Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 Levels in Geological Materials by Direct Nebulisation of Sample HF Solution into FI-ICP-MS

We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma-mass spectrometry fitted with a flow injection system (FI-ICP-MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g-1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS-1, PCC-1, BCR-1, BHVO-1 and AGV-1, GSJ reference materials JB-1, -2, -3, JA-1, -2 and -3, and the Smithsonian reference Allende powder.     

Use of Magnet Technology for Phosphate Elimination from Municipal Sewage

The present report describes the set-up and first operation results of a novel carousel magnetic separator. This carousel magnetic separator is suitable for continuous separation of magnetized particles from water. Continuous operation is achieved by a segmented rotating separation matrix. This matrix also allows the use of low-cost permanent magnets, by means of which magnetic fields of up to 0.5 T can be generated without energy consumption. The suitability of a first prototype of this carousel magnetic separator was tested for elimination of magnetite-containing iron phosphate and iron hydroxide flocs. These flocs result from conventional precipitation/flocculation of municipal sewage with FeCl₃ and the addition of magnetite particles generated by wet-chemical processes. First results demonstrate that the carousel magnetic separator can reduce phosphate concentrations of up to 14 mg/L PO₄^3–-P in the inlet to below 1 mg/L PO₄^3–-P in the outlet at filtration rates of about 40 m/h. Magnetite dosage in the range of 50 mg/L affects phosphate precipitation positively via a slight reduction of the precipitant volume. However, the total amount of chemicals required for phosphate elimination is increased by the substances needed for magnetite production. Therefore, a further reduction of magnetite dosage must be achieved.     

Melt migration and melt-rock reaction in the Alpine-Apennine peridotites:Insights on mantle dynamics in extending lithosphere

The compositional variability of the lithospheric mantle at extensional settings is largely caused by the reactive percolation of uprising melts in the thermal boundary layer and in lithospheric environments.The Alpine-Apennine(A-A)ophiolites are predominantly constituted by mantle peridotites and are widely thought to represent analogs of the oceanic lithosphere formed at ocean/continent transition and slow-to ultraslow-spreading settings.Structural and geochemical studies on the A-A mantle peridotites have revealed that they preserve significant compositional and isotopic heterogeneity at variable scale,reflecting a long-lived multi-stage melt migration,intrusion and melt-rock interaction history,occurred at different lithospheric depths during progressive uplift.The A-A mantle peridotites thus constitute a unique window on mantle dynamics and lithosphere-asthenosphere interactions in very slow spreading environments.In this work,we review field,microstructural and chemical-isotopic evidence on the major stages of melt percolation and melt-rock interaction recorded by the A-A peridotites and discuss their consequences in creating chemical-isotopic heterogeneities at variable scales and enhancing weakening and deformation of the extending mantle.Focus will be on three most important stages:(i)old(pre-Jurassic)pyroxenite emplacement,and the significant isotopic modification induced in the host mantle by pyroxenite-derived melts,(ii)melt-peridotite interactions during Jurassic mantle exhumation,i.e.the open-system reactive porous flow at spinel facies depths causing bulk depletion(origin of reactive harzburgites and dunites),and the shallower melt impregnation which originated plagioclase-rich peridotites and an overall mantle refertilization.We infer that migrating melts largely originated as shallow,variably depleted,melt fractions,and acquired Si-rich composition by reactive dissolution of mantle pyroxenes during upward migration.Such melt-rock reaction processes share significant similarities with those documented in modern oceanic peridotites from slow-to ultraslow-spreading environments and track the progressive exhumation of large mantle sectors at shallow depths in oceanic settings where a thicker thermal boundary layer exists,as a consequence of slow-spreading rate.     

Subduction-zone peridotites and their records of crust-mantle interaction

Subduction is the core process of plate tectonics. The mantle wedge in subduction-zone systems represents a key tectonic unit, playing a significant role in material cycling and energy exchange between Earth's layers. This study summarizes research progresses in terms of subduction-related peridotite massifs, including supra-subduction zone(SSZ) ophiolites and mantle-wedge-type(MWT) orogenic peridotites. We also provide the relevant key scientific questions that need be solved in the future. The mantle sections of SSZ ophiolites and MWT orogenic peridotites represent the mantle fragments from oceanic and continental lithosphere in subduction zones, respectively. They are essential targets to study the crust-mantle interaction in subduction zones. The nature of this interaction is the complex chemical exchanges between the subducting slab and the mantle wedge under the major control of physical processes. The SSZ ophiolites can record melt/fluid-rock interaction, metamorphism,deformation, concentration of metallogenic elements and material exchange between crust and mantle, during the stages from the generation of oceanic lithosphere at spreading centers to the initiation, development, maturation and ending of oceanic subduction at continental margins. The MWT orogenic peridotites reveal the history of strong metamorphism and deformation during subduction, the multiple melt/fluid metasomatism(including silicatic melts, carbonatitic melts and silicate-bearing C-HO fluids/supercritical fluids), and the complex cycling of crust-mantle materials, during the subduction/collision and exhumation of continental plates. In order to further reveal the crust-mantle interaction using subduction-zone peridotites, it is necessary to utilize high-spatial-resolution and high-precision techniques to constrain the complex chemical metasomatism, metamorphism,deformation at micro scales, and to reveal their connections with spatial-temporal evolution in macro-scale tectonics.     

Presumed magnetic biosignatures observed in magnetite derived from abiotic reductive alteration of nanogoethite

The oriented chains of nanoscale Fe-oxide particles produced by magnetotactic bacteria are a striking example of biomineralization. Several distinguishing features of magnetite particles that comprise bacterial magnetosomes have been proposed to collectively constitute a biosignature of magnetotactic bacteria (Thomas-Keprta et al., 2001). These features include high crystallinity, chemical purity, a single-domain magnetic structure, well-defined crystal morphology, and arrangement of particles in chain structures. Here, we show that magnetite derived from the inorganic breakdown of nanocrystalline goethite exhibits magnetic properties and morphologies remarkably similar to those of biogenic magnetite from magnetosomes. During heating in reducing conditions, oriented nanogoethite aggregates undergo dehydroxylation and transform into stoichiometric magnetite. We demonstrate that highly crystalline single-domain magnetite with euhedral grain morphologies produced abiogenically from goethite meets several of the biogenicity criteria commonly used for the identi?cation of magnetofossils. Furthermore, the suboxic conditions necessary for magnetofossil preservation in sediments are conducive to the reductive alteration of nanogoethite, as well as the preservation of detrital magnetite originally formed from goethite. The findings of this study have potential implications for the identification of biogenic magnetite, particularly in older sediments where diagenesis commonly disrupts the chain structure of magnetosomes. Our results indicate that isolated magnetofossils cannot be positively distinguished from inorganic magnetite on the basis of their magnetic properties and morphology, and that intact chain structures remain the only reliable distinguishing feature of fossil magnetosomes.     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

LA-ICP-MS Analysis of Magnetite and Application in Genesis of Mineral Deposit

Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is well characterized by the in-situ, real time, lower limit of detection and high space resolution, etc. Therefore, it is more excellent in the analysis of trace element for varied minerals in comparison to other micro-zone analysis technologies. Magnetite as a common mineral from different deposits and rocks has been focused on chemical compositions by researchers worldwide. In fact, as the insignificant matrix effect for most elements in magnetite, analysis results could be calculated effectively against Fe-rich silicate glass as the reference material. Therefore, researches on trace element distribution of magnetite have been developed rapidly in recent years, and it has a wide application prospect in reflecting the condition of ore-forming, discriminating different deposit types and indicating prospecting exploration. Comparing varied previous discrimination diagrams about magnetite via collecting trace element data from available literatures based on 25 deposits, we found that there was an urgent need for further detailing and reexamining the boundary of fields representing different genetic types, and it was vital for interpreting the data through carefully petrographical observation before analysis. In addition, we discussed several complex physicochemical factors, which would influence the element concentration of magmatite in igneous and hydrothermal processes, such as melt/fluid composition, temperature, cooling rate, pressure, oxygen fugacity, sulfur fugacity and silica activity. In magma stage, Magnetite’s components are closely related to melts composition and differentiation, while fluid features would also significantly change magnetie's components. Furthermore, there is serious interference for discriminating the genesis of magnetite because of late stage fluids and equilibrium again in subsolidus condition. This paper reviewed the developments of trace elements analysis by LA-ICP-MS and important applications about magnetite in mineral deposit so that unique thoughts for the research on mineralization and ore-forming processes could be obtained.     

Removal of Ni(II) from Aqueous Solutions by Nanoscale Magnetite

Magnetite nanoparticles were applied to remove Ni(II) from aqueous solutions as a function of pH, contact time, supporting electrolyte concentration, and analytical initial Ni(II) concentration. The highly crystalline nature of the magnetite structure with diameter of around 10 nm was characterized with transmission electron microscopy (TEM) and X‐ray diffractometry (XRD). The surface area was determined to be 115.3 m²/g. Surface chemical properties of magnetite at 25°C in aqueous suspensions were investigated. The point of zero charge (pHzpc) was found to be 7.33 and the intrinsic acidity constants (${\rm p}K_{{\rm a}1}^{{\rm s}} $ and ${\rm p}K_{{\rm a}2}^{{\rm s}} $ ) were found to be 9.3 and 5.9, respectively. The surface functional groups were investigated with Fourier transform‐infrared spectroscopy (FTIR) as well. Batch experiments were carried out to determine the adsorption kinetics and mechanism of Ni(II) by these magnetite nanoparticles. The adsorption process was found to be pH dependent. In NaCl solutions, Ni(II) adsorption increased with increasing ionic strength while in NaClO₄ solutions, Ni(II) adsorption exhibited little dependence on the ionic strength of the solution. The adsorption process better followed the pseudo‐second order equation and Freundlich isotherm.     

云南西双版纳曼远铁矿矿床地质

曼远铁矿以磁铁矿、赤铁矿、磁赤铁矿为主,赋存于澜沧群勐井山组上段中部。该组地层中夹多层中性—基性火山岩、火山凝灰岩,属典型的火山沉积变质型铁矿。     

地幔橄榄岩中橄榄石的指示意义

橄榄石是地幔橄榄岩和辉石岩的主要组成矿物,但也经常以斑晶和捕虏晶的形式出现在玄武质岩石中。结合近年来在地幔橄榄岩的主要元素(如Mg和Fe)组成特征以及Li、Mg和Fe稳定同位素地球化学方面的研究成果,重点对橄榄石的地球化学特征与华北克拉通岩石圈地幔演化过程之间的联系进行了讨论,旨在加深对华北克拉通岩石圈地幔演化过程的理解。现有研究表明:地幔橄榄岩中橄榄石的矿物学特征、元素和同位素地球化学组成能够很好地指示岩石圈地幔的特征及其演化过程,因而具有重要的意义。对于克拉通地区的地幔橄榄岩来说,橄榄石的Mg#通常可以指示岩石圈地幔的属性,古老、难熔的地幔橄榄岩中的橄榄石一般具有较高的Mg#(>92),而新生的岩石圈地幔橄榄岩中的橄榄石则具有较低的Mg#(<91)。因此,地幔橄榄岩中橄榄石的Mg#在一定程度上具有年龄意义。橄榄岩中橄榄石的Li、Mg和Fe同位素组成也可以明确指示岩石圈地幔的属性及其所经历的演化过程,正常地幔的δ7Li、δ26Mg和δ57Fe组成相对均一,如果上述同位素组成偏离正常地幔值,则说明岩石圈地幔经历了熔体/流体的交代作用。华北克拉通地区地幔橄榄岩捕虏体中橄榄石的Li、Mg和Fe同位素组成研究表明:该区的岩石圈地幔经历了多个阶段、不同来源的熔体/流体的改造过程。