Improved methods for selective dissolution of Mn oxides: applications for studying trace element associations

The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl₂(Mn^IV₂Mn^III)O₆(OH)₆ was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn₈O₁₆) and/or coronadite (PbMn₈O₁₆) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.     

An evaluation of trace element release associated with acid mine drainage

The determination of trace element release from geologic materials, such as oil shale and coal overburden, is important for proper solid waste management planning. The objective of this study was to determine a correlation between trace element residency and concentration to trace element release using the following methods: (1) sequential selective dissolution for determining trace element residencies, (2) toxicity characteristic leaching procedure (TCLP), and (3) humidity cell weathering study simulating maximum trace element release. Two eastern oil shales were used, a New albany shale that contains 4.6 percent pyrite, and a Chattanooga shale that contains 1.5 percent pyrite. Each shale was analyzed for elemental concentrations by soluble, adsorbed, organic, carbonate, and sulfide phases. All leachates were analyzed to determine total trace element concentrations. The results of the selective dissolution studies show that each trace element has a unique distribution between the various phases. Thus, it is possible to predict trace element release based on trace element residency. The TCLP results show that this method is suitable for assessing soluble trace element release but does not realistically assess potential hazards. The results of the humidity cell studies do demonstrate a more reasonable method for predicting trace element release and potential water quality hazards. The humidity cell methods, however, require months to obtain the required data with a large number of analytical measurements. When the selective dissolution data are compared to the trace element concentrations in the TCLP and humidity cell leachates, it is shown that leachate concentrations are predicted by the selective dissolution data. Therefore, selective dissolution may represent a rapid method to assess trace element release associated with acid mine drainage.     

Phase associations and potential selective extraction methods for selected high-tech metals from ferromanganese nodules and crusts with siderophores

Deep-sea ferromanganese deposits contain a wide range of economically important metals. Ferromanganese crusts and nodules represent an important future resource, since they not only contain base metals such as Mn, Ni, Co, Cu and Zn, but are also enriched in critical or rare high-technology elements such as Li, Mo, Nb, W, the rare earth elements and yttrium (REY). These metals could be extracted from nodules and crusts as a by-product to the base metal production. However, there are no proper separation techniques available that selectively extract certain metals out of the carrier phases. By sequential leaching, we demonstrated that, except for Li, which is present in an easily soluble form, all other high-tech metals enriched in ferromanganese nodules and crusts are largely associated with the Fe-oxyhydroxide phases and only to subordinate extents with Mn-oxide phases. Based on this fact, we conducted selective leaching experiments with the Fe-specific organic ligand desferrioxamine-B, a naturally occurring and ubiquitous siderophore. We showed by leaching of ferromanganese nodules and crusts with desferrioxamine-B that a significant and selective extraction of high-tech metals such as Li, Mo, Zr, Hf and Ta is possible, while other elements like Fe and the base metals Mn, Ni, Cu, Co and Zn are not extracted to large extents. The set of selectively extracted elements can be extended to Nb and W if Mn and carbonate phases are stripped from the bulk nodule or crust prior to the siderophore leach by e.g. a sequential leaching technique. This combination of sequential leaches with a siderophore leach enhanced the extraction to 30–50% of each Mo, Nb, W and Ta from a mixed type Clarion-Clipperton Zone (CCZ) nodule and 40–80% from a diagenetic Peru Basin nodule, whilst only 5–10% Fe and even less Mn are extracted from the nodules. Li is extracted to about 60% from the CCZ nodule and a maximum of 80% Li is extracted from the Peru Basin nodule.Our pilot work on selective extraction of high-tech metals from marine ferromanganese nodules and crusts showed that specific metal-binding organic ligands may have promising potential in future processing technologies of these oxide deposits.     

Some geochemical controls on Ni and Co concentrations in marine ferromanganese deposits

The uptake of Ni and Co in the hydrous Mn oxide or the amorphous Fe-oxide phases of ferromanganese deposits in the oceans was studied by electron-microprobe analyses of 17 natural manganese nodules and by experiments on desorption-dissolution of these metals from synthetic Fe oxide or Mn oxides and natural nodule material. Ni was found to occur nearly always in the Mn-oxide phases of natural nodules, while Co occurs both in the Mn-oxide and Fe-oxide phases, with a slight preference for the latter. The solubility of Ni and Co (from coprecipitates of these metals with Fe hydroxides after aging) in seawater was found to depend strongly on the crystallinity of the host phase. The adsorption of Co by the synthetic Mn oxides from seawater was higher than that of Ni. The experimentally determined solubility of Ni and Co in seawater from natural nodule material is extremely low and matches the concentration range of these metals in ocean water.     

Mineralogy and trace element association in an acid mine drainage iron oxide precipitate; comparison of selective extractions

Mineral and trace element characterization of an Fe-rich precipitate from an acid mine system was accomplished by X-ray diffraction (XRD), differential X-ray diffraction, and ICP chemical analysis. A primary objective was to evaluate the effectiveness of common selective dissolution treatments in determining the association of minerals with potentially toxic trace elements. The precipitate consisted primarily of goethite, a poorly crystalline phase resembling synthetic ferrihydrite, dolomite and gypsum in clay-size fractions. The ammonium oxalate and EDTA treatments, which are thought by some workers to dissolve only poorly crystalline phases, were found to dissolve a significant amount of crystalline goethite. However, the oxalate extraction did dissolve more ferrihydrite than the other treatments tested. A solution of 0.1 M hydroxylamine hydrochloride in 0.1 M HNO₃, which is thought by some to dissolve mostly the highly soluble Mn-oxides was found to also dissolve goethite, as did 0.25 M hydroxylamine hydrochloride in 25% (v/v) acetic acid, 0.25 M hydroxylamine hydrochloride in 0.25 M HCI, 0.5 M HCI, and Na-dithionite buffered with Na-citrate and 1.0 M NaHCO₃. Both trace and major elements that were extracted with the various treatments were found to vary significantly and non-systematically when compared to the proportion of total extractable Fe. These selective extractions cannot be used to make reliable conclusions about trace metal and mineral associations. Gypsum was identified by XRD in claysize separations from the sample, but this phase was not detected in diffraction scans of the bulk sample. This finding indicates that individual phases can be segregated by particle size.     

Potential contaminants at a dredged spoil placement site,Charles City County,Virginia, as revealed by sequential extraction

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.     

伴生金赋存状态的几种主要研究方法

作者总结了在多年研究伴生金赋存状态中常采用的光学显微镜法、电子探针分析法、元素的化学分析法、选择性溶解法及元素平衡配分法等几种有效的研究方法,并给出一些应用的例子.通过这些研究方法,能够有效、快捷地查清伴生金的赋存状态特征及分布规律,为今后的研究提供可借鉴的经验.     

New CGSP Carbonate Matrix Reference Materials for LA-ICP-MS Analysis

Four CGSP (Chinese Geological Standard Powders) carbonate matrix element reference materials were prepared by a coprecipitation method. The major and trace elements were dissolved from natural rare earth carbonate raw materials in strong acid and precipitated with ammonium bicarbonate or ammonia to form carbonate matrix phases. The carbonate reference materials were ground and pressed into tablets for microanalysis. The element homogeneity and stability in CGSP reference materials were tested by LA-ICP-MS using a calibration strategy without an internal standard element and evaluated mainly following ISO Guide 35: 2017 and JJF 1343-2012. Although the homogeneity of most of elements in the CGSP series were comparable to the repeatability obtained from homogeneous glasses, some elements (e.g., Mo, Se, Ga, Ge, Cd, Ni, Co, U) were found to have some degree of heterogeneity. All of elements passed the t-test evaluation in a 32-month stability examination except for Mo in CGSP-A, Na, Ge, Mo in CGSP-B, Ni, Cd, Sn in CGSP-C, and Al, P, Tb, Ho in CGSP-D. The certified element mass fraction values and uncertainties were determined with the characterisation of a non-operationally defined measurand using various bulk analysis methods in eight laboratories. GGSPs will provide a new carbonate calibration reference option for microanalysis.     

Chemical and mineralogical investigations on deep sea manganese nodules from the Southern Ocean

Deep sea manganese nodules from the Southern Ocean have been studied using chemical analysis, X-ray diffraction, optical mineragraphic and electron probe microanalysis techniques. The nodules were lower in manganese, iron and associated elements than the average grade of manganese nodules from other localities. A number of chemical relationships have been observed. Nickel, copper, cobalt, barium, zinc, molybdenum, strontium, sulphur and phosphorus are associated with the manganese rich phases and titanium with the iron rich phases. X-ray diffraction analysis and electron probe microanalysis results indicate that the manganese phases are similar to the disordered -MnO₂ and manganite phases reported by other workers.

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Zusammenfassung Tiefsee-Manganknollen aus dem südlichen Ozean wurden mit Hilfe von chemischen Analysen, Röntgenbeugung, mikroskopischer Untersuchung und Anwendung von Mikroelektronensonden untersucht. Die Knollen enthielten weniger Mangan, Eisen und Begleitelemente als das Durchschnittsquantum in Manganknollen aus anderen Gebieten. Eine Anzahl chemischer Ähnlichkeiten wurde beobachtet. Nickel, Kupfer, Kobalt, Barium, Zink, Molybdän, Strontium, Schwefel und Phosphor treten gemeinsam mit den manganreichen Erscheinungsformen, und Titan zusammen mit den eisenreichen auf. Ergebnisse der Röntgenbeugungsanalyse und Mikroelektronensondenuntersuchung ergaben, daß die Manganphasen Ähnlichkeit haben mit ungeordneten -MnO₂ und manganitischen Erscheinungsformen, über die andere Wissenschaftler berichtet haben.

     

Modelling of major elements in mantle-melt systems using trace element approaches

Major elements can be modelled in ways similar to the quantitative petrogenetic modelling used for trace elements. In contrast to modelling with trace elements, however, modelling with major elements is constrained by the stoichiometry of the solid phases. Within these constraints, the same equations for partial melting and crystallization which have been used to such advantage for trace elements may be used for major elements.Calculated MgO and FeO abundances in a mantle-melt system are used as an example of the modelling technique. Such modelling yields limited fields of permissible melts and residues for a given parent composition, but does not give the paths of melting. It does allow the temperature and extent of melting which gave rise to a melt to be determined from the MgO and FeO abundances of the melt or residual solid. Applying the results of the modelling to igneous rocks and ultramafic nodules leads to the following conclusions, which are subject to the uncertainties in the available distribution coefficients. Least differentiated basalt glasses from the ocean floor are derived from parent melts with less than 15.5 weight % MgO and 8.2 wt. % FeO. Komatiites may be derived by less than 60% melting of a pyrolite source leaving a residue of olivine and pyroxene. Many nodules from the subcontinental mantle appear to be residues of large fractions of melting (>30%) at high temperature and pressure, whereas ultramafic nodules from oceanic basalts appear to be residues of smaller fractions of melting (<30%) at lower temperatures and pressures.     

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

东太平洋CCFZ区多金属结核元素富集机制:来自结核剖面原位微区分析

多金属结核微层原位微区分析能够更好地揭示结核生长过程中元素的赋存和迁移过程,为认识多金属结核元素富集机制和成因提供新的证据.通过使用电子探针(EPMA)和激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)等手段对采集自东太平洋克拉里昂?克利珀顿断裂区(CCFZ区)的多金属结核进行了分析研究.研究结果表明,结核矿物主要为...     

关键金属元素分析测试技术方法应用进展

以稀有、稀散、稀土、铂族元素为主体的战略性关键金属矿产资源,在新材料、新能源和信息技术等新兴产业中发挥着越来越关键的作用。随着我国关键矿产资源地质调查的不断深入,关键金属元素以其赋存基体复杂、不同矿物含量差异大、化学性质不稳定等特点对分析测试技术提出了新的挑战。本文根据化学组成不同,对关键金属元素主要赋存基体进行了分类,主要分为硅酸盐、碳酸盐、硫酸盐、钨酸盐、磷酸盐、氧化物、硫化物、卤化物等。对于不同的基体岩石矿物,通常采用酸溶法(硝酸-氢氟酸组合、王水)或碱熔法等传统溶样方法进行化学消解。评述了当前关键金属元素测试常用的电子探针、电感耦合等离子体质谱、电感耦合等离子体发射光谱、X射线荧光光谱等仪器的特点及应用,总结了关键金属元素分析过程中出现的样品难溶解、回收率不完全、测试过程氧化物和同质异位素干扰、样品和标准基体不一致等常见问题,并提出了相应的解决方案。微区原位分析凭借其高效率、低成本、高空间分辨率的优势,以及野外现场分析凭借其简单快速、贴近野外工作的特点是关键金属元素测试技术发展的主要趋势。     

Rates of accumulation of manganese nodules and associated sediment from the equatorial Pacific

The accumulation rates and trace element contents of manganese nodules and coexisting sediment in a core collected from the central equatorial Pacific indicate that the nodules are chemically very similar and accumulated at similar rates, but that each stopped growing when it was buried. Elements largely confined to authigenic phases accumulate at comparable rates in nodules and sediment, whereas elements associated with detrital phases accumulate much more rapidly in the sediment.     

Assessment of Dissolution of Silicate Rock Reference Materials with Ammonium Bifluoride and Nitric Acid in a Microwave Oven

The complete dissolution of representative test portions of powdered rock samples for the determination of the mass fractions of trace elements by ICP‐MS relies either on aggressive and time‐consuming acid digestions or fusion/sintering with appropriate fluxes. Here, we evaluate a microwave oven dissolution method that employs a solution of NH₄HF₂ and HNO₃. The entire procedure occurs in a closed vessel system and takes up to 4 h. In hundreds of digestions, the precipitation of fluorides was never observed. Replicate decomposition of 100 mg of twenty‐one international reference materials (RMs) of igneous rocks, and also one of a shale presented mostly satisfactory recoveries of forty‐one trace elements. Important exceptions were Zr and Hf in G‐2 and GSP‐2 (mean recoveries of ca. 70%), although for four other felsic rock RMs, the digestion was complete. For ultramafic rock RMs, we present Cr results that indicate quantitative dissolution of Cr‐bearing phases. We discuss the findings and conclude that advances in sample preparation of geological materials for instrumental analysis would benefit from a better understanding of how specific characteristics, such as composition and crystallinity of certain minerals, may affect their reactivity.     

敞口酸溶-电感耦合等离子体质谱法同时测定地质样品中45个元素

改进了三酸(HCl-HNO3-HF)或四酸(HCl-HNO3-HF-HClO4)溶矿对难溶元素分解不彻底及对易挥发元素测定结果不稳定的现象,建立了地质样品中15个稀土元素及其常规微量元素一次溶矿、一次测定的分析方法,提高了分析质量。采用HCl-HNO3-HF-HClO4-H2SO4混合酸一次分解样品,用50%的逆王水复溶提取后定容,以Rh为内标元素,三通在线进样方式,电感耦合等离子体质谱法同时测定地质样品中45个元素的含量。讨论了分解方法对易挥发元素、难溶元素的影响,对岩石标准物质(GBW07106)、水系沉积物标准物质(GBW07303)和土壤标准物质(GBW07429)的测定值与标准值相一致,方法精密度为0.03%～4.97%。方法准确度高,简单、快捷、实用。     

鄂尔多斯盆地延长组长7油层组碳酸质喷积岩初探

鄂尔多斯盆地延长组长7油层组黑色岩系中首次发现主要呈纹层状、脉状等顺层分布于油页岩或凝灰岩中的碳酸质岩浆—热液喷流型沉积岩（简称喷积岩）,具有重要的研究价值。通过野外露头和钻井取心观察,薄片鉴定,扫描电镜、电子探针、全岩元素分析等测试方法,对上述碳酸质喷积岩的岩石学、矿物学、地球化学以及与生烃母质关系特征进行了初探。结果显示,按物质来源、形成方式和结构构造可将长7油层组碳酸质喷积岩划分为碳酸质喷爆岩、碳酸质喷溢岩、碳酸质喷流岩三大类型,三者主量元素、微量元素、稀土元素等地球化学特征具有岩浆碳酸岩和热水沉积岩的双重特征,且与生烃母质的发育具有正相关性。因此,碳酸质喷积岩在鄂尔多斯盆地延长组长7油层组黑色岩系沉积期发育,且对长7油层组生烃研究具有重要的理论和实际意义。     

Improvements in Digestion Protocols for Trace Element and Isotope Determinations in Stream and Lake Sediment Reference Materials (JSd-1, JSd-2, JSd-3, JLk-1 and LKSD-1)

Total dissolution is a critical step in geochemical analysis. Despite the number of published protocols, this issue still draws attention for sediment samples, which are particularly difficult to dissolve due to the common occurrence and high abundance of refractory phases such as zircon. We present tests of different chemical digestion procedures carried out on reference materials (RM) of stream (JSd-1, JSd-2 and JSd-3) and lake (JLk-1 and LKSD-1) sediments from the Geological Survey of Japan (GSJ) and the Canadian Certified Reference Material Programme (CCRPM). We demonstrate that the fusion technique is not appropriate for our studies as not all elements of interest were recovered and blank levels were too high to permit further Sr and Pb isotopic composition measurements. Similarly, conventional HF+HNO₃ dissolution methods were not efficient enough for detrital samples. Our preferred method involved using high pressure Teflon® vessel bombs in association with HClO₄. This protocol ensured a complete dissolution of the powder, as well as a complete recovery of trace elements. Moreover, blank levels were sufficiently low that Sr or Pb isotope compositions could be measured from the same mother solution. We also tested the homogeneity of RM powders by performing tests on various amount of powder.     

缅甸铂族金属砂矿中的矿物种类

采用电子探针分析（ＥＰＭＡ），对缅甸铂族金属砂矿中的矿物种类进行了研究。物质组成研究查明：主要组合矿物是Ｐｔ、Ｉｒ、Ｏｓ、Ｒｕ的自然元素和金属互化物。主要矿物是自然铂矿、铁铂合金、钌铱锇矿、等轴锇铱矿和铱锇矿。次要及稀有矿物是铂族金属的硫化物、砷化物、包括（Ｒｈ、Ｐｄ、Ｐｔ）２Ａｓ和（Ｒｈ、Ｐｄ、Ｐｔ、Ｎｉ）２Ａｓ两种陌生矿物、锑化物，以及含铂族元素的Ｆｅ、Ｎｉ、Ｃｕ硫化物。     

Mn-oxide: a major source of easily mobilisable Co and Ni under reducing conditions in New Caledonia FerralsolsLes oxydes de Mn : une source majeure de Co et Ni facilement mobilisables en conditions réductrices dans les Ferralsols de Nouvelle-Calédonie

Chemical and bacterial reduction and dissolution of Fe and Mn-oxide and the concomitant solubilisation of Co and Ni were studied in a surface horizon of a New-Caledonia Ferralsol. Chemical extractions showed that Mn and Co were in a large part associated in Mn-oxides. The main part of Ni was associated with goethite, but a very small fraction was also associated with Mn-oxides. Anaerobic reducing bacterial activity was responsible for Fe solubilisation at a smaller extent than for Mn solubilisation and consequently for associated metal release. Submicroscopic investigations revealed the presence of a Mn-oxide containing Co, Ni and Al, close to a lithiophorite–asbolane mixed-layers Mn-oxide, which can be considered as a main source of easily available metals in this soil. To cite this article: C. Quantin et al., C. R. Geoscience 334 (2002) 273–278.