Molecular scale speciation of first-row transition elements bound to ligneous material by using X-ray absorption spectroscopy

To develop a solid scientific basis for maintaining soil quality and formulating effective remediation strategies, it is critical to determine how environmentally-important trace metals are sequestered in soils at the molecular scale. The speciation of Mn, Fe and Cu in soil organic matter has been determined by synchrotron-based techniques: extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES). We show the structural similarity between the surface complexes of Mn(II), Fe(III) and Cu(II). These cations are bound to the surface through oxygen atoms. Each one presents a more or less tetragonal-distorted octahedral geometry. The use of X-ray absorption spectroscopy provides a relevant method for determining trace-metal speciation in both natural and contaminated environmental materials.     

Improvement in arsenic speciation,using hydride generation and atomic absorption spectrophotometry

Improvements in arsenic speciation in sea-water using hydride generation, cold trapping and AAS are reported. Progressive addition of sodium tetrahydroborate and pH optimization are essential to obtain reliable results. The response factor for As^III, As^v, methylarsonic acid and dimethylarsinic acid is nearly the same when sulphuric acid is used for the hydride generation step.     

X-ray absorption and X-ray photoelectron spectroscopy of a rhodium colloid

Transition metal colloids are potential precursors of heterogeneous catalysts with application to selective chemical reactions. Sample preparation techniques are described. Experimental details are given of the characterization of these often air-sensitive particles by X-ray photoelectron and X-ray absorption spectroscopy. First results obtained with both techniques for a Rh-colloid show that the metal is mainly present in the zerovalent chemical state. But the spectra indicate further chemical states of Rh which can be assigned to the outermost metal atoms of the colloid interacting with organic ligands or to the educt Rh-halides.     

X-ray absorption and X-ray photoelectron spectroscopy of a rhodium colloid

Transition metal colloids are potential precursors of heterogeneous catalysts with application to selective chemical reactions. Sample preparation techniques are described. Experimental details are given of the characterization of these often air-sensitive particles by X-ray photoelectron and X-ray absorption spectroscopy. First results obtained with both techniques for a Rh-colloid show that the metal is mainly present in the zerovalent chemical state. But the spectra indicate further chemical states of Rh which can be assigned to the outermost metal atoms of the colloid interacting with organic ligands or to the educt Rh-halides.     

X-ray absorption near-edge structure (XANES) spectroscopy identifies differential sulfur speciation in corneal tissue

The chemical composition of tissues can influence their form and function. As a prime example, the lattice-like arrangement of collagen fibrils required for corneal transparency is controlled, in part, by sulfated proteoglycans, which, via core proteins, bind to the collagen at specific locations along the fibril axis. However, to date, no studies have been able to directly identify and characterize sulfur (S) in the cornea as a function of tissue location. In this study, X-ray absorption near-edge structure spectroscopy and micro-beam X-ray fluorescence (μ-XRF) chemical contrast imaging were employed to probe the nature of the mature (bovine) cornea as a function of position from the anterior sub-epithelial region into the deep stroma. Data indicate an inhomogeneity in the composition of S species in the first ≈50 μm of stromal depth. In μ-XRF chemical contrast imaging, S did not co-localize with phosphorous (P) in the deep stroma where sulfates are prominent. Rather, P is present only as isolated micrometric spots, presumably identifiable as keratocytes. This study lends novel insights into the elemental physiology of mature cornea, especially in relation to its S distribution; future studies could be applied to human tissues. Moreover, it defines an analytical protocol for the interrogation of S species in biological tissues with micrometric resolution.

X-ray absorption spectroscopy of transition-metal trichalcogenides

The sulfur K and metal L_III absorption spectra of transition-metal trichalcogenides (TMTC's) were measured. The matrix element effect plays an important role in these spectra. It was considered that the structures up to 5 eV above the absorption edge reflect the chalcogen antibonding band, the metal nonbonding d_z² band, and the metal d bands, and that the higher energy structures are derived from the metal s and p bands. The chalcogen antibonding band arises from chalcogen pairing and the metal d, s, and p bands are the mixture bands with chalcogen p orbitals. Evidence that shows that the lowest conduction band of the group IV TMTC's is the chalcogen antibonding band is presented. The overlap of the metal d and metal s bands is promoted by increasing the atomic number of chalcogen atoms.     

X-ray absorption spectroscopy of selenate reductase

The metal sites of selenate reductase from Thauera selenatis have been characterized by Mo, Se, and Fe K-edge X-ray absorption spectroscopy. The Mo site of the oxidized enzyme has 3 to 4 sulfur ligands at 2.33 A from two molybdopterin cofactors, one Mo=O group at 1.68 A and one Mo-O with an intermediate bond length of 1.81 A. The reduced enzyme has a des-oxo active site, again with about four Mo-S ligands (at 2.32 A) and possibly one oxygen ligand at 2.22 A. The enzyme was found to contain Se in a reduced form (probably organic) although the sequence does not indicate the presence of selenocysteine. The Se is coordinated to both a metal (probably Fe) and a lighter scatterer such as carbon.     

Millisecond kinetics of nanocrystal cation exchange using microfluidic X-ray absorption spectroscopy

We describe the use of a flow-focusing microfluidic reactor to measure the kinetics of the CdSe-to-Ag2Se nanocrystal cation exchange reaction using micro-X-ray absorption spectroscopy (microXAS). The small microreactor dimensions facilitate the millisecond mixing of CdSe nanocrystals and Ag+ reactant solutions, and the transposition of the reaction time onto spatial coordinates enables the in situ observation of the millisecond reaction using microXAS. Selenium K-edge absorption spectra show the progression of CdSe nanocrystals to Ag2Se over the course of 100 ms without the presence of long-lived intermediates. These results, along with supporting stopped-flow absorption experiments, suggest that this nanocrystal cation exchange reaction is highly efficient and provide insight into how the reaction progresses in individual particles. This experiment illustrates the value and potential of in situ microfluidic X-ray synchrotron techniques for detailed studies of the millisecond structural transformations of nanoparticles and other solution-phase reactions in which diffusive mixing initiates changes in local bond structures or oxidation states.     

X-ray absorption spectroscopy of nanostructured polyanilines

In this paper, X-ray absorption near edge spectroscopy at the nitrogen K edge (N K XANES) data of polyaniline (PANI) and its derivatives were revisited and expanded. The N K XANES spectra of PANI nanocomposites and PANI nanofibers were also investigated. The analysis of N K XANES spectra were done by the deconvolution of bands and the 1s → π* and 1s → σ* transitions were assigned by a correlation with the N K XANES spectra of smaller organic compounds. The “free” forms of PANI were dominated by bands from 397.7 eV to 399.1 eV attributed to imine and radical cation nitrogen atoms, respectively. Nitrogen bonded to phenazine-like rings can also be seen, mainly for PANI prepared at pH higher than 3.0. The spectra of nanocomposites show sharper bands than the “free” polymers as well as new bands at 398.8 eV and 405–406 eV. These new bands were assigned to phenazine-like rings and azo bonds in the structure of the polymers (polyaniline, polybenzidine, and poly(p-phenylediamine)) within the galleries of the montmorillonite clay. PANI nanofibers doped with HCl or HClO₄ show bands related to phenazine-like rings and/or dication segments of PANI, indicating that these segments are important in the formation of PANI nanofibers.     

Analysis of mixtures of compounds of copper using K-edge X-ray absorption spectroscopy

Summary A determination is described of copper metal, oxide, and hydroxide in samples containing both nickel and copper. The analysis was based on K-edge x-ray absorption spectra of the copper. This allowed us to consider the chemical states of copper and ignore the nickel also present. The method involved fitting linear combinations of copper standard spectra to the spectrum from copper in the sample. The fit composition that minimized the variance gave the sample composition. The work demonstrated that K-edge x-ray absorption spectra are sufficiently characteristic to allow their use for quantification of components in mixtures. This method of analysis is complemented by diffraction and less general techniques. It is a strength of x-ray absorption edge analysis that it is element-specific and applicable to most elements maintained under any conditions of temperatures, pressure, and atmosphere.     

X-ray absorption spectroscopy measurements of liquid water

Recent studies, based on X-ray absorption spectroscopy (XAS) and X-ray Raman scattering (XRS), have shown that the hydrogen bond network in liquid water consists mainly of water molecules with only two strong hydrogen bonds. Since this result is controversial, it is important to demonstrate the reliability of the experimental data, which is the purpose of this paper. Here we compare X-ray absorption spectra of liquid water recorded with five very different techniques sensitive to the local environment of the absorbing molecule. Overall, the spectra obtained with photon detection show a very close similarity and even the observable minor differences can be understood. The comparison demonstrates that XAS and XRS can indeed be applied reliably to study the local bonding of the water molecule and thus to reveal the hydrogen bond situation in bulk water.     

Development of a method for speciation of inorganic arsenic in waters using solid phase extraction and electrothermal atomic absorption spectrometry

A solid phase extraction (SPE) procedure based on Amberlite IRA 900 resin was developed for speciation and separation of inorganic arsenic species (III, V) and total As in water samples. The As species and total As in eluent solutions were determined by electrothermal atomic absorption spectrometry (ETAAS) using Ni chemical modifier with 1200°C pyrolysis temperature. Experimental parameters such as pH value, sample volume, flow rate, volume and concentration of eluent solution for As(V) were optimised and 98.0 ± 1.9% recovery was found at pH 4.0. Experimental adsorption capacity of the resin for As(V) was investigated and 229.9 mg g^–1 was found. Under optimised experimental conditions, instrumental parameters such as limit of detection (LOD) and limit of quantification (LOQ) found were 0.126 and 0.420 µg L^–1, respectively. Interference effects of coexisting ions in the sample matrix on the recovery of As(V) were investigated. Concentration of As(III) was obtained by subtracting As(V) concentration found at pH 4.0 from total As(III + V) found at pH 8.0. The accuracy of the method proposed by using the resin was tested for analysing As species in a waste water standard reference material (SRM, CWW-TM-D) and spiked real water samples with recovery above 95%. The method proposed was also applied to the determinations of As species and total As in underground hot waters and tap water with relative error below 3%.     

Non-chromatographic screening procedure for arsenic speciation analysis in fish-based baby foods by using electrothermal atomic absorption spectrometry

A procedure for the speciation analysis of arsenic in fish-based baby foods is presented. Inorganic arsenic, methylarsonic acid (MA), dimethylarsinic acid (DMA) and arsenobetaine (AB) were determined by electrothermal atomic absorption spectrometry (ETAAS) using suspensions prepared in a 0.01 mol L⁻¹ tetramethylammonium hydroxide (TMAH) solution. Speciation is based on the use of three different chemically modified ETAAS atomizers to obtain the analytical signals. Using a palladium salt as the chemical modifier, the signal corresponding to the total arsenic concentration is obtained. When palladium is replaced by Ce(IV), the signal is solely due to inorganic arsenic (III and V) + MA. If no signal is obtained in this latter case, it is possible to distinguish between DMA and AB using a zirconium coated atomizer. The signal obtained in this way is due solely to DMA, and the concentration of AB can be obtained by the difference with the total arsenic content. Determinations by ETAAS require the use of the standard additions method. The limits of detection for the determination of AB, DMA and inorganic arsenic (+MA) are 15, 25 and 50 ng g⁻¹ expressed as arsenic, respectively. These detection limits are good enough for the procedure to be appropriate for the rapid determination of these compounds, avoiding extraction processes and/or chromatographic separations. Data for commercial samples, as well as for four standard reference materials, are given.     

原位拉曼光谱与X射线吸收光谱研究能源转换电催化反应

近年来,水分解、氧气/二氧化碳还原等电化学能源转换技术为解决全球能源短缺及环境问题提供了新的思路和方向.然而,对这些能源转换技术的反应机理及其催化剂的活性位点目前仍缺乏深刻的认识和理解,这限制了高效、稳定催化剂的开发,以致阻碍该类电化学技术的进一步发展.原位光谱技术的快速发展为解决上述问题提供了坚实的基础,其中拉曼光谱...     

A systematic resolution of sulfur in reticulated vitreous carbon using X-ray absorption spectroscopy

Sulfur K-edge X-ray absorption spectroscopy (XAS) was used to characterize the approximately 0.1% sulfur found both in native reticulated vitreous carbon (RVC) foam and in RVC oxidatively modified using 0.2 M KMnO4 in 2 M H2SO4. Sulfur valences and functional groups were assessed using K-edge XAS spectral curve-fitting and employing explicit sulfur compounds as models. For native RVC, these were episulfide (approximately 3%), thianthrene (approximately 9%), disulfide (approximately 10%), sulfenate ester (approximately 12%), benzothiophene (approximately 24%), N,N'-thiobisphthalimide (approximately 30%), alkyl sulfonate (approximately 1.2%), alkyl sulfate monoester (approximately 6%), and sulfate dianion (approximately 6%). Permanganate oxidation of RVC diminished sulfenic sulfur to approximately 9%, thianthrenic sulfur to approximately 7%, and sulfate dianion to approximately 1% but increased sulfate monoester to approximately 12%, and newly produced sulfone (approximately 2%) and sulfate diester (approximately 5%). A simple thermodynamic model was derived that allows proportionate functional group comparisons despite differing (approximately +/-15%) total sulfur contents between RVC batches. The limits of accuracy in the XAS curve-fitting analysis are discussed in terms of microenvironments and extended structures in RVC carbon that cannot be exactly modeled by small molecules. Sulfate esters cover approximately 0.15% of the RVC surface, increasing to approximately 0.51% following permanganate/sulfuric acid treatment. The detection of episulfide directly corroborates a proposed mechanism for the migration of elemental sulfur through carbon.     

X-ray absorption spectroscopy of rare earth intermediate oxides

The M_IV–V and L_III absorption spectra (between 850 and 7500 eV) of intermediate rare earth oxides (Pr₇O₁₂ and Pr₉O₁₆) were studied. These oxides required careful preparation and handling in order to assure their composition.The spectra are characterized by multiplet features that are interpreted as having contributions from both trivalent and tetravalent sites. In the M_IV–V spectra the appearance of distinct multiplet lines and additional weaker features demonstrate clearly the increasing ratio of the tetravalent sites as the oxygen content increases from Pr₇O₁₂ to PrO₂. Similar behavior has been observed for the CeO_x and TbO_x systems. These observations show that in these oxides, the trivalent and tetravalent sites are inequivalent and that the evidence of valence transition is seen in the appearance of the complex spectral features originating from the tetravalent sites.     

Local structure of nitrogen atoms in a porphine ring of mesophenyl substituted porphyrin with an electron-withdrawing group using X-ray photoelectron spectroscopy and X-ray absorption spectroscopy.

This study investigated the protonation of nitrogen atoms in porphyrins with meso-phenyl p-substituted by an electron-withdrawing group using N 1s X-ray photoelectron spectroscopy (XPS), the N K X-ray absorption near-edge structure (XANES), and the discrete variational (DV)-Xalpha molecular orbital (MO) method. Both tetraphenylporphyrin (TPP) and tetrakis(p-sulfonatophenyl)porphyrin (TSPP) have a single structure: the former has two protonated and two non-protonated N atoms in the porphine ring; the latter has four protonated N atoms in the porphine ring. In contrast, a combination of XPS, XANES, and DV-Xalpha MO calculations shows that tetrakis(p-carboxyphenyl)porphyrin (TCPP) has a dual structure: one structure has two protonated and two non-protonated N atoms; the other has four protonated N atoms. Furthermore, this result was also considered based on the protonation constants of N atoms in the porphyrins. The correlation between the strength of electron-withdrawing groups and protonation to N atoms in porphyrins can be described using the spectral patterns of the N 1s XPS and N K XANES spectra.     

HPLC-ICP-MS测定中药中砷的形态

报道了高效液相色谱-电感耦合等离子体质谱（HPLC—ICP-MS）联用技术测定中药中砷的形态，采用阴离子交换柱，以0．2mmol／L EDTA和2mmol／L NaH2PO4的溶液为流动相，pH6．0，流速为1．0mL／min，成功分离了亚砷酸（AsⅢ）、砷酸（AsV）、甲基砷（MMA）和二甲基砷（DMA）。检出限分别为0．67μg／L（AsⅢ），0．85μg／L（DMA），0．43μg／L（MMA），0．70μg／L（AsV）。中药样品经过（1＋1）甲醇和水的溶液超声提取，离心、过滤、氮气吹干甲醇，超纯水定容。样品加标平均萃取回收率分别为：92．8％（AsⅢ），108％（DMA），104％（MMA），101％（AsV），相对标准偏差（RsD，n=7）均小于10％。     

HPLC-ICP-MS测定中药中砷的形态

报道了高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)联用技术测定中药中砷的形态.采用阴离子交换柱,以含0.2 mmol/L乙二胺四乙酸(EDTA)和2 mmol/L NaH2PO4的水溶液为流动相,pH 6.0,流速为1.0 mL/min,成功分离了亚砷酸(AsⅢ)、砷酸(AsⅤ)、甲基砷(MMA)和二甲基砷(DMA).检出限分别为0.67 μg/L (AsⅢ),0.85 μg/L (DMA),0.43 μg/L (MMA),0.70 μg/L (AsⅤ).中药样品经过(1 1)甲醇水溶液超声提取,离心、过滤、氮气吹干甲醇,超纯水定容.样品加标平均萃取回收率分别为: 92.8% (AsⅢ),108% (DMA),104% (MMA),101% (AsⅤ),RSD (n=7)均小于10%.     

Chemical-state analysis of organic semiconductors using soft X-ray absorption spectroscopy combined with first-principles calculation

The chemical states of organic semiconductors were investigated by total-electron-yield soft X-ray absorption spectroscopy (TEY-XAS) and first-principles calculations. The organic semiconductors, pentacene (C(22)H(14)) and pentacenequinone (C(22)H(12)O(2)), were subjected to TEY-XAS and the experimental spectra obtained were compared with the 1s core-level excited spectra of C and O atoms, calculated by a first-principles planewave pseudopotential method. Excellent agreement between the measured and the calculated spectra were obtained for both materials. Using this methodology, we examined the chemical states of the aged pentacene, and confirmed that both C-OH and C═O chemical bonds are generated by exposure to air. This result implies that not only oxygen but also humidity causes pentacene oxidation.