Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.     

Reflectance spectroscopic characterisation of mineral alteration footprints associated with sediment-hosted gold mineralisation at Mt Olympus (Ashburton Basin,Western Australia)

Hydrothermal ore deposits are typically characterised by footprints of zoned mineral assemblages that extend far beyond the size of the orebody. Understanding the mineral assemblages and spatial extent of these hydrothermal footprints is crucial for successful exploration, but is commonly hindered by the impact of regolith processes on the Earth's surface. Hyperspectral drill core (HyLogger?-3) data were used to characterise alteration mineralogy at the Mt Olympus gold deposit located 35 km southeast of Paraburdoo along the Nanjilgardy Fault within the northern margin of the Ashburton Basin in Western Australia. Mineralogy interpreted from hyperspectral data over the visible to shortwave (400–2500 nm) and thermal (6000–14500 nm) infrared wavelength ranges was validated with X-ray diffraction and geochemical analyses. Spaceborne multispectral (ASTER) and airborne geophysical (airborne electromagnetic, AEM) data were evaluated for mapping mineral footprints at the surface and sub-surface. At the deposit scale, mineral alteration patterns were identified by comparing the most abundant mineral groups detected in the HyLogger data against lithology logging and gold assays. Potential hydrothermal alteration phases included Na/K-alunite, kaolin phases (kaolinite, dickite), pyrophyllite, white mica, chlorite and quartz, representing low-T alteration of earlier greenschist metamorphosed sediments. The respective zoned mineral footprints varied depending on the type of sedimentary host rock. Siltstones were mainly characterised by widespread white-mica alteration with proximal kaolinite alteration or quartz veining. Sandstones showed (1) distal white mica, intermediate dickite, and proximal alunite + kaolinite or (2) widespread white-mica alteration with associated intervals of kaolinite. In both, sandstones and siltstones, chlorite was distal to gold mineralisation. Conglomerates showed distal kaolinite/dickite and proximal white-mica/dickite alteration. Three-dimensional visualisation of the gold distribution and spatially associated alteration patterns around Mt Olympus revealed three distinct categories: (1) several irregular, poddy, SE-plunging zones of >0.5 ppm gold intersected by the Zoe Fault; (2) sulfate alteration proximal to mineralisation, particularly on the northern side of the Mt Olympus open pit; and (3) varying Al^IVAl^VISi^IV_–1(Mg,Fe)^VI_–1 composition of white micas with proximity to gold mineralisation. Chlorite that developed during regional metamorphic or later hydrothermal alteration occurs distal to gold mineralisation. ASTER mineral mapping products, such as the MgOH Group Content used to map chlorite (±white mica) assemblages, showed evidence of correlation to mapped, local structural features and unknown structural or lithological contacts as indicated by inversion modelling of AEM data.     

同步辐射软X射线吸收谱与发射谱测定天然针铁矿能带结构

天然半导体矿物由于成分、缺陷复杂,传统测试方法如紫外可见漫反射等难以准确测定其禁带宽度.本文以针铁矿为例,通过第一性原理计算得到纯针铁矿及掺Al针铁矿的电子结构.计算结果显示,纯针铁矿导带底与价带顶均由Fe3d与O2p轨道组成,而当含杂质Al时,Al2p与O2p发生杂化参与了价带组成.在此基础上,利用同步辐射X射线氧的K边吸收谱与发射谱对纯针铁矿及天然针铁矿的能带结构进行了测定.结果表明,天然含Al的针铁矿禁带宽度为2.30eV,小于纯针铁矿(2.57eV).本研究提供了一种测定天然氧化物矿物禁带宽度的新方法,为深入研究天然半导体可见光催化活性产生机制提供了理论依据.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

Application of Geochemistry and VNIR Spectroscopy in Mapping Heavy Metal Pollution of Stream Sediments in the Takab Mining Area, NW of Iran

This study considered the possibility of using visible and near infrared (VNIR) spectral absorption feature parameters (SAFPs) in predicting the concentration and mapping the distribution of heavy metals in sediments of the Takab area. In total, 60 sediment samples were collected along main streams draining from the mining districts and tailing sites, in order to measure the concentration of As, Co, V, Cu, Cr, Ni, Hg, Ti, Pb and Zn and the reflectance spectra (350–2500 nm). The quantitative relationship between SAFPs (Depth500nm, R610/500nm, R1344/778nm, Area500nm, Depth2200nm, Area2200nm, Asym2200nm) and geochemical data were assessed using stepwise multiple linear regression (SMLR) and enter multiple linear regression (EMLR) methods. The results showed a strong negative correlation between Ni and Cr with Area2200nm, a significant positive correlation between As and Asym2200nm, Ni and Co with Depth2200nm, as well as Co, V and total values with Depth500nm. The EMLR method eventuated in a significant prediction result for Ni, Cr, Co and As concentrations based on spectral parameters, whereas the prediction for Zn, V and total value was relatively weak. The spatial distribution pattern of geochemical data showed that mining activities, along with the natural weathering of base metal occurrences and rock units, has caused high concentrations of heavy metals in sediments of the Sarough River tributaries.     

Composition and origin of the volatile components released from the Pesyanoe aubrite by stepwise crushing and heating

Aubrites are achondritic meteorites (enstatite pyroxenites) that were formed in highly reduced magmatic environments on a differentiated parent body sharing a common oxygen isotope reservoir with enstatite chondrites (EC), Earth and Moon, and could be considered as a geochemical model of the early proto-Earth. Some pyroxenes of the Pesyanoe aubrite have high abundance of gaseous inclusions, captured during the crystallization of the rocks. Investigation of the inclusions by IR spectroscopy reveals presence of OH⁻ groups and C–H bonds. The former are assigned to protonated point defects in enstatite lattice and the latter to compounds occupying void walls. Molecular water and CO₂ were not observed. Volatile components released from the samples of the Pesyanoe enstatite by stepwise crushing and heating are composed of CO₂, H₂O and a non-condensable phase. Hydrogen isotopic composition of volatiles extracted in form of molecular water in Px-separates varies in the range δD = −61 – −84‰ with mean value of δD = −73 ± 16‰ VSMOW and is within the ranges of ECs and Earth’s mantle. The total abundance of H₂ in the pyroxene of Pesyanoe were estimated as at least 0.047 ppm that is too low in comparison with that of enstatite chondrites (≥30 ppm H₂) and could indicate nearly complete degassing of the Pesyanoe primitive precursor material during the Pesyanoe parent body accretion or a mantle degassing in igneous differentiation process. In a last case a primitive precursor could have D/H ratio different from that of enstatite chondrites.     

微波等离子体原子发射光谱法测定偏远矿区海泡石中的主微量元素

海泡石是具有层状结构的含水富镁硅酸盐黏土矿物,其中无机元素含量是揭示其成矿物质来源、成矿流体性质和矿床成因的重要依据,通常采用电感耦合等离子体发射光谱/质谱法(ICP-OES/MS)进行测定,等离子体(ICP)的高温激发会产生成大量谱线干扰,维持ICP稳定工作需使用高纯氩气,持续供气对于偏远矿区海泡石的检测还将面对气体采购和运输不便的问题。本文基于微波等离子体原子发射光谱(MP-AES)的低温激发技术减少光谱干扰,建立了准确测定偏远矿区海泡石中主量元素Mg、Al、Ca、Fe、K、Na和微量元素Cu、Zn、Mn、Pb含量的分析方法。利用硝酸-盐酸-氢氟酸混合酸对海泡石进行微波消解,避免了样品处理过程中分析元素的损失,加快了样品处理速度,同时提高了样品溶液的稳定性。通过选择各元素光谱线的分析波长,并利用快速线性干扰校正(FLIC)技术校正光谱干扰,以Lu为内标元素校正基体效应,提高了灵敏度和准确度。各元素的检出限为0.19～14.6μg/L。海泡石国家标准物质(GBW07138)各元素测定值与认定值的相对误差在-5.0%～6.7%之间。本方法具有检出限低、线性范围宽、结果准确等优点;MP-AES采用自带的氮气发生器为等离子体提供氮气作为工作气,无需引入复杂气体,提高了分析效率,尤其适用于气体采购和运输不便的偏远矿区。     

新疆奇台县黄羊山石墨矿床特征、物质来源及成因

黄羊山石墨矿床位于新疆东准噶尔造山带南部的卡拉麦里地区东南段,是近年来新发现的国内外首个产于花岗岩体中的超大型石墨矿床。成矿地质条件、矿床地质特征研究表明,该矿床与黄羊山碱性花岗岩体具有密切的时空及成因联系,矿石具独特的球状构造,球体中石墨与长英质矿物及磁黄铁矿、黄铜矿等金属硫化物密切共生。为确定黄羊山石墨矿床的成因和成矿物质来源,本文开展了球状矿石中的石墨拉曼光谱分析和C同位素测试,对与石墨密切共生的金属硫化物开展S-Pb同位素分析。结果表明,黄羊山矿床球状矿石不同部位石墨的拉曼谱峰相似,显示具有很高的结晶程度,估算结晶温度为750～800℃;7件石墨样品的δ~(13)C值在-19.27‰～-19.90‰,分布非常集中,介于岩浆碳值和有机碳值之间,表明具有两者的混合来源。4件磁黄铁矿样品的δ~(34)S值集中在-2.3‰～-2.9‰之间,接近原始地幔值;在Pb同位素构造环境判别图解上,Pb同位素比值(~(206)Pb/~(204) Pb=18.114～19.040,~(207)Pb/~(204) Pb=15.448 ～ 15.543,~(208) Pb/~(204)Pb=38.253～38.915)显示较好的线性关系,延伸方向与地幔演化曲线的延伸方向基本一致;S-Pb同位素测试结果表明,与石墨共生金属硫化物具有幔源特征。综合黄羊山矿床成矿地质条件、成矿特征、石墨及共生硫化物的物质来源等研究结果,本文初步认为,黄羊山石墨矿床形成于碱性花岗岩的岩浆作用阶段,矿石中的金属硫化物来自岩浆混合作用中的幔源基性端元,碳质由于岩浆同化混染作用达到饱和,在硫化物的催化下沉积形成石墨。     

土壤粒径的光谱响应特性研究

以实验室制备的5个不同粒径水平的土壤样本和室内高光谱数据为基础,通过对光谱数据进行重采样、数学变换等预处理并进行单因素方差分析、相关性分析和回归分析,探讨土壤粒径的高光谱特性,建立了光谱数据预测土壤粒径的校正模型。结果表明,土壤粒径对反射光谱有显著的影响,波长越长影响越大;在全波段范围内土壤粒径和光谱数据都呈负相关关系,对原始光谱数据进行微分变换能增加其与土壤粒径的相关性;以反射率一阶微分建立的回归模型为反演土壤粒径的最佳模型,其建模决定系数■、预测决定系数■、预测相对偏差RPD分别为0.666,0.653,2.043,预测均方根误差RMSE为0.175。     

Retrieving volume FeO and TiO_2 abundances of lunar regolith with CE-2 CELMS data using BPNN method

The volume FeO and TiO_2 abundances(FTAs) of lunar regolith can be more important for understanding the geological evolution of the Moon compared to the optical and gamma-ray results. In this paper, the volume FTAs are retrieved with microwave sounder(CELMS) data from the Chang'E-2 satellite using the back propagation neural network(BPNN) method. Firstly, a three-layered BPNN network with five-dimensional input is constructed by taking nonlinearity into account. Then, the brightness temperature(TB) and surface slope are set as the inputs and the volume FTAs are set as the outputs of the BPNN network.Thereafter, the BPNN network is trained with the corresponding parameters collected from Apollo, Luna,and Surveyor missions. Finally, the volume FTAs are retrieved with the trained BPNN network using the four-channel TBderived from the CELMS data and the surface slope estimated from Lunar Orbiter Laser Altimeter(LOLA) data. The rationality of the retrieved FTAs is verified by comparing with the Clementine UV-VIS results and Lunar Prospector(LP) GRS results. The retrieved volume FTAs enable us to re-evaluate the geological features of the lunar surface. Several important results are as follows. Firstly, very-low-Ti(<1.5 wt.%) basalts are the most spatially abundant, and the surfaces with TiO_2> 5 wt.% constitute less than 10% of the maria. Also, two linear relationships occur between the FeO abundance(FA) and the TiO_2 abundance before and after the threshold, 16 wt.% for FA. Secondly, a new perspective on mare volcanism is derived with the volume FTAs in several important mare basins, although this conclusion should be verified with more sources of data. Thirdly, FTAs in the lunar regolith change with depth to the uppermost surface,and the change is complex over the lunar surface. Finally, the distribution of volume FTAs hints that the highlands crust is probably homogeneous, at least in terms of the microwave thermophysical parameters.