slip Ware.     

A study of a crude oil spill site for selected metal concentrations remediated by a controlled burning in Southwest Louisiana

On August 17, 2002 an oil spill occurred at the Chevron Texaco No. 2 Bayou Tank Battery in the Sabine National Wildlife Refuge, in Southwest Louisiana. The spill covered approximately 3.5 acres of the surrounding marsh. A controlled and in-situ burn of the oil was conducted on August 20, 2002 along with some post-burn “mopping up” on the following day. Within a few days after the burn the growth of new vegetation was observed. A year after the burn, the affected marsh seemed to be no different from the rest of the marsh in the area, as if no spill or burn ever occurred. Analysis of the oil from the No. 2 Bayou Tank Battery showed that there were very low (below detection limit of ICP-OES), if any, concentrations of selected trace metals. Soil cores and grass samples were taken on December15, 2003 and July 15, 2004 from the Sabine National Wildlife Refuge oil spill site for metal determination and compared to cores and grasses taken from the surrounding marsh and confirmed that there was no increase in concentration of any metal that was examined as a result of the oil spill or controlled burn.     

Application of gas chromatography-mass spectrometry analysis to the study of works of art: paint media identification in polychrome multi-material sculptures

A new gas chromatographic-mass spectrometric procedure for characterizing both drying oils and proteinaceous binders in samples of painted artworks has been developed. Furthermore, a new analytical procedure for analysis of polysaccharide materials through identification of the monosaccharide constituents is proposed. The methods have been applied to characterizing binding media of the different layers of the polychrome surface in the multi-material sculptures from the sanctuary of Santa Maria delle Grazie in Mantova, Italy. It was found that animal glue was the main binder in the priming layer of all statues, whereas more complex mixtures were used in the paint layers. Generally, a drying oil was present, most often linseed oil alone or in combination with other organic binders.     

Scalable properties of metal clusters: a comparative study of modern exchange-correlation functionals

The performance of eight generalized gradient approximation exchange-correlation (xc) functionals is assessed by a series of scalar relativistic all-electron calculations on octahedral palladium model clusters Pd(n) with n = 13, 19, 38, 55, 79, 147 and the analogous clusters Au(n) (for n up through 79). For these model systems, we determined the cohesive energies and average bond lengths of the optimized octahedral structures. We extrapolate these values to the bulk limits and compare with the corresponding experimental values. While the well-established functionals BP, PBE, and PW91 are the most accurate at predicting energies, the more recent forms PBEsol, VMTsol, and VT{84}sol significantly improve the accuracy of geometries. The observed trends are largely similar for both Pd and Au. In the same spirit, we also studied the scalability of the ionization potentials and electron affinities of the Pd clusters, and extrapolated those quantities to estimates of the work function. Overall, the xc functionals can be classified into four distinct groups according to the accuracy of the computed parameters. These results allow a judicious selection of xc approximations for treating transition metal clusters.     

Design of experiment for evaluation of uncertainty from sampling in the framework of the fitness for purpose concept: a case study

The design of an experiment for the evaluation of sampling uncertainty in the framework of the fitness for purpose concept is described in terms of probabilities (risks of the user) of type 1 and type 2 errors in decisions concerning the significance of effects influencing the sampling uncertainty and the measurement results. As a case study, an experiment based on the duplicate method for quantification of the sampling uncertainty and inhomogeneity (heterogeneity) of a melt of tin-free bronze produced in a 10-ton reflective oven is analyzed. The melt is defined as the sampling target. It is shown that the number of such targets (melts), the number of samples under analysis and the number of replicate analyses can be minimized, i.e., the size and cost of the experiment can be reduced, if the user knows which risks are acceptable. When inhomogeneity of the sampling target has a systematic character, like the decrease of the mass fraction of aluminum from the beginning to the end of the melt pouring in the case study, the inhomogeneity effect can be separated from the sampling uncertainty and evaluated according to the user’s needs.     

Comparative study of two analytical methods to the determination of boron in leachate samples from sanitary landfills and groundwater for routine analysis and feasible on-site environmental monitoring

Two analytical methods as inductively coupled plasma optical emission spectrometry (inductively coupled plasma optical emission spectroscopy (ICP-OES)) and azomethine-H UV-Vis-based method were compared statistically, to evaluate their analytical characteristics and applicability to the determination of boron in leachates (complex matrix) from sanitary landfills (SLs) and groundwater (simple matrix) from different sampling points near SLs. Calibration curves and standard addition methods were used for this purpose. Azomethine-H UV-Vis-based procedure has proven better precision and accuracy than ICP-OES. However, statistical analysis (F-test and t-test) does not show significant differences between these two methods, achieving concentration range of up to 10 mg L^?1 of the boron in both simple and complex matrices. Due to low cost and gentle-to-operate easy-accessible system, the azomethine-H UV-Vis-based method was therefore proposed (rather than ICP-OES) for routine analysis and for feasible on-site monitoring of boron in SLs, with respect to satisfy Chilean Standard 409 (NCh409) related to drinking water policy.     

Rare earth tungsten bronzes: a new method of synthesis. Perspectives for their application as inert matrices for transmutation of long-life actinide elements

A new method of synthesis of oxide tungsten bronzes containing lanthanide (Ln) Nd and Eu, based on thermal degradation of polyoxotungstate compounds, is proposed. The simplicity of the method allows to consider this class of compounds with chemical formula, Ln_xWO₃, as potential inert target for incineration or transmutation of minor actinides, Am and Cm, in neutron reactors. Nd and Eu were used as analogues of transplutonium elements. Powder X-ray diffraction patterns of compounds synthesized reveal a cubic perovskite structure. The lanthanide content in bronzes was determined by optical spectroscopy analysis. The experimental density of the pressed bronze samples was estimated at 6.58 g cm⁻³, i.e., 89% of the crystallographic value. The thermal stability of the bronzes synthesized was checked up to 900°C in an inert atmosphere. Leaching tests were performed for europium bronzes in nitric acid solutions using luminescence technique.     

FT-IR microscopic imaging of calcified deposit of rotator cuff tendonitis: A pilot study and a randomised identification of the compositional components after extrusion from tendon to muscle

Fourier transform infrared (FT-IR) microspectroscopy with mapping system was applied to identify and evaluate what difference in the distribution and compositional components of the calcified deposit of rotator cuff tendonitis after dislocation from tendon to muscle. A 49 year-old female patient suffered from severe shoulder pain was enrolled in this study. Diagnostic high-resolution ultrasonography (HRUS) was initially carried out to verify the calcific tendonitis. The calcified deposits were then examined by histopathologic assessment and FT-IR microspectroscopy. Diagnostic HRUS reveals that the calcified deposits were observed in the subscapularis tendon and infraspinatus muscle of the shoulder for this patient. FT-IR microspectroscopic imaging results clearly indicate that both IR spectra of the calcified deposits in tendon and muscle were almost the same as that of the IR spectrum of hydroxyapatite except the peak at 873 cm⁻¹. It is also found that the peak intensity at 1030 cm⁻¹ for tendon sample was somewhat more intense than that of the peak at 1031 cm⁻¹ for muscle sample, implying that the calcified sample in the tendon seems to be mature than that in the muscle. The second-derivative IR spectra of two calcified samples exhibit two specific sharp peaks at 880 and 872 cm⁻¹, indicating that the type A and type B carbonated apatites were markedly co-existed in both calcified deposits of tendon and muscle even the calcified deposit was dislocated from tendon to muscle. These carbonated apatites presented in the calcified deposits of either tendon or muscle of the shoulder were also consistent with the nodular or nodular nodular-cystic morphology of calcified plaque of the shoulder after HRUS examination.     

On-Line Standard Addition Technique for the Determination of Elements in the Samples with High Dissolved Solids by ICP-OES: Application to Determination of Rare Earth Elements in Geological Samples

A simple and rapid on-line standard addition method for analysis of samples with high dissolved solids by ICP-OES is reported. The method involves on-line addition of standard solutions to the sample using a T-piece, prior to the sample introduction system. The standard addition method is commonly used in the analysis of samples with complex matrices. However, the conventional standard addition method is a tedious and time-consuming process. Therefore, in this study, on-line standard addition technique was offered to significantly decrease the analysis time and increase the simplicity of the standard addition method. The performance of the proposed method was tested by determination of rare earth elements in geological samples. This method showed a high level of accuracy in comparison with external calibration and internal standard addition methods.     

Single vessel procedure for acid vapor partial digestion of bovine liver in a focused microwave: multielement determination by ICP-OES

An acid vapor partial digestion procedure for bovine liver is proposed using a focused microwave oven and a laboratory-made PTFE support. The support is equipped with three cups of approximately 4 ml volume each one and the cups were adapted to the glass reaction vessel of the microwave oven. A mixture containing HNO₃ plus H₂SO₄ is heated to 120 °C to generate acid vapor. Bovine liver (50-90 mg) were directly weighed into the cups followed by addition of a mixture containing NaClO+H₂O₂. Samples were exposed to acid vapor during 15-25 min and then diluted with distilled and deionized water to final masses of 3.0 g. Recoveries of Al, Ca, Cu, Fe, Mg, Mn, and Zn were evaluated using an ICP-OES with axially-viewed configuration. The effects of both particle sizes and acid vapor exposure time were evaluated and recoveries of most elements were quantitative when using 25 min of heating and 50 mg of samples. Slightly better recoveries were reached using particles smaller than 44 μm, but this effect was mainly observed for hardly extracted elements such as Al and Fe.     

Microanalysis of blue pigments from the Ptolemaic temple of Hathor (Thebes), Upper Egypt: a case study

The aim of the present work was to characterize blue pigment samples collected from the Ptolemaic temple of Hathor (Thebes), the western bank of Luxor, Upper Egypt. The characterization of the examined pigments was carried out by means of optical microscopy, scanning electron microscopy equipped with an energy dispersive X‐ray detector, micro X‐ray fluorescence spectrometry and Fourier transform infrared spectroscopy. On the basis of the chemical composition and microstructure of the samples, the blue pigments were identified as Egyptian blue (cuprorivaite, CaCuSi₄O₁₀). Moreover, the micro X‐ray fluorescence analysis revealed significant quantities of lead in the glass phase suggesting that a leaded bronze scrap was used to produce the pigment. The optical examination of the paint layers showed that the pigments were applied on a thin layer consisting of gypsum (CaSO₄?2H₂O) and dolomite (CaMg(CO₃)₂). In addition, some pigment samples showed discoloration mainly in the form of green and black hues. The obtained results helped in improving our knowledge about some painting materials used during the Ptolemaic era of ancient Egypt. Copyright © 2012 John Wiley & Sons, Ltd.     

The Crystal Structure of Kx(MgxIn1–x)F3 (x = 0.38): a New Magnéli‐Bronze Type Fluoride

K_x(Mg_xIn_1–x)F₃ (x = 0.38) is monoclinic, pseudo tetragonal: a = 12.781(2) Å, b = 12.787(2) Å, c = 7.930(1) Å, β = 90,00(1)°, Z = 20. The crystal structure was solved in the space group P2₁/a (No. 14), subgroup of the tetragonal space group P4/mbm (No. 127), from X‐ray single crystal data using 4302 unique reflections (1770 with F_o/σ(F_o) > 4). The final observed R factor is 0.053. K_x(Mg_xIn_1–x)F₃ has the Magnéli‐bronze structural type, which consists in a tridimensional framework of mixed [(Mg_xIn_1–x)F₆] octahedra linked together by corners. The potassium ions are mainly located in large almost fully occupied 15‐coordinated sites and in practically empty 12‐coordinated cavities.     

Determination of cadmium copper, iron, nickel, lead and zinc in crawfish [Procambrus clarkii] by inductively coupled plasma optical emission spectrometry: a study over the 2009 season in Southwest Louisiana

Following a mini-review of crawfish aquaculture, the concentrations (mean in micrograms of analyte per gram of dried sample ± 95% confidence interval, range) determined by inductively coupled plasma-optical emission spectrometry of cadmium (0.49 ± 0.14, 0.34-0.79 ), copper (34.9 ± 5.3, 23.8-44.2), nickel (1.83 ± 0.54, 1.08-3.39), lead (18.0 ± 4.0, 9.9-23.), iron, and zinc (47.3 ± 4.6, 41.3-55.8) were relatively constant with a slight increase in iron (620.4 ± 205.8, 328.8-1072.8) in whole crawfish in a season of 4 months (February through May 2009) in Southwest Louisiana. The temperature of the crawfish ponds was monitored weekly but had no effect on the metal concentration in the crawfish trial. The copper and zinc concentrations in the crawfish pond soil decreased with increasing temperature. The other four metals showing no effect of temperature variations (increase). A comparison with a previous study showed no significant changes in the metal concentrations in the crawfish.