多接收器等离子体质谱法Zn同位素比值的高精度测定

详细报道了Zn同位素比值的多接收器等离子体质谱(MC-ICP-MS)高精度测定方法,包括:MC-ICP-MS Zn同位素测量过程中的质量歧视校正、同质异位素干扰评估、基质效应调查和同位素测量的长期重现性检验.研究表明,在测定条件下,运用标样一样品交叉法能有效地进行仪器质量歧视校正.同质异位素干扰的评估通过3种方式进行,即:在高分辨状态下同质异位数干扰信号的直接测定,低分辨状态下Zn同位素原始数据间相关关系的检验和低分辨下浓度梯度效应研究.结果表明,在低分辨模式下,尽管66Zn、67Zn、68Zn的同质异位素干扰信号很小,但的确存在,要获得准确同位素比值,必须使标样和样品的浓度在合适的范围内匹配.在基质效应方面,主要考察Fe对Zn同位素比值测定的影响.结果表明,当溶液中Fe/Zn(质量比)不大于0.2时,Fe对Zn同位素比值测定无影响.重复性测定中,δ66ZnGSB-Romil=6.96‰±0.11‰(2sd),δ67ZnGSB-Romil=10.4‰±0.20‰(2sd),δ68ZnGSB-Romil=13.8‰±0.22‰(2sd),达到国际同类实验室先进水准.运用所建立的方法,对地质岩石成分分析国家标准物质GBW 07270(闪锌矿)进行了Zn同位素平均成分测定为:δ66Zn=6.71‰±0.03‰(20),δ67Zn=10.08‰±0.05‰(20),δ68Zn=13.37‰±0.07‰(2σ).     

玄武岩标准样品铁铜锌同位素组成

报道了三种玄武岩标准样品(BCR-2、BIR-1a和GBW 07105)的铁铜锌同位素数据。实验使用HNO3-HF混合酸消解玄武岩标准样品;AGMP-1阴离子交换树脂分离提纯样品中的铜铁锌,利用多接收等离子体质谱仪(MC-ICPMS)测定铁铜锌同位素比值,分析过程中使用样品-标准-样品交叉法校正仪器的质量分馏。实验得到BCR-2、BIR-1a和GBW 07105标准样品的高精度铁铜锌同位素组成(95%置信水平的不确定度)分别为:δ56FeBCR-2-IRMM014=0.070‰±0.018‰(2SD),δ65 CuBCR-2-SRM976=0.16‰±0.04‰(2SD),δ66 ZnBCR-2-IRMM3702=-0.072‰±0.020‰(2SD);δ56 FeBIR-1a-IRMM014=0.044‰±0.026‰(2SD),δ65CuBIR-1a-SRM976=0.027‰±0.019‰(2SD),δ66 ZnBIR-1a-IRMM3702=0.085‰±0.032‰(2SD);δ56FeGBW 07105-IRMM014=0.126‰±0.039‰(2SD),δ65 CuGBW 07105-SRM976=0.12‰±0.01‰(2SD),δ66ZnGBW 07105-IRMM3702=0.22‰±0.03‰(2SD)。这些数据在误差(不确定度)范围内与国际上已发表的数据是一致的。三个玄武岩标准样品的铁铜锌同位素组成数据的发表为铁铜锌同位素研究提供了统一的标准,使地质样品的铁铜锌同位素数据的质量监控成为可能。     

Fe同位素的MC-ICP-MS测试方法

过渡族元素同位素研究是新兴的研究领域和国际研究前沿, 是同位素地球化学研究的热点。本研究利用Neptune型多接收等离子质谱(MC-ICP-MS), 采用标准-样品-标准交叉校正和以Cu为内标的方法对仪器的质量歧视进行校正, 对浓度效应、基质效应、干扰元素扣除和测试的长期重现性进行了检验, 建立了高精度的Fe同位素测试技术。这两种校正方法对实验室标准HSP I Fe在一段时间内δ56Fe和δ57Fe的测试结果分别为0.08‰(2SD)和0.14‰(2SD)分析精度达到国际同类实验室水平, 测试结果在误差范围内与文献值完全一致。     

大型高分辨率多接收等离子体质谱准确测定地质标样的铁同位素组成

使用AGMP-1M阴离子交换树脂提纯样品中的Fe同位素,利用Nu1700大型多接收等离子体质谱在高分辨率模式下测定铁同位素比值,采用标样-样品交叉法校正仪器的质量歧视效应,对回收率、化学流程本底、酸度效应、浓度效应进行了检验,建立了可靠的高精度铁同位素分析技术。本文测定了常用地质标准样品(BCR-2,BHVO-2,AGV-2,GSR-2,GSR-3)的Fe同位素组成,测定结果与文献报道值在误差范围内一致,其测试精度优于(BCR-2,BHVO-2,AGV-2,GSR-3)0.03‰(2SD)。GSR-2可能受Fe含量较低(TFe_2O_3=4.95%)和均一性的影响,获得的δ~(56)Fe和δ~(57)Fe的测试精度分别为0.05‰和0.07‰(2SD)。     

地质样品铜、铁、锌同位素标准物质的研制

合适的标准物质是进行同位素准确分析的基础和关键,本文介绍了基于地质样品的铜、铁、锌同位素分析标准参考物质的研制过程.所研制的标准物质为CAGSR-1,用于该标准物质研制的原始样品为玄武质组分的岩石成分分析国家标准物质GBW07105.按照国家一级标准的要求,对该标准物质进行了严格的均一性、稳定性检验和同位素定值分析.标准物质CAGSR-1的主要特性量值δ65Cu、δ56Fe、δ66Zn的推荐值及95%置信水平的不确定度为:δ65CuSRM976(‰)=0.10±0.02、δ56FeIRMM014(‰)=0.12±0.02、δ66ZnRomil(‰)=7.45±0.01.该标准物质可用于地质与环境样品铜、铁、锌同位素测定中化学流程评价和验证、质谱仪的校正及整个过程的分析质量控制.     

少量AG1-X4阴离子交换树脂分离地质标样中的铁及铁同位素测定

报道了利用少量AG1-X4阴离子交换树脂分离地质样品中Fe及测定Fe同位素的方法。对少量AG1-X4和AG MP-1树脂的分离效果进行了比较,测定了经过AG1-X4分离后的地质标样BCR-2、BHVO-2、BIR-1a、AGV-2、W-2、GSP-2、COQ-1、DTS-2b、JB-2、Jsd-1、GBW07105和GBW07267的Fe同位素组成,其结果与文献参考值在误差范围内一致。这些数据的发表对于地质样品Fe的化学分离和同位素测定提供了参考依据。此方法可以大大减少化学试剂用量,是一种快速有效分离铁的方法。     

绿片岩-低角闪岩相变质条件下磁铁铁矿与黄铁矿间的Fe同位素分馏

对辽宁省鞍山一本溪地区经历了绿片岩一低角闪岩相变质的新太古代条带状铁建造中磁铁矿和黄铁矿矿物对的Fe同位素分析结果显示:相对于标准IRMM-014,所有样品的磁铁矿和黄铁矿均显示Fe的重同位素富集;且黄铁矿的Fe同位素比值均大于磁铁矿的Fe同位素比值(ε57Fe黄铁矿ε57Fe磁铁矿),两种矿物的Fe同位素比值之差为△57Fe黄铁矿-磁铁矿=2.23～5.13.黄铁矿富集铁的重同位素表明矿物的Fe同位素组成并不代表其原始沉积的特征,而是在区域变质作用过程中Fe同位素发生了交换的结果.由同位素平衡判别图解可知,在绿片岩一低角闪岩相变质作用中,磁铁矿-黄铁矿间的Fe同位素基本达到了平衡,且在平衡条件下黄铁矿比磁铁矿更富集Fe的重同位素,二者之间的Fe同位素平衡分馏系数α黄铁矿-磁铁矿≈1.000 4‰±0.06‰(2σ).这一研究成果是对变质作用过程中Fe同位素的地球化学行为认识的重要进展.     

海南岛屯昌玄武质科马提岩Sm-Nd同位素年龄及其地质意义

海南岛屯昌玄武质科马提岩成岩时代一直未获解决。作者利用Sm-Nd同位素法测试了5件样品,获得岩石Sm-Nd同位素等时线年龄1687±10Ma,及与其相近的Nd模式年龄1637-1756Ma。同时获得了钕同位素初始比值I_Nd=0.510796±0.000006(2σ),ε_Nd(T)=+6.64。表明玄武质科马提岩结晶年龄为古元古代(1687Ma),反映了海南岛在古元古时期的壳-幔分异与地壳增生的重要过程。     

MC-ICP-MS高精度Cu、Zn同位素测试技术

过渡族元素同位素是国际上同位素地球化学研究的热点。测试技术的限制是制约过渡元素同位素研究发展的关键。笔者利用Neptune型多接收等离子质谱(MC-ICP-MS),采用Cu、Zn互为内标的方法对仪器的质量歧视进行了校正,对基质效应和测试方法的重现性进行了检验,建立了高精度的Cu、Zn同位素测试技术。在5个月内对实验室标准IMRCu和IMRZn进行了测量,结果分别为δ65CuNIST976=(0.34±0.08)‰(2SD,n=32),δ66ZnJMCZn=(-9.64±0.05)‰(2SD,n=26),δ67ZnJMCZn=(-14.37±0.16)‰(2SD,n=26),δ68ZnJMCZn=(-19.01±0.08)‰(2SD,n=26),分析精度达到国际同类实验室先进水平。对Cu、Zn同位素参考物质进行了对比测量,分析结果与报道值在误差范围内完全一致。     

常用锂同位素地质标准物质的多接收器电感耦合等离子体质谱分析研究

锂同位素研究是非传统稳定同位素地球化学研究的前沿,已广泛应用于从地表到地幔的岩石圈及流体等固体地球科学的研究领域。准确测定锂同位素比值是应用该同位素体系的前提。本文报道了国际上7种常用地质标准物质(BHVO-2、JB-2、BCR-2、AGV-2、NKT-1、L-SVEC、IRMM-016)的锂同位素组成数据。分析中采用硝酸-氢氟酸混合酸消解岩石标准样品,通过3根阳离子交换树脂(AG50W-X8,200~400目)填充的聚丙烯交换柱和石英交换柱对锂进行分离富集,利用Neptune型多接收器电感耦合等离子体质谱(MC-ICPMS)测定锂同位素比值,使用标准-样品交叉法(SSB)校正仪器的质量分馏。实验得到这7种常用地质标准物质的锂同位素组成与测试精度(2SD)分别为:δ7LiBHVO-2—L-SVEC=4.7‰±1.0‰(n=53),δ7LiJB-2—L-SVEC=4.9‰±1.0‰(n=20),δ7LiBCR-2—L-SVEC=4.4‰±0.8‰(n=8),δ7LiAGV-2—L-SVEC=6.1‰±0.4‰(n=14),δ7LiNKT-1—L-SVEC=9.8‰±0.2‰(n=3),δ7LiL-SVEC—L-SVEC=-0.3‰±0.3‰(n=10),δ7LiIRMM-016—L-SVEC=0.0‰±0.5‰(n=10),这些数据在误差范围内与国际上已发表的数据一致。Li同位素分析精度可以达到大约0.5‰,长期的分析精度即外部重现性≤±1.0‰,达到了国际同类实验室水平。7种常用地质标准物质的锂同位素组成数据的发表为锂同位素研究提供了统一的标准,使地质样品的锂同位素数据的质量监控成为可能。在基质效应的研究中,使用不同量的IRMM-016配制的标准溶液过柱,深入探讨了样品量对锂同位素测定值的影响,结果表明,在现有测试精度下,只要分析样品的锂含量达到100μg/L,且不超过树脂的承载量,样品的锂同位素组成在误差范围内与真值吻合,样品量的大小不影响锂同位素测定结果的准确性。     

Fe Isotope Geochemistry of Hydrothermal Fe Exhalites

The sediments atop the sequence of ophiolite usually contain Fe(-Mn-Si)exhalites,chemical sediments that aremainlycomposedofamorphousFe-Mn oxy-hydroxides and chert/jasper.They were precipitated from hydrothermal fluids produced by deep leaching of basalt particularly during volcano activity or seafloor spreading.These hydrothermal Fe exhalites provide a good record for the depositional environment and the ocean environment as well.A well-preserved Phanerozoic Fe deposit,Motuosala Fe-Mn deposit,resulted from hydrothermal exhalation,was investigated for its trace element and Fe isotope geochemistry.The deposit is located in Xinjiang province,China and is hosted in a suit of Carboniferous volcano-sedimentary clastic rocks.The Fe deposit is mainly composed of massive hematite Fe oreand banded hematite-jasper ore.The hematite ore/band and jasper band were subjected to be analyzed.They are both composed mainly of Fe2O3 and Si O2,with very low contents of Al2O3 and Ti O2(1%),indicating they werechemical precipitates with little detrital contamination.They both show slightly LREE depleted or near flat PAAS-normalised REE patterns,with positive Eu anomalies and Y anomolies,indicating that they were sourced from a mixture of high-temperature fluids and seawater.Compared to the hematite Fe ore/band,the jasper band shows higher EuSN/EuSN*but lower Y/Ho values.δ56Fe values for the hematite Fe ores are clustered around-0.3‰,similar to those for high-temperature fluids.The jasper samples show heavier Fe isotope compositions varying from-0.1‰to0.5‰,indicating that they were resulted from partial Fe precipitation.For all samples,δ56Fe values are related to Y/Ho and EuSN/EuSN*values.The results indicate that the hematite Fe ore and jasper were deposited in different environments.The jasper was deposited in a more anoxic condition with higher hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was more intense;while the hematite Fe ore was deposited in a more oxic condition with lower hydrothermal fluids/seawater ratio,probably when the hydrothermal activity was weaker.     

Investigation of the Matrix Effect of Mg, Si, Ca, Sc, Fe, Y, La and Lu in Pyroxene Composition Synthetic Silicate Glasses by Ion Microprobe

The dependence of the count rate of singly charged secondary ions of the elements Mg, Si, Ca, Sc, Fe, Y, La and Lu on the bulk composition of the sample (known as the matrix effect) was systematically investigated for synthetic silicate glasses using a Cameca IMS 3f ion microprobe. Matrix elements in these samples, with the composition of a Mg-Fe-Ca pyroxene, comprised Mg, Si, Ca and Fe to which were added the minor elements Sc, Y, La and Lu (each at 0.1 atom %). The matrix dependence of all elements was determined quantitatively by ratioing their count rate response to the Ca or Fe yields of the sample. Measurements were conducted using four energy offsets: 0 eV, 40 eV, 80 eV and 120 eV (each 20 eV) with primary beam currents of between 0.5 and 3 nA. For the four minor elements investigated, a non-linear dependence of the absolute sensitivity factors on the Fe content was found at all the energy ranges studied. This matrix effect decreased with increasing secondary ion energy. For the major elements Mg, Si, Ca and Fe, linear as well as non-linear dependences of the absolute sensitivity factors on the Fe content were found, depending on the element and the energy level considered. Because of their importance in the geosciences, relative sensitivity factors of the elements under study relative to Si as reference element (in some cases also relative to Mg) were determined. For low energy ions, a Fe-dependent matrix effect also occurred. For Mg, Y, La and Lu, the matrix effect vanished for some values of the secondary ions energy range.     

Reductive biotransformation of Fe in shale-limestone saprolite containing Fe(III) oxides and Fe(II)/Fe(III) phyllosilicates

A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)_TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)_TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe²⁺, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)₂, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products.     

57Fe NCR of Fe phases in “magnetic cassiterites”

A pyralspite garnet from an anomalously magnetic concentrate of a pegmatitic cassiterite ore has been investigated using ⁵⁷Fe nuclear gamma-ray resonance spectroscopy. The quadrupole splitting and isomer shift values of 3.6 mm/s and 1.4 mm/s, respectively, are among the largest observed for Fe²⁺ ions and indicate a very low covalency of the dodecahedral Fe²⁺ — O²-bonds. These data support the more recent and lower value (10.2–10.1 kcal/ mole) of White and Moore (1972) for the CFSE of the dodecahedral Fe²⁺ ion and suggest that the CFSE should be a useful approximation to the site preference energy of Fe²⁺ for this site.     

Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)

Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl⁻) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using ⁵⁷Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60-80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl⁻ (∼10 mM HNO₃) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl⁻ solutions.The average measured equilibrium isotope fractionations, Δ_{Fe(III)-Fe(II)}, in 0, 11, and 111 mM Cl⁻ solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured Δ_{Fe(III)-Fe(II)} fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl⁻ solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: where the isotopic fractionation is independent of Cl⁻ contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl⁻ contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation.     

57Fe mössbauer study of synthetic Fe3+-melilites

Synthetic Fe³⁺-melilites containing NaCaFe³⁺-Si₂O₇-, Ca₂Fe³⁺AlSiO₇- or Sr₂Fe³⁺AlSiO₇-components have been studied by ⁵⁷Fe Mössbauer spectroscopy. The spectrum of åkermanite containing an NaCaFe³⁺Si₂O₇-component consists of one doublet identified to belong to Fe³⁺ in T1 sites. The spectra of åkermanite and gehlenite containing Ca₂Fe³⁺ AlSiO₇- or Sr₂Fe³⁺ AlSiO₇-component consist of two doublets. The inner and outer doublets are identified to belong to Fe³⁺ in the less distorted T1 and that in the more distorted T2 sites, respectively. The area ratios of the spectra show that the site occupancy of Fe³⁺ (T1) in gehlenite is less than that in åkermanite in which the distribution of Fe³⁺ in T1 and T2 sites is apparently random. The different distributions can be explained in terms of competition between minimizing the deficiency in the electrostatic valence and the preference of Al for T1 sites which the isomer shift measurements show to be more ionic.     

Cu and Fe chalcopyrite leach activation energies and the effect of added Fe

The leaching kinetics of chalcopyrite (CuFeS₂) concentrate in sulfuric acid leach media with and without the initial addition of Fe³⁺ under carefully controlled solution conditions (E_h 750 mV SHE, pH 1) at various temperatures from 55 to 85 °C were measured. Kinetic analyses by (i) apparent rate (not surface area normalised), and rate dependence using (ii) a shrinking core model and (iii) a shrinking core model in conjunction with Fe³⁺ activity, were performed to estimate the activation energies (E_a) for Cu and Fe dissolution.The E_a values determined for Cu and Fe leaching in the absence of added Fe³⁺ are within experimental error, 80 ± 10 kJ mol⁻¹ and 84 ± 10 kJ mol⁻¹, respectively (type iii analyses E_a are quoted unless stated otherwise), and are indicative of a chemical reaction controlled process. On addition of Fe³⁺ the initial Cu leach rate (up to 10 h) was increased and Cu was released to solution preferentially over Fe, with the E_a value of 21 ± 5 kJ mol⁻¹ (type ii analysis) suggestive of a transport controlled rate determining process. However, the rate of leaching rapidly decreased until it was consistently slower than for the equivalent leaches where Fe³⁺ was not added. The resulting E_a value for this leach regime of 83 ± 10 kJ mol⁻¹ is within experimental error of that determined in the absence of added Fe³⁺. In contrast to Cu release, Fe release to solution was consistent with a chemical reaction controlled leach rate throughout. The Fe release E_a of 76 ± 10 kJ mol⁻¹ is also within experimental error of that determined in the absence of added Fe³⁺. Where type (ii) and (iii) analyses were both successfully carried out (in all cases except for Cu leaching with added Fe³⁺, <10 h) the E_a derived are within experimental error. However, the type (iii) analyses of the leaches in the presence of added Fe³⁺ (>10 h), as compared to in the absence of added Fe³⁺, returned a considerably smaller pre-exponential factors for both Cu and Fe leach analyses commensurate with the considerably slower leach rate, suggestive of a more applicable kinetic analysis.XPS examination of leached chalcopyrite showed that the surface concentration of polysulfide and sulfate was significantly increased when Fe³⁺ was added to the leach liquor. Complementary SEM analysis revealed the surface features of chalcopyrite, most likely due to the nature of the polysulfide formed, are subtly different with greater surface roughness upon leaching in the absence of added Fe³⁺ as compared to a continuous smooth surface layer formed in the presence of added Fe³⁺. These observations suggest that the effect of Fe³⁺ addition on the rate of leaching is not due to the change in the chemical reaction controlled mechanism but due to a change in the available surface area for reaction.     

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

Fe2+–Fe3+ ordered distribution in chromite spinels

Mossbauer measurements have been carried out on three natural chromite minerals from different locations in China over the temperature range 50 to 750 K. The experiments showed these samples to be magnesioferrochromites. The Mossbauer spectra measured could be decomposed into three doublets: two attributed to the tetrahedral T-site Fe²⁺ ions and the third to the octahedral M-site Fe³⁺ ions. Thus for the chromite spinels the results strongly supported the ordered distribution with Fe²⁺ in the T-site and Fe³⁺ in M-site.