Improved Platinum-Group Element Extraction by NiS Fire Assay from Chromitite Ore Samples Using a Flux Containing Sodium Metaphosphate

Many chromite-rich rocks contain relatively high concentrations of the platinum-group elements (PGE). In many cases, the phases carrying PGE occur as either platinum-group minerals (PGM) or as base metal sulfides in solid solution in sulfides. In some cases, such as the UG-2 unit of the Bushveld Complex, the PGM are occluded inside chromite grains. Chromites are notably difficult to dissolve in most fluxes and if the chromite contains some PGM the possibility exists that not all the PGE will be recovered during fusion. In this work, shortcomings in published methods of analysis based on the nickel sulfide fire assay procedure were investigated and a new procedure developed based on the addition of sodium metaphosphate to the fusion mixture. Optimum composition of the fusion mixture was found to be 10 g sodium metaphosphate and 9 g silica to 10 g sample, 15 g sodium carbonate, 30 g lithium tetraborate, 7.5 g nickel and 4.5 g sulfur to achieve complete dissolution of chromite grains. The new flux mixture was evaluated by the analysis of reference material CHR-Pt+ (which is known to contain PGM inside chromite grains) and no undissolved chromite grains were found in the glassy slag. Analysis of the nickel sulfide beads from this fire assay using neutron activation analysis showed similar results for Rh and Ru when compared with published conventional true (or accepted) values, while Au, Ir, Os, Pd and Pt values determined here were 10 to 30% higher than the corresponding published conventional true values. It was concluded that the addition of sodium metaphosphate improved chromite dissolution in the flux and appears to improve PGE recovery.     

全新世长江泥沙堆积的时空分布及通量估算

利用长江中下游、河口及口外、浙-闽沿岸陆架6个主要沉积盆地的40个晚第四纪钻孔及其年代学数据和长江口外、陆架的浅地层剖面,计算了全新世不同阶段各沉积盆地的沉积速率,并进行了近7 000年来泥沙堆积通量的估算。研究发现全新世早期距今10 000年至8 000年间长江口下切古河谷是长江泥沙的主要堆积中心,沉积速率可高达15m/ka。随着海平面上升,全新世中期长江中下游也成为长江泥沙的重要沉积盆地,其中江汉盆地的沉积速率可达10m/ka。近2 000年来,口外、陆架的堆积呈明显增加趋势,反映长江中下游盆地和河口可容空间日益减小。根据沉积速率估算,距今7 000年来长江中下游堆积泥沙约13 074×108 t,同期水下三角洲和陆架的泥沙堆积量约为9 470×108 t。研究还发现全新世以来有两个异常低沉积速率时期：距今8000-7 000年期间上述各沉积盆地沉积速率均显著低,未见长江泥沙的沉积中心; 距今4 000-2 000 年期间长江口呈现低沉积速率。 这两次异常的原因推测与海平面、气候波动事件密切相关。     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Acid leaching of ash and coal: Time dependence and trace element occurrences

The leaching of coal and coal/asphaltite/wood-ashes in sulfuric acid (pH 1.0, 25 °C, S/L, 1:10) was studied as a function of time; acid consumption and extracted metal concentrations are presented. Whole coals consumed acid rapidly during the first few minutes, followed by slow acid consumption. Wood-, lignite-, and asphaltite-ashes consumed acid in two stages, the rapid phase extending < 30 min and the slow phase extended up to 10 days. The rapid phase was dominated by the dissolution of Ca, K and Mg ions for wood-ash, by Ca, Al and Mg ions for lignite-ash and Ca and Mg ions for asphaltite-ash. The sulfur concentration in solution and the concentrations of Ca, Fe, K, Mg, Na, P, Al and Mn in the aqueous phase verified the neutralizing capacity of the untreated ashes as well as the formation of insoluble sulfates in the residues. The slow phase kinetics differed for different fuels and exhibited leaching of several abundant elements—Fe, Al, K, Na and Mn. Trace elements (Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Th, U, V, Zn) sometimes required up to 32 h for maximal extraction from ashes. Suggestions are presented regarding the chemical nature of trace elements in the untreated coals and ashes and suitable residence times for economical industrial processes. We think it possible to combine bacteriological oxidation of sulfidic concentrates of acid leaching from ash of various qualities or even whole coals.     

Class distribution and locality in rural areas: an example from Gloucestershire

The analysis of rural social change has reached a point of somewhat saturated orthodoxy. Numerous studies over the last 20 years have served to reinforce a standard view that it is the ‘newcomer vs local’ conflict which lies at the heart of social and cultural changes in rural communities. Moreover, these broad categorisations have often been translated into class terms without due regard for the detailed circumstances of locality or intra-class fractions. This paper presents some evidence from an intensive study of 10 parishes in rural Gloucestershire, and seeks to provide a detailed background to the distribution of selected indicators of social change in that area. It focuses on the diversions and needs experienced by different social groups and suggests additional complexities to those recognised in traditional treatments of rural conflict.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

深水沉积层序特点及构成要素

本文在回顾当前国际上深水沉积研究热点的基础上,结合在墨西哥湾深水研究的成果系统描述了深水沉积的定义、形成机理、深水沉积层序及深水沉积构成要素的特点.深水沉积主要是在重力流作用下深水环境的沉积,主要形成于相对水平面下降和早期上升的时期,主要分布在低位体系域中.深水层序以凝缩段为边界,块状搬运沉积最早形成并直接位于层序界面上,其上被河道-天然堤沉积所覆盖.典型深水沉积的要素主要由河道、天然堤及越岸沉积、板状砂、块状搬运沉积等构成,这些沉积要素时空上有序地分布.深水河道是物源的主要通道和沉积的重要场所,从上游至下游河道弯曲度增加,能量逐渐减弱.侧向迁移明显,垂向上由富砂的顺直河道演化为相对富泥的弯曲河道.天然堤及越岸沉积以泥质为主,天然堤沿河道呈楔状分布,其近端砂岩含量高,地层厚且倾角较陡;远端砂岩含量低,地层薄且平缓,侧向连续性好但垂向连续性差.板状砂主要为深水扇前缘非限制性沉积,可分为块型和层型.块型侧向连续性好,同时垂向连通性高.层型侧向连续性好,垂向连通性差.块状搬运沉积主要是低水位期坡上沉积物失稳形成的各类滑塌体及碎屑流,其对下伏地层侵蚀明显,分布广泛,变形构造常见,可作为油气良好的封盖层.     

Geology of the Victor Kimberlite, Attawapiskat, Northern Ontario, Canada: cross-cutting and nested craters

The pipe shapes, infill and emplacement processes of the Attawapiskat kimberlites, including Victor, contrast with most of the southern African kimberlite pipes. The Attawapiskat kimberlite pipes are formed by an overall two-stage process of (1) pipe excavation without the development of a diatreme (sensu stricto) and (2) subsequent pipe infilling. The Victor kimberlite comprises two adjacent but separate pipes, Victor South and Victor North. The pipes are infilled with two contrasting textural types of kimberlite: pyroclastic and hypabyssal-like kimberlite. Victor South and much of Victor North are composed of pyroclastic spinel carbonate kimberlites, the main features of which are similar: clast-supported, discrete macrocrystal and phenocrystal olivine grains, pyroclastic juvenile lapilli, mantle-derived xenocrysts and minor country rock xenoliths are set in serpentine and carbonate matrices. These partly bedded, juvenile lapilli-bearing olivine tuffs appear to have been formed by subaerial fire-fountaining airfall processes.

The Victor South pipe has a simple bowl-like shape that flares from just below the basal sandstone of the sediments that overlie the basement. The sandstone is a known aquifer, suggesting that the crater excavation process was possibly phreatomagmatic. In contrast, the pipe shape and internal geology of Victor North are more complex. The northwestern part of the pipe is dominated by dark competent rocks, which resemble fresh hypabyssal kimberlite, but have unusual textures and are closely associated with pyroclastic juvenile lapilli tuffs and country rock breccias±volcaniclastic kimberlite. Current evidence suggests that the hypabyssal-like kimberlite is, in fact, not intrusive and that the northwestern part of Victor North represents an early-formed crater infilled with contrasting extrusive kimberlites and associated breccias. The remaining, main part of Victor North consists of two macroscopically similar, but petrographically distinct, pyroclastic kimberlites that have contrasting macrodiamond sample grades. The juvenile lapilli of each pyroclastic kimberlite can be distinguished only microscopically. The nature and relative modal proportion of primary olivine phenocrysts in the juvenile lapilli are different, indicating that they derive from different magma pulses, or phases of kimberlite, and thus represent separate eruptions. The initial excavation of a crater cross-cutting the earlier northwestern crater was followed by emplacement of phase (i), a low-grade olivine phenocryst-rich pyroclastic kimberlite, and the subsequent eruption of phase (ii), a high-grade olivine phenocryst-poor pyroclastic kimberlite, as two separate vents nested within the original phase (i) crater. The second eruption was accompanied by the formation of an intermediate mixed zone with moderate grade. Thus, the final pyroclastic pipe infill of the main part of the Victor North pipe appears to consist of at least three geological/macrodiamond grade zones.

In conclusion, the Victor kimberlite was formed by several eruptive events resulting in adjacent and cross-cutting craters that were infilled with either pyroclastic kimberlite or hypabyssal-like kimberlite, which is now interpreted to be of probable extrusive origin. Within the pyroclastic kimberlites of Victor North, there are two nested vents, a feature seldom documented in kimberlites elsewhere. This study highlights the meaningful role of kimberlite petrography in the evaluation of diamond deposits and provides further insight into kimberlite emplacement and volcanism.     

Multi‐stage Melting Processes of Ophiolitic Chromitites from Purang Peridotite,the Western Yarlung‐Zangbo Suture Zone,Tibet

The Purang ophiolite, which crops out over an area of about 600 km2 in the western Yarlung‐Zangbo suture zone, consists chiefly of mantle peridotite, pyroxenite and gabbro. The mantle peridotites are mostly harzburgite and minor lherzolite that locally host small pods of dunite. Some pyroxenite and gabbro veins of variable size occur in the peridotites, and most of them strike NW. On the basis of their mineral chemistry podiform chromitites are divided into high‐alumina (Cr# = 20‐60) (Cr# = 100*Cr/(Cr+Al)) and high‐chromium (Cr# = 60‐80) varieties (Thayer, 1970). Typically, only one type occurs in a given peridotite massif, although some ophiolites contain several massifs which can have different chromitite compositions. However, the Purang massif contains both high chrome and high alumina chromitites within a single mafic‐ultramafic body. Seven small, lenticular bodies of chromitite ore have been found in the harzburgite, with ore textures ranging from massive to disseminated to sparsely disseminated; no nodular ore has been observed. Individual ore bodies are 2‐6 m long, 0.5‐2 m wide and strike NW, parallel to the main structure of the ophiolite. Ore bodies 1 and 6 consist of Al‐rich chromitite (Cr# = 52‐55), whereas orebodies 2, 3, 4 and 5 are Cr‐rich varieties (Cr # = 63 to 89). In addition to magnesiochromite, all of the orebodies contain minor olivine, amphibole and serpentine. Mineral structures show that the peridotites experienced plastic deformation and partial melting. On the basis of magnesiochromite and olivine/clinopyroxene compositions two stages of partial melting are identified in the Purang peridotites, an early low‐partial melting event (about 8%), and a later high‐partial melting event (about 40%). We interpret the Al‐rich chromitites as the products of early MORB magmas, whereas the Cr‐rich varieties are thought to have been generated by the later SSZ melts..     

Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH

Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 μmol/m² on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom exchange process appears to be a significant subsystem within macroscopic pH-dependent Fe(II) adsorption.