漫反射光谱测定云南元谋盆地古红土铁氧化物

铁氧化物矿物是现代土壤和古土壤的重要组成,其数量和形态是反映土壤成土条件和土壤风化发育程度的重要指标。鉴于其粒度细小、结晶度差、含量低、与粘土矿物密切共生, 加之基体效应的影响,难以快速准确测定其含量;鉴于某些测试方法自身的限制,能用于铁氧化物矿物定量分析的方法也很少。在分析目前常用测量方法的基础上,选择漫反射光谱法（DRS）对云南元谋盆地所采古红土样品中的铁氧化物进行定量研究,结果表明：漫反射光谱法测得土壤样品在400~2 500 nm之间,间隔2 nm共1 061个波段的光谱反射率最高45%左右,各样品反射率特征较为一致;漫反射光谱一阶导数显示,光谱主峰位于575 nm处,为赤铁矿的指示波谱段,次级峰位于435 nm处,为针铁矿的指示波谱段;确定云南元谋古红土存在赤铁矿和针铁矿,其含量范围3~5和5~10 g·kg-1,此结果获得XRD方法分析方法的佐证。     

Iron-rich spinels from Brazilian soils

Tropical soils often contain high amounts of iron oxides. Hematite (αFe₂O₃) and goethite (αFeOOH) are the most widespread iron oxides, but magnetite (Fe₃O₄) and maghemite (γFe₂O₃) occur in magnetic pedons. A wide range of spinel compositions in the Fe₃O₄-γFe₂O₃ series has been identified in magnetic Brazilian soils. Isomorphic substitution of mainly Ti⁴⁺, Al³⁺ and Mg²⁺, but also of Cr³⁺ and Mn²⁺ and other minor elements for iron are related to changes in their structural stability and magnetic properties. Magnetic iron oxides of selected Brazilian pedodomains are discussed, distinguishing those produced from mafic rocks (tuffite, basalt), where primary magnetite transforms to maghemite, from those produced in non-mafic lithologies (such as steatite), where inherited magnetite may be exceptionally stable in the soil. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism study of selenium retention by iron minerals during coal combustion

The interactions between selenium vapors and coal accessory Ca/Fe-minerals favor selenium emission control by transferring selenium into fly ash during coal combustion. Considering the complicated effects of iron transformation on selenium retention, iron species in fly ashes from seven coal-fired power plants were distinguished and the associations between selenium and iron minerals were assessed. Iron oxides (including Fe₃O₄, γ-Fe₂O₃ and ɑ-Fe₂O₃) were determined as the main form of iron minerals in fly ash. The adsorption of selenium vapors by different iron oxides was conducted at temperatures ranging from 300 to 900 °C and the species of captured selenium were identified. Furthermore, reaction sites on the surfaces of fresh and reacted iron oxides were compared to investigate the mechanism regarding selenium adsorption over these iron oxides, which were further clarified through density functional theory study. The results showed that iron oxides were surely to play a significant role in selenium retention mainly through chemisorption and the reactions probably occurred at temperatures below 900 °C. At 300 °C, ɑ-Fe₂O₃ had better selenium adsorption performance than Fe₃O₄/γ-Fe₂O₃. Regardless of iron species, Fe atoms on iron oxides participated in the selenium adsorption by forming a Se–O–Fe Structure. With temperature increasing, selenium adsorption by Fe atoms was suppressed, which caused a drop off in selenium capture capacity of Fe₃O₄ and ɑ-Fe₂O₃. Differently, increasing temperature promoted selenium adsorption over γ-Fe₂O₃, which owned a high selenium adsorption capacity even at 700 °C. Further analysis confirmed that the presence of O₂/H₂O(g) in the flue gas contributed to the formation of oxygen vacancies on the surface of γ-Fe₂O₃ at high temperatures and facilitated selenium vapors to react with Fe atoms.     

The characterization of soils, clays, and clay firing products

Mössbauer spectroscopic studies of soils are generally centered around the characterization of Fe³⁺ oxides, making use of distinctive magnetic properties of the different oxides and the high sensitivity of the technique for magnetically ordered phases. Most work on clays and clay minerals, in contrast, focuses on the determination of the oxidation state of iron, iron structural site occupancies and distortions, and the transformations that take place during clay firing.     

网纹红土中铁矿物与粘土矿物赋存关系的X射线衍射证据

高纯度的粘土矿物样品是粘土矿物学重建古气候的关键,然而,土壤中的铁矿物(如针铁矿和赤铁矿等)和有机质的存在导致粘土矿物与非粘土矿物相互包裹,使富集的粘土矿物样品常含有其他矿物杂质。土壤沉积物中有机质去除的研究已较为充分,但铁矿物在土壤沉积物中的赋存状态倍受争议,制约了高纯度粘土矿物样品的制备。该研究将以长江中下游九江网纹红土作为研究对象,通过逐级分离试验对网纹红土中铁矿物与粘土矿物的赋存关系进行研究,为土壤沉积物中铁矿物的去除提供一定的启示。试验结果表明,针铁矿和赤铁矿等铁矿物可能主要呈现被膜状吸附在羟基间层蒙脱石和伊利石的表面,也有部分被高岭石吸附。     

过氧化氢和连二亚硫酸钠-柠檬酸钠-碳酸氢钠处理对红土中黏土矿物的影响

过氧化氢(H₂O₂)和连二亚硫酸钠-柠檬酸钠-碳酸氢钠(DCB)作为土壤沉积物前处理的经典方法,对土壤沉积物中黏土矿物的富集有着举足轻重的作用,但关于二者对黏土矿物的影响研究较少。运用X射线衍射作为检测技术,对比研究H₂O₂和DCB两种前处理方法对红土中黏土矿物的影响。结果表明,H₂O₂或DCB处理均可促进土壤矿物颗粒的充分分散,有效地将石英等杂质分离,进而提取到很纯的黏土矿物。同时发现,DCB处理由于其Na+与黏土矿物层间阳离子交换导致数据失真,而H₂O₂处理可以保证数据的真实性。结果表明：采用H₂O₂进行前处理能获取较为准确的黏土矿物学信息。     

Microanalysis of clay‐based pigments in painted artworks by the means of Raman spectroscopy

FT Raman spectroscopy and micro‐Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro‐samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X‐ray diffraction and micro‐diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO₂) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro‐samples of artworks. In those cases, it is always necessary to use powder X‐ray micro‐diffraction to avoid misleading interpretations of the pigment's composition. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparative treatment with NaOH to selectively concentrate iron oxides of a Chilean volcanic soil?material to produce effective heterogeneous Fenton catalyst

A Chilean volcanic Ultisol material was first size-fractionated so as to obtain the fraction with mean particle sizes ??<?53 ??m. This sample was then sequentially treated three or five times with 5 mol L^???1 NaOH, in an attempt to evaluate the effectiveness of the selective chemical dissolution to concentrate iron oxides, as a preparation procedure before using the materials as heterogeneous Fenton catalysts. The effects of those treatments on the iron oxides mineralogy were monitored with Mössbauer spectroscopy. The NaOH-treated samples were tested as catalysts towards the H₂O₂ decomposition. Three or five sequential NaOH treatments were found to be comparably effective, by concentrating nearly the same proportion of iron oxides in the remaining solid phase (25.1 ± 0.4 and 23.3 ± 0.2 mass%, respectively). 298 K-Mössbauer patterns were similar for both samples, with a central (super)paramagnetic Fe^3?+? doublet and a broad sextet, assignable to several closely coexisting magnetically ordered forms of iron oxides. Despite of this nearly similar effect of the two treatments, the Ultisol material treated three times with NaOH presents higher heterogeneous catalytic efficiency and is more suitable to decompose H₂O₂ than that with five treatments.     

Characterization of iron oxide layers using Auger electron spectroscopy

Metals can form several kinds of oxides. Iron forms wustite (FeO), magnetite (FeO + Fe₂O₃ or Fe₃O₄) and haematite (Fe₂O₃). Iron oxides, especially magnetite, are used for insulation between the lamellas of an electromotor made of electromagnetic sheet. In this work, iron oxide layers were characterized on industrial samples of electromagnetic sheet by AES depth profile analysis, and iron oxides with known chemical composition were used as reference samples, i.e. a magnetite mineral and a standard haematite reference sample. The magnetite mineral was chosen because it can be found in nature in a very pure form. The selection of reference samples was also verified on samples with an oxide layer of known composition, which were prepared by sputter deposition. The composition of the sputtered oxide layers was analysed by the weight-gain method and Rutherford backscattering without the use of standard reference materials (SRM), and the results were then compared with those obtained by AES depth profile analysis.     

Characterization of a mechanochemically activated titanium-hematite mixture: Mössbauer spectroscopy study

Mechanochemical processes involving reactions between metals and crystalline oxides are of interest because of their potential technological applications in structural, magnetic or electric materials. In addition they can contribute to the understanding of the natural occurring processes that lead to the formation of minerals and soils. The controlled studies of how the distribution of cations in the titanomagnetites takes place can help toward building a model for the nature of their magnetism and, since they are the primary carriers of rock and soil magnetism, are therefore intensively investigated in many experimental and theoretical studies.In behalf of a better comprehension of the thermal, physical–chemical, magnetic and hyperfine behavior, we have considered a titanium and hematite mixture, with molar ratio Ti:Fe₂O₃ of 1:2, mechanochemically activated during different activation times. We have studied the development of new phases by X-ray diffraction, scanning electron microscopy and Mössbauer spectroscopy. The evolution from the starting materials affected by different milling times and subsequent annealing shows that Ti reduces the Fe ions in the Fe₂O₃ lattice, partly to Fe²⁺ and partly to metallic Fe.     

An AES analysis of oxide films on iron

The Auger spectra of the iron oxides have been investigated. The relative amplitudes of the Auger lines from oxygen and iron have been determined for FeO, Fe₃O₄, α-Fe₂O₃, γ-Fe₂O₃, and FeOOH. It was found that the amplitude ratio s of the O (510 eV)/Fe (703 eV) lines was, to a first approximation, directly proportional to the ratio of oxygen and iron in the chemical formula. Structure was observed in the spectra resulting from the Fe M_2,3 VV transition. Different spectra were observed for Fe, FeO, Fe₃O₄, Fe₃O₃, and FeOOH; however, the same spectra were obtained for α- and γ-Fe₂O₃.     

艾比湖滨岸盐碱土中碳酸盐的XRD衍射特征与微观形态分析

结合X射线衍射(XRD)、扫描电镜(SEM)和能谱分析(EDS)方法,对现代盐湖沉积环境下,新疆艾比湖滨岸盐碱土中碳酸盐的分布特征、存在形式以及与其他土壤原生、次生矿物之间的关系进行探讨,结果表明：艾比湖滨岸盐碱土中的原生矿物主要是石英和长石,粘土矿物主要为绿泥石和伊利石,土壤矿物的风化程度顺序为北部>西部>东部,西部样点的现代盐湖化学沉积作用最为显著,北部样点则生物风化过程十分强烈;XRD方法和气量法分别测得的碳酸盐含量之间呈极显著正相关关系,判定系数R2达0.640 9。当盐碱土中含有较高的绿泥石时,碳汇潜力会增加,同时,XRD方法对碳酸盐相对含量的鉴定误差也明显增加,衍射峰形变得复杂,碳酸盐含量明显被低估,低估原因可能与有机质含量高导致的弥散散射增加及粘土矿物含量高使得类质同象现象增加有关;西部和北部土壤矿物溶蚀强烈,石膏以纤维状或长柱状晶体分散或放射状分布于方解石晶体之间,方解石则以异质成核形式呈颗粒状或片状在其他矿物或底质表面生长,表现为次生碳酸盐形貌特征。     

Characterization of iron(III) oxide films used for photoelectrode by means of cems

Thin iron oxides deposited on semi-conductive glass by a spray pyrolysis technique were analysed by Conversion Electron Mössbauer Spectrometry (CEMS). Iron oxide deposited on SnO₂ coated glass was composed of a large grained particles of crystalline α?Fe₂O₃, which showed sextet. The doublet and sextet appeared in CEM spectra of iron oxides deposited on In₂O₃ and WO₃ coated glasses. The sextet was due to α?Fe₂O₃ and the doublet was attributted to the superparamagnetic microcrystalline α?Fe₂O₃ (≈15nm) rather than to spinel compounds of iron. The iron oxide deposited on ZnO coated glass gave a doublet in CEM spectra. It was supporsed to be due to very fine particle of α?Fe₂O₃ (<100nm). It was found that iron oxide films obtained by spray pyrolysis were dependent on the kinds and the temperature of the semi-conductive materials coated on glass.     

A study of nanostructures formed in the hydrogen reduction of Fe(OH)<Subscript>3</Subscript>

A complex study of the hydrogen reduction of nanosized iron hydroxide Fe(OH)₃ at 400°C was performed. It was shown that, during the reduction of Fe(OH)₃ to iron metal α-Fe, intermediate compounds such as Fe(OH)₂, α-FeOOH, β-FeOOH, γ-FeOOH, δ-FeOOH, and FeO are formed along with stable iron oxides α-Fe₂O₃, γ-Fe₂O₃, and Fe₃O₄. A scheme of chemical and structural transformations that occur in the reduction of nanosized Fe(OH)₃ is presented. The scheme takes into account the possibility of the bifurcation mechanism of reaction development.     

Electrical conductivity and structure of CaO-stabilized zirconia doped with copper and iron

The investigation of the influence of copper and iron oxides on the electrical conductivity, the lattice defects and the structure of calcia-stabilized zirconia has shown that (i) the influence of copper is negligible due to the evaporation of this element at the sintering temperature as a consequence of its high volatility; (ii) the presence of iron in the sample prevents sintering of the calcia-stabilized zirconia; (iii) the addition of iron causes decomposition of the cubic solid solution Ca_xZr_1?xO_2?x into monoclinic ZrO₂, the vacant phase Ca_0.1Zr_0.9O_1.9, calcium ferrite and iron oxides; the solubility limit of iron oxide was found to be ≈1 mol%; (iv) the calcia-stabilized zirconia doped with iron is a mixed conductor at low temperatures; at high temperatures (>1073 K) it is a dominant ionic conductor.     

铁氧化物中电子隧道现象的扫描隧道显微术研究

报道了利用扫描隧道显微术(STM)对金属表面氧化物层进行电子隧道谱研究的结果。在对两类铁晶体表面氧化层进行的隧道谱和势垒高度测量结果进行分析后表明,常温条件下形成的氧化层(Ⅰ类)应主要是Fe₃O₄;而在高温氧化条件下形成的表面层(Ⅱ类)的主要成分则应是Fe₂O₃。从而表明(STM)可用于研究铁表面氧化过程的不同阶段,并且由Ⅰ类氧化层的低势垒特性说明STM还可以用于观测此类氧化层的内部结构。类似研究方法还可应用到对一系列 关键词：     

Application of XANES spectroscopy to investigate Sb species in corroded bullets crust material oriented to evaluate the potential toxic effects in the environment

Lead, antimony, and other toxic metals from pellets alloy are dispersed in the soil of the shooting fields. As long as the corroding bullets are present in soil, secondary Pb and Sb phases appear in the weathering crusts being an important source of bioavailable Pb and Sb. Knowledge about the corrosion mechanism of Sb from the bullet is limited, and reports on Sb speciation in crust and soils are still scarce. Considering that Sb species have different toxicological properties in the environment, this work has focused attention in X‐ray Absorption Near Edge Structure measurements at the Sb L‐edges in order to identify its chemical speciation in crust (Sb(0), Sb(III), and Sb(V)). X‐ray Absorption Near Edge Structure measurements were carried out at the D04A Soft X‐ray Spectroscopy beamline at the LNLS. Samples consisted of dust crust taken from physically deformed and strongly corroded metallic bullets retained in soil samples sieving from shooting fields of the North and East region of Córdoba, Argentina. The results showed that the main species found in all samples were Sb(V)(Sb₂O₅) followed by Sb(0) (metallic). Sb(III) was not observed, and it is known that Sb(III) is more toxic than Sb(V). The results suggested that in these environmental conditions, pentavalent Sb was the predominant species after weathering of metallic Sb from corroding bullets.     

利用反射光谱研究砂岩风化与排氮作用——以江西龙虎山为例

近期,《Nature》、《Science》等世界顶级期刊揭示了地表岩石与全球氮循环的相互作用,认为岩石是氮素的重要储库,其风化排氮是生态系统氮素的主要来源之一,对局部乃至全球氮循环具有重大影响。陆地地表岩石分布面积75%是沉积岩,丹霞地貌是受沉积岩风化侵蚀作用形成的重要地貌类型之一,研究丹霞地貌沉积岩的风化与排氮作用对深入了解全球氮循环过程具有重要意义。以江西龙虎山丹霞地貌出露的红色砂岩为研究对象,在系统的野外样品采集工作基础上,利用偏光显微镜、ASD光谱仪和碳氮分析仪对样品的矿物组成、光谱曲线和氮素含量进行鉴定和测量。结果表明：龙虎山砂岩主要为长石砂岩,颗粒矿物为长石和石英,胶结物以铁质、钙质为主,次为泥质;砂岩的化学风化类型主要有胶结物溶蚀和颗粒矿物水化两种,其中胶结物溶蚀以铁质溶蚀为主,溶蚀后岩石的光谱曲线在902 nm处（Fe3+的特征吸收波段）的吸收指数下降,而颗粒矿物水化则主要体现为长石向粘土矿物转变,水化后岩石的光谱曲线在2 210 nm处（粘土Al-OH的特征吸收波段）的吸收指数上升。针对同一件样品,已被化学风化的部分与未被风化的部分相比,其氮元素含量有所下降,且氮元素含量与2 210 nm处的吸收指数存在一定的负相关系（R2=0.802 6）,说明岩石风化有助于氮排放;针对不同样品,氮元素含量与2 210 nm处的吸收指数相关性很差（R2=0.025 6）,说明岩石矿物组成与结构差异对岩石初始氮含量和吸收指数产生影响,从而降低两者间的相关性。以上研究说明,反射光谱为砂岩风化程度检测与氮排放研究提供了一种重要的技术手段,但研究时必须注意岩性的一致性。     

Surface XPS characterization of NiTi shape memory alloy after advanced oxidation processes in UV/H2O2 photocatalytic system

Surface structure of NiTi shape memory alloy (SMA) was modified by advanced oxidation processes (AOP) in an ultraviolet (UV)/H₂O₂ photocatalytic system, and then systematically characterized with x-ray photoelectron spectroscopy (XPS). It is found that the AOP in UV/H₂O₂ photocatalytic system leads to formation of titanium oxides film on NiTi substrate. Depth profiles of O, Ni and Ti show such a film possesses a graded interface structure to NiTi substrate and there is no intermediate Ni-rich layer like that produced in conventional high temperature oxidation. Except TiO₂ phase, some titanium suboxides (TiO, Ti₂O₃) may also exist in the titanium oxides film. Oxygen mainly presents in metal oxides and some chemisorbed water and OH⁻ are found in titanium oxides film. Ni nearly reaches zero on the upper surface and relatively depleted in the whole titanium oxides film. The work indicates the AOP in UV/H₂O₂ photocatalytic system is a promising way to favor the widespread application of biomedical NiTi SMA by improving its biocompatibility.     

Clays and clay minerals: The firing process

⁵⁷Fe Mössbauer spectroscopy reveals changes in iron valence and iron site geometry when clays and clay minerals are heated, and allows a distinction to be made between paramagnetic and magnetically ordered phases. Mössbauer spectra can thus reveal the extent of iron retention in silicate structures upon heating, the identity of iron oxides initially present or formed during the heating process and their transformations, and the character of the atmosphere under which heating was carried out. This makes Mössbauer spectroscopy the most effective tool for the characterization of changes induced by heating phyllosilicates and iron oxides.