Determination of adsorption and speciation of chromium species by saltbush (Atriplex canescens) biomass using a combination of XAS and ICP-OES

Studies were performed to determine the effect of pH on chromium (Cr) binding by native, esterified, and hydrolyzed saltbush (Atriplex canescens) biomass. In addition, X-ray absorption spectroscopy studies were performed to determine the oxidation state of Cr atoms bound to the biomass. The amounts of Cr adsorbed by saltbush biomass were determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES). For Cr(III), the results showed that the percentages bound by native stems, leaves, and flowers at pH 4.0 were 98%, 97%, and 91%, respectively. On the other hand, the Cr(VI) binding by the three tissues of the native and hydrolyzed saltbush biomass decreased as pH increased. At pH 2.0 the stems, leaves, and flowers of native biomass bound 31%, 49%, and 46%, of Cr(VI), respectively. The results of the XAS experiments showed that Cr(VI) was reduced in some extend to Cr(III) by saltbush biomass at both pH 2.0 and pH 5.0. The XANES analysis of the Cr(III) reaction with the saltbush biomass parts showed an octahedral arrangement of oxygen atoms around the central Cr(III) atom. The EXAFS studies of saltbush plant samples confirmed these results.     

Binding of erbium(III) and holmium(III) to native and chemically modified alfalfa biomass: a spectroscopic investigation

Traditional treatment methods used to clean-up heavy metal contamination of soils and waters are cost intensive whereas more cost effective methods need to be developed. The use of plant materials to remediate heavy contamination has been studied for the past two decades. This technique has shown much promise for many of the common heavy metal contaminants, but few studies have focused on the lanthanide series elements. By investigating the binding and interactions of the lanthanide elements to alfalfa biomass, a more complete understanding of the binding mechanisms and the interactions of heavy metals with biomaterials can be obtained. Different chemical functional groups on the alfalfa biomass, carboxyl, amino, sulfur, and ester groups, were modified to investigate the binding mechanisms of erbium(III) and holmium(III). Batch experiments were performed with native and chemically modified alfalfa biomass suggesting that the carboxyl groups play a major role in the binding of erbium(III) and holmium(III) to the alfalfa biomass. In addition, X-ray absorption spectroscopy (XAS) studies corroborated the data obtained from the batch experiments.     

XAS and XPS studies on chromium-binding groups of biomaterial during Cr(VI) biosorption

The reduction of toxic Cr(VI) to the less or nontoxic Cr(III) may be an useful detoxification technique for the treatment of Cr(VI)-contaminated waters. Recently, the protonated biomass of brown seaweed, Ecklonia, was shown to completely reduce Cr(VI) to Cr(III) in the pH range 1-5. The reduction of Cr(VI) to Cr(III) appeared to occur at the surface of the biomass. In this study, abiotic Cr(VI) reduction by the biomass was performed with various contact times, pHs and initial Cr(VI) concentrations, and surface and bulk characteristics of the Cr-laden biomass was then investigated using X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The XPS spectra indicated that the Cr(VI) bound to the biomass was completely reduced to Cr(III) at tested various conditions. XANES and EXAFS spectra of the Cr-laden biomass were very similar to those of Cr(III)-acetate, which means that the Cr bound to the biomass during Cr(VI) reduction had an octahedral geometrical arrangement. The bonding distance of the chromium oxygen atoms was approximately 1.97-1.99 A. In conclusion, it was obvious that oxygen containing groups, such as carboxyl and phenolic groups, play a major role in the binding of the Cr(III) resulting from the abiotic reduction of Cr(VI) by the biomass.     

A solution study on the local and global structure changes of cytochrome c: an unfolding process induced by urea

The local and global structural changes of cytochrome c induced by urea in aqueous solution have been studied using X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). According to the XAS result, both the native (folded) protein and the unfolded protein exhibit the same preedge features taken at Fe K-edge, indicating that the Fe(III) in the heme group of the protein maintains a six-coordinated local structure in both the folded and unfolded states. Furthermore, the discernible differences in the X-ray absorption near-edge structure (XANES) of these two states are attributed to a possible spin transition of the Fe(III) from a low-spin state to a high-spin state during the unfolding process. The perseverance of six-coordination and the spin transition of the iron are reconciled by a proposed ligand exchange, with urea and water molecules replacing the methionine-80 and histidine-18 axial ligands, respectively. The SAXS result reveals a significant morphology change of cytochrome c from a globular shape of a radius of gyration R(g) = 12.8 A of the native protein to an elongated ellipsoid shape of R(g) = 29.7 A for the unfolded protein in the presence of concentrated urea. The extended X-ray absorption fine structure (EXAFS) data unveil the coordination geometries of Fe(III) in both the folded and unfolded state of cytochrome c. An initial spin transition of Fe(III) followed by an axial ligand exchange, accompanied by the change in the global envelope, is proposed for what happened in the protein unfolding process of cytochrome c.     

Use of chemical modification and spectroscopic techniques to determine the binding and coordination of gadolinium(III) and neodymium(III) ions by alfalfa biomass

Metal pollution in the aqueous environment has become an important issue in the past few decades leading to extensive research in the area of pollution remediation. Most of the recent research in this area has been in bioremediation including phytofiltration and phytoextraction. Although there has been a lot of research done in the field of metal interactions with plants, the actual mechanism(s) and ligands involved are not well understood. Through a series of batch experiments, including pH profiles, time dependency studies, and capacity experiments, we have investigated the binding of Gd(III) and Nd(III) to alfalfa biomass. Batch pH studies showed that the optimum binding was at pH 5.0 for both elements. The time dependency experiments showed that the binding occurs within the first 5 min of contact and remains constant for up to 60 min. In addition, chemical modifications to the alfalfa biomass were performed to indirectly determine the ligands on the biomass responsible for metal binding. For Gd(III) binding, it was shown that the carboxyl groups on the biomass play the most important role in metal ion binding. However, for Nd(III), not only was it found that the carboxyl groups play an important role in the binding, but in addition, the amino groups on the biomass also play an important role in the binding of the metal ions. Further studies using X-ray absorption spectroscopy (XAS) showed that the Gd(III) and Nd(III) ions were bound to the alfalfa biomass through oxygen (or nitrogen ligands), which were coordinated to carbon atoms. The lanthanide complexes within the biomass included some coordinated water molecules.     

Iron (Fe) speciation in xylem sap by XANES at a high brilliant synchrotron X-ray source: opportunities and limitations

The development of highly brilliant synchrotron facilities all around the world is opening the way to new research in biological sciences including speciation studies of trace elements in plants. In this paper, for the first time, iron (Fe) speciation in xylem sap has been assessed by X-ray absorption near-edge structure (XANES) spectroscopy at the highly brilliant synchrotron PETRA III, beamline P06. Both standard organic Fe-complexes and xylem sap samples of Fe-deficient tomato plants were analyzed. The high photon flux provided by this X-ray synchrotron source allows on one side to obtain good XANES spectra in a reasonable amount of time (approx. 15 min for 200 eV scan) at low Fe concentrations (sub parts-per-million), while on the other hand may cause radiation damage to the sample, despite the sample being cooled by a stream of liquid nitrogen vapor. Standard Fe-complexes such as Fe(III)-succinate, Fe(III)-α-ketoglutarate, and Fe(III)-nicotianamine are somehow degraded when irradiated with synchrotron X-rays and Fe(III) can undergo photoreduction. Degradation of the organic molecules was assessed by HPLC-UV/Vis analyses on the same samples investigated by X-ray absorption spectroscopy (XAS). Fe speciation in xylem sap samples revealed Fe(III) to be complexed by citrate and acetate. Nevertheless, artifacts created by radiation damage cannot be excluded. The use of highly brilliant synchrotrons as X-ray sources for XAS analyses can dramatically increase the sensitivity of the technique for trace elements thus allowing their speciation in xylem sap. However, great attention must be paid to radiation damage, which can lead to biased results.

X-ray spectroscopic and diffraction study of the structure of the active species in the Ni(II)-catalyzed polymerization of isocyanides.

The structure of the active complex in the Ni-catalyzed polymerization of isocyanides to give polyisocyanides is investigated. It is shown by X-ray absorption spectroscopy (XAS), including EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure), and single-crystal X-ray diffraction, to contain a carbene-like ligand. This is the first structural characterization of a crucial intermediate in the so-called merry-go-round mechanism for Ni-catalyzed isocyanide polymerization.     

EXAFS studies on gold nanoparticles over novel catalytic materials

Novel nanogold catalytic systems made up of gold nanoparticles (∼2–6 nm) supported on niobium, ytterbium, lanthanum and cerium oxide materials were synthesized. XAS is uniquely suited for studying catalytic systems with low metal and high metal dispersion. Au L₃ edge X-ray absorption spectroscopic measurements were carried out over a series of supported gold nanoparticles. The interesting results obtained from EXAFS and XANES confirms the typical characteristics and structure of gold nanoparticles in these materials.     

Nucleation and growth mechanism of Pd/Pt bimetallic clusters in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles as studied by in situ X-ray absorption spectroscopy

We report in situ X-ray absorption spectroscopy (XAS) investigations on the formation of palladium-platinum (Pd/Pt) bimetallic clusters at the early stage within the water-in-oil microemulsion system of water/AOT/n-heptane. The reduction of palladium and platinum ions and the formation of corresponding clusters are monitored as a function of dosage of reducing agent, hydrazine (N(2)H(5)OH). Upon successive addition of the reducing agent, hydrazine (N(2)H(5)OH), five distinguishable steps are observed in the formation process of Pd/Pt clusters at the early stage. Both in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis for both the Pd K-edge and Pt L(III)-edge revealed the formation of Pd/Pt bimetallic clusters. A corresponding structural model is proposed for each step to provide a detailed insight into the nucleation and growth mechanism of Pd/Pt bimetallic clusters. We also discussed the atomic distribution of Pd and Pt atoms in Pd/Pt bimetallic clusters based on the calculated XAS structural parameters.     

Surface arsenic speciation of a drinking-water treatment residual using X-ray absorption spectroscopy

Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing >90% of the initial added As (15,000 mg kg(-1)) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg(-1)) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.     

巨大芽孢杆菌D01吸附金(AU3+)的谱学表征

对休眠的巨大芽孢杆菌(Bacillus megatherium)D01菌体吸附Au^3 的作用过程进行了谱学表征．运用AAS考察了pH、时间和温度对D01菌体吸附Au^3 过程的化学动力学和热力学相关参数的影响．D01菌粉中硫元素含量的EDX分析说明该菌体中对Au^3 具有还原作用的L-半胱氨酸和蛋氨酸的含量极少;D01菌体水解后葡萄糖含量的UV-vis测定说明该菌体水解产物中含有一定量的还原糖,空白的和吸附Au^3 的D01菌体的FFIR检测表明该菌体细胞壁肽聚糖层糖类化合物的羟基和肽链侧链氨基酸残基离子化羧基为吸附Au^3 的活性基团;肽聚糖层部分多糖的水解产物低聚糖、二糖及单糖等还原糖的半缩醛羟基游离态醛基为电子供体,将Au^3 原位还原成Au^0．葡萄糖和Au^3 相互作用的XRD和FFIR表征证明Au^3 是在还原糖的醛基上直接被还原成Au^0．     

Adsorption mechanism of arsenate by zirconyl-functionalized activated carbon

Arsenate [As(V)] and arsenite [As(III)] sorption at the solid-water interface of activated carbon impregnated with zirconyl nitrate (Zr-AC) was investigated using X-ray absorption spectroscopy (XAS) and surface complexation modeling. The XAS data at the Zr K-edge suggest that the structure of the zirconyl nitrate coating is built from chains of edge-sharing ZrO8 trigonal dodecahedra bound to each other through two double hydroxyl bridges. The 8-fold coordination of each Zr atom is completed by four O atoms, which share a bit less than the two theoretically possible bidentate nitrate groups. On impregnation, two of the O atoms may lose their nitrate group and be transformed to hydroxyl groups ready for binding to carboxylic or phenolic ligands at the AC surface. As K-edge XANES results showed the presence of only As(V) on adsorption regardless of the initial As oxidation state. Oxidation to As(V) is probably mediated by available carbon species on the AC surface as found by batch titration. Zr K-edge EXAFS data indicate that arsenate tetrahedra form monodentate mononuclear surface complexes with free hydroxyl groups of zirconyl dodecahedra, whereby each bidentate nitrate group is exchanged by up to two arsenate groups. The inner-sphere arsenate binding to the Zr-AC surface sites constrained with the spectroscopic results was used in the formulation of a surface complexation model to successfully describe the adsorption behavior of arsenate in the pH range between 4 and 12. The results suggest therefore that Zr-AC is an effective adsorbent for arsenic removal due to its high surface area and the presence of high affinity surface hydroxyl groups.     

Defining chemical species in complex environments using K-edge X-ray absorption spectroscopy: vanadium in intact blood cells and Henze solution from the tunicate Ascidia ceratodes

A K-edge X-ray absorption spectrum (XAS) fitting approach has been developed to speciate elements of interest in complex materials and used here to model the storage of biological vanadium within whole blood cells from the tunicate Ascidia ceratodes. The response of the K-edge XAS of solution-phase V(III) to increasing c(sulfate) at constant pH 1.8 produced specific and systematic effects in the preedge transition at 5468.8 eV (preedge transitions: 1s-->4A2 at 5464.9 +/- 0.1 eV, 1s-->4T2 at 5466.9 +/- 0.1 eV, and 1s-->4T1 at 5468.8 +/- 0.1 eV for 11 different V(III)/sulfate solutions). In contrast, variations in acidity (as pH) at constant c(sulfate) systematically modified the V(III) preedge XAS at 5466.9 eV. The energy position of the K-edge absorption maximum also serially shifted -0.32 eV/pH unit, from 5483.7 eV (pH 3.0) to 5484.7 eV (pH 0.3). Fits to the V-K XAS of two samples of A. ceratodes whole blood cells representing dozens of animals implied storage of V(III) ions in four predominant solution regimes: approximately 10% high sulfate/pH 0 acid; approximately 40% high sulfate/pH 1.8 acid; approximately 40% moderate sulfate/pH 1.8 acid; approximately 10% moderate sulfate/pH 3 acid. For lysed blood cells, the best fit represented 63% of the V(III) in a pH 1.6 sulfate-free environment and a further 16% in acidic sulfate solution. Nearly 18% of lysed cells vanadium(III) appeared in a tris(catecholate)-like environment. A detailed speciation of biological vanadium complex ions was calculated from these fits by application of the known equilibrium constants governing V(III) and sulfate in acidic aqueous solution. The utility of blood cell V(III) to ascidians is discussed. Fits to K-edge XAS spectra using the XAS spectra of appropriate models are suggested to be generally applicable to elucidating the state of metal ions in a wide variety of complex environments.     

Characterization of Sol-Gel-synthesized LiFePO4 by multiple scattering XAFS

X-ray absorption spectroscopy (XAS) was used to investigate the local structure arrangements of submicrocrystalline lithium iron phosphate and its precursors. The former material, proven to be very promising as active cathode material in lithium metal and lithium-ion batteries, was synthesized through a new procedure that combines a simple sol-gel precipitation with a moderate temperature (e.g., low cost) heat treatment. X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra taken at the Fe K-edge pointed out the modification of the Fe site during the synthesis steps that allow one to produce the submicrometer size crystalline LiFePO4 (active material) useful for batteries applications. The XAS investigation has shown that such a material is different from the conventional crystalline LiFePO4 on the short-range order. The difference is attributed to the synthesis procedure.     

Gallium-containing zeolites: characterization of catalytic role of gallium species in converting light paraffins to aromatics

The structures and the chemical nature of gallium species in gallium-containing zeolite catalysts prepared by hydrothermal synthesis and post-synthesis treatments are discussed based on the results of X-ray absorption spectroscopy (XAS), including X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS), and nuclear magnetic resonance (NMR) investigations. The in-situ analysis of properties of gallium active sites during oxidation/reduction cycles has been found to be further helpful on the understanding of the catalytic role of gallium species in the aromatization of alkanes.     

X-ray Absorption Spectroscopic Investigation of Arsenite and Arsenate Adsorption at the Aluminum Oxide-Water Interface

We investigated the As(III) and As(V) adsorption complexes forming at the gamma-Al(2)O(3)/water interface as a function of pH and ionic strength (I), using a combination of adsorption envelopes, electrophoretic mobility (EM) measurements, and X-ray absorption spectroscopy (XAS). The As adsorption envelopes show that (1) As(III) adsorption increases with increasing pH and is insensitive to I changes (0.01 and 0.8 M NaNO(3)) at pH 3-4.5, while adsorption decreases with increasing I between pH 4.5 and 9.0, and (2) As(V) adsorption decreases with increasing pH and is insensitive to I changes at pH 3.5-10. The EM measurements show that As(III) adsorption does not significantly change the EM values of gamma-Al(2)O(3) suspension in 0.1 M NaNO(3) at pH 4-8, whereas As(V) adsorption lowered the EM values at pH 4-10. The EXAFS data indicate that both As(III) and As(V) form inner-sphere complexes with a bidentate binuclear configuration, as evidenced by a As(III)-Al bond distance of congruent with3.22 ? and a As(V)-Al bond distance of congruent with3.11 ?. The As(III) XANES spectra, however, show that outer-sphere complexes are formed in addition to inner-sphere complexes and that the importance of outer-sphere As(III) complexes increases with increasing pH (5.5 to 8) and with decreasing I. In short, the data indicate for As(III) that inner- and outer-sphere adsorption coexist whereas for As(V) inner-sphere complexes are predominant under our experimental conditions. Copyright 2001 Academic Press.     

XAS study on copper red in ancient glass beads from Thailand

Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.     

Picosecond X-ray absorption spectroscopy of a photoinduced iron(II) spin crossover reaction in solution

In this study, we perform steady-state and time-resolved X-ray absorption spectroscopy (XAS) on the iron K-edge of [Fe(tren(py)3)](PF6)2 dissolved in acetonitrile solution. Static XAS measurements on the low-spin parent compound and its high-spin analogue, [Fe(tren(6-Me-py)3)](PF6)2, reveal distinct spectroscopic signatures for the two spin states in the X-ray absorption near-edge structure (XANES) and in the X-ray absorption fine structure (EXAFS). For the time-resolved studies, 100 fs, 400 nm pump pulses initiate a charge-transfer transition in the low-spin complex. The subsequent electronic and geometric changes associated with the formation of the high-spin excited state are probed with 70 ps, 7.1 keV, tunable X-ray pulses derived from the Advanced Light Source (ALS). Modeling of the transient XAS data reveals that the average iron-nitrogen (Fe-N) bond is lengthened by 0.21+/-0.03 A in the high-spin excited state relative to the ground state within 70 ps. This structural modification causes a change in the metal-ligand interactions as reflected by the altered density of states of the unoccupied metal orbitals. Our results constitute the first direct measurements of the dynamic atomic and electronic structural rearrangements occurring during a photoinduced FeII spin crossover reaction in solution via picosecond X-ray absorption spectroscopy.     

用密度泛函和XANES计算研究Zn2+在水锰矿表面的吸附和沉淀

用密度泛函理论(density function theory, DFT)和X射线近边结构(X-ray absorption near edge structure, XANES)模拟计算了不同酸度(pH = 7.0, 7.5 和 8.0)下Zn(II)在水锰矿表面的吸附. 优化的几何结构表明, 只有双边吸附方式的水解簇既能解释H+ 释放机制, 又能与扩展X射线吸收精细结构(extended X-ray absorption fine structure, EXAFS)实验键长值相吻合. 吸附能计算表明, 各种吸附方式的稳定性双边(DE)>双角(DC)>B型单边(SE-B)>A型单边(SE-A)；水解能计算表明各种吸附态Zn2+ 均比溶液中水合锌离子易水解. 各种吸附簇模型的XANES计算谱未能与实验谱吻合, 即, 表面发生的并不是简单的吸附. pH=7.5和pH=8.0吸附样品的XANES实验谱与Zn5(OH)6(CO3)2的实验谱非常接近, 因此认为pH=7.5和pH=8.0下Zn(II)在水锰矿表面发生沉淀, Zn(II)是Zn—O八面体和Zn—O四面体的混合, 它们按类似Zn5(OH)6(CO3)2结构中的八面体和四面体排列方式排列. pH=7.0时, Zn(II)在水锰矿表面发生的主要是边连接方式的吸附.     

In situ extended X-ray absorption fine structure study during selective alcohol oxidation over Pd/Al2O3 in supercritical carbon dioxide

High-pressure in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data are reported during the selective oxidation of benzyl alcohol to benzaldehyde in supercritical carbon dioxide over a Pd/Al(2)O(3) catalyst (shell impregnated). For this purpose, a continuous-flow system with a spectroscopic cell suitable for in situ X-ray absorption studies on heterogeneous catalysts up to 200 degrees C and 200 bar has been developed. Due to the high contribution of the dense fluid to the overall X-ray absorption, high stability of the process pressure is mandatory, particularly when recording EXAFS spectra. According to EXAFS and XANES results, the palladium particles were fully reduced after exposure to benzyl alcohol in scCO(2). In contrast to Pd-catalyzed liquid-phase oxidation, a higher oxygen tolerance of the catalyst was observed. Palladium was partially oxidized on the surface under typical reaction conditions (0.9 mol % benzyl alcohol/0.5 mol % O(2) in carbon dioxide), which gradually increased when the concentration of oxygen in the feed was raised. Both XANES and EXAFS data uncovered that palladium is mainly oxidized on the surface or within the outermost layers. These results are in accordance with simulations of the XANES data using the FEFF8.20 code (program for ab initio calculations on multiple scattering XAS) and EXAFS data fitting/simulation.