不同产地几种中药材中重金属含量测定及砷的形态分析

通过对不同产地几种中药材中砷、铅、镉、铜以及无机砷、三价砷含量的分析测定,得出样品中砷、铅、镉、铜以及无机砷、无机三价砷的测定RSD〈3%,加标回收率在91.32%—109.7%之间。11个样品的总砷含量在0.047—1.681μg/g之间,均低于2μg/g;无机砷含量为0.023—1.294μg/g;无机三价砷含量为0.019—0.918μg/g;铅含量两份样品未检出,其余样品为0.007—0.786μg/g,均低于5μg/g;镉的测定,两份样品未检出,其余样品含量为0.007—2.129μg/g,其中两份样品大于0.3μg/g;铜含量为4.441—14.07μg/g,均低于20μg/g。研究发现同种药材不同产地的重金属含量差异较大,部分产地金银花中镉含量超标严重,无机砷和三价砷含量相对较高,需引起重视。     

Complementary use of X‐ray methods to study ancient production remains and metals from Northern Portugal

Archaeological artefacts recovered at Castanheiro do Vento (Northern Portugal) were characterised by integrating macro and micro‐energy dispersive X‐ray fluorescence spectrometry (EDXRF) and scanning electron microscopy with X‐ray microanalysis. The collection includes metallurgical remains (ceramic crucibles, a metallic nodule and a vitrified fragment) and metals (tools and ornaments) whose chronology spans from the Chalcolithic to the Roman Age. The study of production remains was able to identify distinct copper‐based metallurgical operations including the smelting of copper ores, the melting of copper and tin and/or the melting of bronze scrap. Micro‐EDXRF identified copper and arsenical copper tools as well as bronze and leaded bronze ornaments. The composition of tools (Cu with varying As contents: 0.46–3.6%) reveals an incipient technology, typical of the Chalcolithic till the Middle Bronze Age. On the contrary, ornaments are composed by different alloys – low tin bronze (4.8% Sn), high tin bronze (14.9% Sn) and high tin‐leaded bronze (16.5% Sn and 2.4% Pb) ? evidencing technological and economic choices that clearly indicate a late period such as the Roman Age. In conclusion, this multiproxy approach was able to study those ancient artefacts with a minimum impact on their archaeological and museological significance while providing important answers to the interpretation of the archaeological settlement and to better understand the metallurgical evolution in the Portuguese territory. Copyright © 2014 John Wiley & Sons, Ltd.     

Colouration mechanism of underglaze copper‐red decoration porcelain (AD 13th–14th century), China

Underglaze copper‐red decoration, i.e. the copper colourant used to paint diversified patterns on the surface of a body and then covered by transparent glaze and fired at high temperature in a reductive firing environment, is famous all over the world. However, the red colouration mechanism generated by underglaze copper remains unclear. In particular, the fact that the edges of the red patterns are orange has been ignored in previous research. Here, non‐destructive analysis has been carried out on a precious fragment of early underglaze red porcelain using synchrotron radiation X‐ray fluorescence, X‐ray absorption near‐edge spectroscopy (XANES) and reflection spectrometry techniques. The results suggest that the copper content in the red region is higher than that in the orange region, and other colour generation elements do not have obvious content difference, indicating that the colour generation effect of the underglaze red product is related to the copper content. XANES analysis shows that the valence states of copper in the red and orange regions are similar and metal copper contributes to their hues. The results of reflection spectrometry demonstrate that tiny orange hues could be attributed to the Mie scatting effect. Therefore, light‐scattering effects should be considered when researching the colouration mechanism of underglaze red.     

Beam‐induced redox transformation of arsenic during As K‐edge XAS measurements: availability of reducing or oxidizing agents and As speciation

During X‐ray absorption spectroscopy (XAS) measurements of arsenic (As), beam‐induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam‐induced redox reactions as a function of sample properties including the redox state of FeS and the solid‐phase As speciation. The beam‐induced oxidation of reduced As species was found to be mediated by the atmospheric O₂ and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface‐complexed As(III) readily underwent the photo‐oxidation upon exposure to the atmospheric O₂ during XAS measurements. With strict O₂ exclusion, however, both As(0) and arsenic sulfide were less prone to the photo‐oxidation by Fe(III) (oxyhydr)oxides than NaAsO₂ and/or surface‐complexed As(III). In case of unaerated As(V)‐reacted FeS samples, surface‐complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo‐reduction.     

Preparation of arsenic‐containing white rice grains as calibration standards for X‐ray fluorescence analysis of total arsenic in cereals

A preparation method of arsenic‐containing white rice grains as calibration standards was developed for the X‐ray fluorescence (XRF) analysis of arsenic in rice grains. Calibration standards were prepared by adding 10 g of white rice grains (from Japan) to 100 ml methanol‐containing dimethylarsinic acid corresponding to 2–100 µg arsenic. The mixture was heated, dried at 150 °C, cooled to room temperature, and then stored in a silica gel desiccator. A total of 5.0 g of each calibration standard was packed into a polyethylene cup (32 mm internal diameter and 23 mm height) covered with a 6‐µm‐thick polypropylene film and then analyzed by wavelength‐dispersive XRF spectrometry. The calibration curve for arsenic obtained from the white rice grains containing arsenic showed good linearity over a concentration range of 0.21–5.00 mg kg^?1 arsenic. The limit of detection of arsenic was 0.080 mg kg^?1. To check the reliability of the XRF method, the concentrations of arsenic in six samples of grain cereals and two samples of flour were compared with those obtained by atomic absorption spectrometry after acid decomposition. The values obtained by both analytical methods showed good agreement. Copyright © 2016 John Wiley & Sons, Ltd.     

On‐site analysis of Limoges enamels from sixteenth to nineteenth centuries: an attempt to differentiate between genuine artefacts and copies

A selection of 15 painted enamels, most of which belong to Limoges productions, from 1500 to 1900 A.D. , has been studied on‐site in the storage rooms of musée des Arts décoratifs in Paris. The Raman signatures of the transparent and/or opacified glass matrix are discussed and compared with those which were previously recorded on glazed pottery, enamelled and stained glasses as well as Chinese cloisonné enamels. Analysed enamels mostly belong to soda‐lime‐based glass. Three types of compositions such as soda‐lime (fifteenth to sixteenth century), soda‐rich (fifteenth, sixteenth/nineteenth centuries) and lead‐potash‐lime (sixteenth and nineteenth centuries) are identified on the basis of the Raman signature of the glaze according to the wavenumber maxima of the Si O stretching and bending multiplets. The pigment signatures are similar to those recorded on ceramic glazes and glass enamels, which proves the similarity of the technologies. Cassiterite as an opacifier and hematite red and Naples yellow pigment variations give characteristic Raman signatures. The presence of lead arsenate as a pigment opacifier in nineteenth‐century samples is confirmed. Attempts are made to establish tools for the differentiation between genuine artefacts and nineteenth‐century restoration or fakes. Copyright © 2010 John Wiley & Sons, Ltd.     

Study of the effects of chronic arsenic poisoning in rat kidneys by means of synchrotron microscopic x‐ray fluorescence analysis

Synchrotron microscopic x‐ray fluorescence analysis (µ‐SRXRF) was used for determining the two‐dimensional distribution of Cl, K, Fe, Cu, Zn, As and Br concentrations in rat kidney slices. The animals received drinking water containing 100 ppm of sodium arsenite ad libitum for 30 and 60 days. Lyophilized kidneys sectioned from normal and treated rats were scanned with a collimated white synchrotron spectrum (300 × 300 µm). The accumulation of arsenic and copper in the rat kidney induced by arsenic exposure was corroborated, and the spatial distributions of these elements were studied in detail. While copper was restricted to the renal cortex, arsenic showed changes in its spatial distribution suggesting nephrotoxicity. A correlation between the spatial distributions of zinc and arsenic was observed, which appears to be caused by the antioxidant properties of zinc. Chlorine and potassium also changed their spatial distributions under arsenic exposure, showing a correlation probably to maintain electrical neutrality. There were no significant changes in iron and bromine but the patterns of their spatial distributions were clearly identified. The obtained results show that µ‐SRXRF is a very well‐positioned and precise technique to detect the spatial distributions of elements in mammalian tissues in healthy and diseased conditions and suggest interesting hypotheses. Copyright © 2006 John Wiley & Sons, Ltd.     

A new ultra‐high‐vacuum variable temperature and high‐magnetic‐field X‐ray magnetic circular dichroism facility at LNLS

X‐ray magnetic circular dichroism (XMCD) is one of the most powerful tools for investigating the magnetic properties of different types of materials that display ferromagnetic behavior. Compared with other magnetic‐sensitive techniques, XMCD has the advantage of being element specific and is capable of separating the spin and magnetic moment contributions associated with each element in the sample. In samples involving, for example, buried atoms, clusters on surfaces or at interfaces, ultrathin films, nanoparticles and nanostructures, three experimental conditions must be present to perform state‐of‐the‐art XMCD measurements: high magnetic fields, low temperatures and an ultra‐high‐vacuum environment. This paper describes a new apparatus that can be easily installed at different X‐ray and UV beamlines at the Brazilian Synchrotron Light Laboratory (LNLS). The apparatus combines the three characteristics described above and different methods to measure the absorption signal. It also permits in situ sample preparation and transfer to another chamber for measurement by conventional surface science techniques such as low‐energy electron diffraction (LEED), reflection high‐energy electron diffraction (RHEED), X‐ray photoelectron spectroscopy (XPS) and X‐ray photoelectron diffraction (XPD). Examples are given of XMCD measurements performed with this set‐up on different materials.     

XAFS study of aqua (diethylenetriamine)(isonicotinato)‐copper(II) complex – inference of square‐pyramidal geometry

X‐ray absorption fine structure (XAFS) of aqua (diethylenetriamine) (isonicotinato) copper(II) complex has been investigated. The crystal structure of the complex is unavailable. The X‐ray absorption near edge structure (XANES) spectrum of the complex has been compared with those of the standard compounds to estimate the coordination geometry and oxidation state of copper. This study indicates that the copper center has +2 oxidation state and that it may be penta or hexa‐coordinated. The spectrum has been further compared with those of the earlier studied complexes having square‐pyramidal geometry. Similarity has been observed between them indicating that the complex should have penta‐coordinated square‐pyramidal geometry. The same inference has been obtained from the study of the characteristic pre‐edge and XANES features. This inference has been further examined by analysis of the extended X‐ray absorption fine structure (EXAFS) spectrum. The experimental EXAFS data has been fitted with three different theoretical models for tetra‐coordination, penta‐coordination, and hexa‐coordination. The tetra model is unable to provide a satisfactory fit so it has been ignored. Although the penta and hexa models give comparable results, the parameters obtained indicate that the penta‐coordinated model fits better to the experimental data than the hexa‐coordinated model. This penta‐coordinated model has been further fitted to the experimental data by allowing the coordination number to vary. Such fitting also shows that the penta‐coordinated model is a satisfactory model for the studied complex. The obtained values of mean‐square disorder indicate that the force constants are different for the equatorial and axial bonds. Copyright © 2014 John Wiley & Sons, Ltd.     

On‐site analysis of Chinese Cloisonné enamels from fifteenth to nineteenth centuries

A selection of 22 rare Chinese cloisonné enamels, from fifteenth century to nineteenth century A.D ., has been studied on‐site in the storage rooms of the musée des Arts décoratifs in Paris. The Raman signatures of the transparent and/or opacified glass matrix are discussed and compared with those that were previously recorded on glazed pottery, enameled and stained glasses. Enamels mostly belong to lead‐based potash‐lime glasses. Three different compositions, lead‐potash‐lime (fifteenth, sixteenth, eighteenth and nineteenth century), soda‐rich (sixteenth–seventeenth century) and soda‐lime (seventeenth century) are identified according to the wavenumber maxima of the Si O stretching and bending multiplets. Most of the pigment signatures are similar to those recorded on ceramic glazes and glass enamels, which proves the link between the technologies but a specific opacifier is observed: fluorite (CaF₂). Naples Yellow pigment variations give characteristic signatures. Additionally, a comparison is made with Limoges enamels (sixteenth–nineteenth century A.D. ). Copyright © 2009 John Wiley & Sons, Ltd.     

Deformable broadband metamaterial absorbers engineered with an analytical spatial Kramers‐Kronig permittivity profile

Electromagnetic (EM) materials with perfect absorption have long been investigated for their important applications in many practical technologies. The trial‐and‐error method has been mostly employed to achieve this target, either by varying the constituent compositions for traditional natural material absorbers or by running computer simulations for general metamaterial (MM) absorbers. In this work, the authors propose a new method with analytical guidance to build omnidirectional perfect absorbers inspired by the recently proposed spatial Kramers‐Kronig (KK) nonreflecting dielectric profile. The subtle combination of the spatial and time dispersions in the metamaterial‐engineered KK profile gives the desired broadband response property. More importantly, these features remain invariant when the sample is uniformly compressed or stretched with large thickness change, i.e., this particular broadband absorber is deformable, which has been firstly reported in the literature. The current results will pave a new way to design high‐efficiency EM absorbers that could also be extended in general to manipulate waves for other fields or applications.

     

Use of synchrotron radiation X‐ray fluorescence and X‐ray absorption spectroscopy to investigate bioaccumulation,molecular target,and biotransformation of volcanic elements

Because environment pollutants have a strong impact on ecosystems, including human health, methods of their determination and mitigation have received special attention in recent years. Taking advantage of the wide range of data that can be obtained by synchrotron radiation X‐ray fluorescence spectroscopy (SRXRF) in the field of environmental sciences, different instrumental setups were used to study the biological fates of toxic elements in volcanic environments. The elemental composition of plants, algae, and bacteria in Copahue and Domuyo volcanoes from Argentinean Patagonia was determined by SRXRF and the volcanic elements Ti, Fe, and Zn were abundant in these organisms. Interestingly, a high As concentration was found in cyanobacteria (26.2 μg/g) living in As contaminated stream (250 μg/ml). Because arsenic is toxic and human carcinogen, element‐retention capacity, element‐protein associations, and arsenic metabolism in this As resistant organism were analyzed by SRXRF. A high capacity (100–95%) of Ti > Fe > Cr > Sr > Ni > Cu > Mn > Zn > As retention was found after aqueous/alcoholic extraction assisted by ultrasonication. The cyanobacterial proteins were separated by SDS‐PAGE, electro‐transferred to nitrocellulose, and mapped by SRXRF. Defined protein bands containing Ca, Ti, Mn, Fe, and/or Zn were observed. Their ability to metabolize arsenic was revealed by combining SRXRF and X‐ray absorption near edge spectroscopy and Dimethylarsenic was found. Based on results, we speculate that these cyanobacteria could be interesting candidates for water treatment. Finally, we conclude that SRXRF is a valuable tool to study the biological cycle of environmental pollutants, including their accumulation, molecular targets, and metabolism. The SRXRF may also assist in remediation researches.     

Application of synchrotron‐radiation‐induced TXRF‐XANES for arsenic speciation in cucumber (Cucumis sativus L.) xylem sap

Synchrotron‐radiation‐induced total reflection x‐ray fluorescence (SR‐TXRF) analysis was used for x‐ray absorption near edge structure (XANES) measurements for the speciation of arsenic in cucumber (Cucumis sativus L.) xylem sap. The objective of the presented work was to exploit the advantages of the TXRF geometry for XANES analysis. Measurements were accomplished at the bending magnet beamline L of HASYLAB, Hamburg, Germany, using a Si(111) double crystal monochromator and a silicon drift detector (SDD). Experiments were performed by growing cucumber plants in hydroponics containing arsenite [As(III)] or arsenate [As(V)] in order to identify the arsenic species of the collected xylem saps by K‐edge SR‐TXRF XANES. Cucumber xylem saps, as well as nutrient solutions containing arsenic in the two above‐mentioned species, were analyzed and compared with arsenate and arsenite standard solutions. Arsenic speciation in xylem sap down to 30 ng/ml (30 ppb) was achieved, and no alteration of the oxidation state was observed during the measurements. Analysis of xylem saps showed that As(V) taken up from the nutrient solution was reduced to As(III). As(III) contained in the nutrient solutions was found to be partially oxidized to As(V). These results confirmed the preliminary measurements obtained with flow injection analysis (FIA) and high‐performance liquid chromatography‐high resolution inductively coupled plasma mass spectrometry (HPLC‐HR‐ICP‐MS) and showed the competitive capability of SR‐TXRF XANES analysis for this application. Copyright © 2007 John Wiley & Sons, Ltd.     

A One‐Dimensional Particle‐in‐Cell Model of Plasma Build‐Up in Vacuum Arcs

Understanding the mechanism of plasma build‐up in vacuum arcs is essential in many fields of physics. A one‐dimensional particle‐in‐cell computer simulation model is presented, which models the plasma developing from a field emitter tip under electrical breakdown conditions, taking into account the relevant physical phenomena. As a starting point, only an external electric field and an initial enhancement factor of the tip are assumed. General requirements for plasma formation have been identified and formulated in terms of the initial local field and a critical neutral density. The dependence of plasma build‐up on tip melting current, the evaporation rate of neutrals and external circuit time constant has been investigated for copper and simulations imply that arcing involves melting currents around 0.5–1 A/μm², evaporation of neutrals to electron field emission ratios in the regime 0.01 – 0.05, plasma build‐up timescales in the order of ～ 1 – 10 ns and two different regimes depending on initial conditions, one producing an arc plasma, the other one not. Also the influence of the initial field enhancement factor and the external electric field required for ignition has been explored, and results are consistent with the experimentally measured local field value of ～ 10 GV/m for copper (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Engineering Materials

The existence of the Stone, Bronze, and Iron Ages points to the importance of materials in humankind's development. The corresponding materials were used for art and jewelry, but most prominently for structural applications—as tools and weapons. While the ages themselves define step changes in material strength and durability, there was also significant material development within each age, such as the evolution from pure copper to alloys with tin, arsenic, and other metals in the Bronze Age. In a sense, we are still partially in the Iron Age, as steel (along with concrete) is the dominant structural material in our modern infrastructure, and continues to evolve in performance. For example, today's steels are significantly stronger and less prone to embrittlement than steel used for the RMS Titanic a century ago. On the other hand, we increasingly use specialty materials, such as polymer-metal composites, for high strength-to-weight ratio applications, and thermal-barrier coatings on Ni-based superalloys to operate turbines at very high temperatures. Most recently, the additive manufacturing revolution has opened up new possibilities for materials by design, where enhanced flexibility in composition, microstructure, and topological optimization relative to conventional processing methods offers many new opportunities and challenges.     

Characterization of Nano‐Particles Using Laser‐Induced Incandescence

Laser‐induced incandescence (LII) is introduced as a valuable tool for the characterization of nanoparticles. This optical measurement technique is based on the heating of the particles by a short laser pulse and the subsequent detection of the thermal radiation. It has been applied successfully for the investigation of soot in different fields of application, which is described here in the form of an overview with a focus on work done at the LTT‐Erlangen during the last 10 years. In laboratory flames the soot primary particle size, volume concentration, and relative aggregate size have been determined in combination with the number density of primary particles. Furthermore, the primary particle sizes of carbon blacks have been measured in situ and online under laboratory conditions and also in production reactors. Measurements with different types of commercially available carbon black powders, which were dispersed in a measurement chamber yielded a good correlation between LII results and the specified product properties. Particle diameters determined by LII in a furnace black reactor correlate very well with the CTAB‐absorption number, which is a measure for the specific surface area. It turned out that the LII method is not affected by variations of the aggregate structure of the investigated carbon blacks. The LII signal also contains information on the primary particle size distribution, which can be reconstructed by the evaluation of the signal decay time at, at least, two different time intervals. Additionally, soot mass concentrations have been determined inside diesel engines and online measurements were performed in the exhaust gas of such engines for various engine conditions simultaneously providing information about primary particle size, soot volume, and number concentration. The LII results exhibit good correlation with traditional measurement techniques, e.g., filter smoke number measurements. In addition to the soot measurements, primarily tests with other nanoparticles like TiO₂ or metal particles are encouraging regarding the applicability of the technique for the characterization of such different types of nanoparticles.     

Inclusions and metal composition of ancient copper‐based artefacts: a diachronic view by micro‐EDXRF and SEM‐EDS

A diachronic view of the metallurgy in the Portuguese territory during the first three millennia after its appearance in the Iberian Peninsula is presented based on the current state of the art. Results of micro‐energy dispersive X‐ray fluorescence (micro‐EDXRF) analyses made on metal artefacts to determine their composition and scanning electron microscopy with energy dispersive analysis (SEM‐EDS) analyses to study microstructural features as inclusions are shown to illustrate trends and specificities of each chronological period. Generally, in early periods, namely during the Copper Age and first stages of the Bronze Age, unalloyed copper and arsenical copper were at use, and only by the Late Bronze Age (LBA) did tin bronze substitute almost completely the previous role of copper. In the Early Iron Age, during the Orientalising period, a general decrease in the average tin content in bronzes seems to happen. Regarding the inclusions observed in the metal matrix, these seem to suffer a diversification with the appearance of tin bronzes. By the Copper Age, only Cu? O and Cu? As? O inclusions are observed, while by the LBA Cu? S inclusions become regular, besides others less frequent, as Sn? O, Cu? S? Fe and Pb globules. Overall, with the present analytical study, the complementary character of micro‐EDXRF and SEM‐EDS in the study of ancient metals is demonstrated, providing a first general overview of the ancient metallurgy at the Portuguese territory which is of key importance to specific investigations of the future. Copyright © 2011 John Wiley & Sons, Ltd.     

Light‐induced degradation in copper‐contaminated gallium‐doped silicon

To date, gallium‐doped Czochralski (Cz) silicon has constituted a solar cell bulk material free of light‐induced degradation. However, we measure light‐induced degradation in gallium‐doped Cz silicon in the presence of copper impurities. The measured degradation depends on the copper concentration and the material resistivity. Gallium‐doped Cz silicon is found to be less sensitive to copper impurities than boron‐doped Cz silicon, emphasizing the role of boron in the formation of copper‐related light‐induced degradation. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)