Platinum group minerals in podiform chromitites of the Bou Azzer ophiolite, Anti Atlas, Central Morocco

Summary The Neoproterozoic Bou Azzer ophiolite complex hosts numerous, small lenticular bodies of massive and disseminated chromite. Metallurgical-grade high-Mg and high-Cr spinels (cores with 48–62 wt% Cr₂O₃) reveal complex alteration patterns of successive Cr and Mn enrichment and loss of Al towards the rims, while the Mg# ratios [(Mg/(Mg + Fe²⁺)] remain almost constant. Concentration patterns of platinum-group elements are typical for ophiolitic chromitite poor in sulfides, with predominance of the IPGE, variable Rh, and low Pt and Pd. The most abundant platinum-group mineral is Rh-bearing laurite that occurs either included in spinel or in silicate matrix, whereas Os-Ir-Ru alloy is always included in spinel. Laurite inclusions reveal complex intergrowth textures with Rh-Ru-Pt rich alloy, and with Rh-rich sulfide. Most laurites display trends to sulfur-poor compositions leading to local formation of very fine-grained Ru-Os-Ir alloy phases. Ni-Co-Fe sulfides, arsenides and sulfarsenides devoid of PGE are associated with the alteration of chromite. Textural position and chemical composition of the base metal inclusions, as well as comparison of alteration features between chromite and accessory chromian spinel in the Co-Ni-As ores of the Bou Azzer ophiolite indicate a close connection. It is suggested that hydrothermal fluids percolated through the marginal zones of the ophiolite belt during greenschist facies metamorphism and deposited Ni-Co-Fe arsenides, sulfarsenides and minor sulfides as accessories within altered chromitites, and also in structurally favourable zones as Ni-Co-As ores. Author’s address: Dr. Frank Melcher, Federal Institute for Geosciences and Natural Resources, Stilleweg 2, 30655 Hannover, Germany     

Pretreatment of high strength waste emulsions by combined vibratory shear enhanced process with Fenton oxidation

Pretreatment of waste emulsions with high organic content by a combined process of vibratory shear enhanced process and Fenton’s oxidation prior to biological treatment was investigated. Vibrating membrane had shown good performance in chemical oxygen demand and oil removals and the mitigation of concentration polarization. However, the permeate after filtration processing still contained high content of organics. Thus, additional Fenton oxidation was applied to reduce the organic loading, and improve the biodegradability of the wastewater. The optimal molar ratio of ferrous iron to hydrogen peroxide was 0.05 obtained from the jar-test experiments. Removal of organics was enhanced by increasing hydrogen peroxide dosage, while efficiency of hydrogen peroxide reached maximum of 1.11(w/w) at the hydrogen peroxide dosage of 6.8 g/L. Furthermore, the biological experiments indicated that the high concentration of organics could inhibit microbial activity, which decreased the chemical oxygen demand degradation rates. The adaptive period of the microbe was greatly shortened using Fenton’s reagent at the low dosages. The improvement of the biodegradability could be explained by partial mineralization and chemical transformation of parent organic compounds after Fenton oxidation.     

Lu–Hf and U–Pb isotope systematics of zircons from the Storgangen intrusion, Rogaland Intrusive Complex, SW Norway: implications for the composition and evolution of Precambrian lower crust in the Baltic Shield

The Storgangen orebody is a concordantly layered, sill-like body of ilmenite-rich norite, intruding anorthosites of the Rogaland Intrusive Complex (RIC), SW Norway. 17 zircon grains were separated from ca. 5 kg of sand-size flotation waste collected from the on-site repository from ilmenite mining. These zircons were analysed for major and trace elements by electron microprobe, and for U–Pb and Lu–Hf isotopes by laser ablation microprobe plasma source mass spectrometry. Eight of the zircons define a well-constrained (MSWD=0.37) concordant population with an age of 949±7 Ma, which is significantly older than the 920–930 Ma ages previously reported for zircon inclusions in orthopyroxene megacrysts from the RIC. The remaining zircons, interpreted as inherited grains, show a range of ²⁰⁷Pb/²⁰⁶Pb ages up to 1407±14 Ma, with an upper intercept age at ca. 1520 Ma. The concordant zircons have similar trace element patterns, and a mean initial Hf isotope composition of ¹⁷⁶Hf/¹⁷⁷Hf_{949 Ma}=0.28223±5 (_Hf=+2±2). This is similar to the Hf-isotope composition of zircons in a range of post-tectonic Sveconorwegian granites from South Norway, and slightly more radiogenic than expected for mid-Proterozoic juvenile crust. The older, inherited zircons show Lu–Hf crustal residence ages in the range 1.85–2.04 Ga. One (undated) zircon plots well within the field of Hf isotope evolution of Paleoproterozoic rocks of the Baltic Shield. These findings indicate the presence of Paleoproterozoic components in the deep crust of the Rogaland area, but do not demonstrate that such rocks, or a Sveconorwegian mantle-derived component, contributed significantly to the petrogenesis of the RIC. If the parent magma was derived from a homogeneous, lower crustal mafic granulite source, the lower crustal protolith must be at least 1.5 Ga old, and it must have an elevated Rb/Sr ratio. This component would be indistinguishable in Sr, Nd and Hf isotopes from some intermediate mixtures between Sveconorwegian mantle and Paleoprotoerzoic felsic crust, but it cannot account for the initial ¹⁴³Nd/¹⁴⁴Nd of the most primitive, late Sveconorwegian granite in the region, without the addition of mantle-derived material.     

Accumulation and Post-Sedimentary Diagenesis of Tonsteins

The work is devoted to specific features of sedimentogenesis and multistage alterations of eolian volcanic ash and epiclastic clay in paleopeat bogs and their transformation into ortho- and paratonsteins, respectively. The hydrolysis of aluminosilicate minerals and volcanic glass and their alteration into monotonous submonomineral clay, which is compositionally similar to epiclastic clay, is associated with the diagenesis stage. During the catagenesis, submonomineral clay is lithified and transformed into tonsteins, which undergo recrystallization as the temperature increases. Clay minerals are replaced by illite and chlorite, while tonsteins are transformed into metatonsteins. Paragenetic relationships of clay minerals are discussed.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Composition of sand storm particles in the Southern Far East

Lithostructural composition of the dust storm material (DMS) sampled in the southern Far East in the spring of 2002–2004 has been analyzed. Samples were taken near Vladivostok, where the eolian dust precipitation varied from 0.1 to 6.5 g/m² at that time. Pelitic and fine-silt particles predominate in eolian dust. Grain size, mineral, and chemical compositions of the DSM are compared to data on the DSM in adjacent territories of China, Korea, and Japan, as well as to background data on aerosol precipitation in southern Primorye. Possible mechanisms of the eolian dust transport from inner parts of Asia at different climatic variations in the Pleistocene-Holocene are discussed.     

Eclogite and carpholite-bearing metasedimentary rocks in the North Qilian suture zone, NW China: implications for Early Palaeozoic cold oceanic subduction and water transport into mantle

Low‐temperature eclogite and eclogite facies metapelite together with serpentinite and marble occur as blocks within foliated blueschist that was originated from greywacke matrix; they formed a high‐pressure low‐temperature (HPLT) subduction complex (mélange) in the North Qilian oceanic‐type suture zone, NW China. Phengite–eclogite (type I) and epidote–eclogite (type II) were recognized on the basis of mineral assemblage. Relic lawsonite and lawsonite pseudomorphs occur as inclusions in garnet from both types of eclogite. Garnet–omphacite–phengite geothermobarometry yields metamorphic conditions of 460–510 °C and 2.20–2.60 GPa for weakly deformed eclogite, and 475–500 °C and 1.75–1.95 GPa for strongly foliated eclogite. Eclogite facies metasediments include garnet–omphacite–phengite–glaucophane schist and various chloritoid‐bearing schists. Mg‐carpholite was identified in some high‐Mg chloritoid schists. P–T estimates yield 2.60–2.15 GPa and 495–540 °C for Grt–Omp–Phn–Gln schist, and 2.45–2.50 GPa and 525–530 °C for the Mg‐carpholite schist. Mineral assemblages and P–T estimates, together with isotopic ages, suggest that the oceanic lithosphere as well as pelagic to semi‐pelagic sediments have been subducted to the mantle depths (≥75 km) before 460 Ma. Blueschist facies retrogression occurred at c. 454–446 Ma and led to eclogite deformation and dehydration of lawsonite during exhumation. The peak P–Tconditions for eclogite and metapelite in the North Qilian suture zone demonstrate the existence of cold subduction‐zone gradients (6–7 °C km^?1), and this cold subduction brought a large amount of H₂O to the deep mantle in the Early Palaeozoic times.     

Timing and setting of skarn and iron oxide formation at the Smältarmossen calcic iron skarn deposit, Bergslagen, Sweden

Abundant iron oxide deposits including banded iron formations, apatite iron oxide ores, and enigmatic marble/skarn-hosted magnetite deposits occur in the Palaeoproterozoic Bergslagen region, southern Sweden. During the last 100 years, the latter deposit class has been interpreted as contact metasomatic skarn deposits, metamorphosed iron formations, or metamorphosed carbonate replacement deposits. Their origin is still incompletely understood. At the Smältarmossen mine, magnetite was mined from a ca. 50-m-thick calcic skarn zone at the contact between rhyolite and stratigraphically overlying limestone. A syn-volcanic dacite porphyry which intruded the footwall has numerous apophyses that extend into the mineralized zone. Whole-rock lithogeochemical and mineral chemical analyses combined with textural analysis suggests that the skarns formed by veining and replacement of the dacite porphyry and rhyolite. These rocks were added substantial Ca and Fe, minor Mg, Mn, and LREE, as well as trace Co, Sn, U, As, and Sr. In contrast, massive magnetite formed by pervasive replacement of limestone. Tectonic fabrics in magnetite and skarn are consistent with ore formation before or early during Svecokarelian ductile deformation. Whereas a syngenetic–exhalative model has previously been suggested, our results are more compatible with magnetite formation at ca. 1.89 Ga in a contact metasomatic skarn setting associated with the dacite porphyry.     

The Taihua group on the southern margin of the North China craton: further insights from U–Pb ages and Hf isotope compositions of zircons

The "Taihua Group" is a collective term for a series of old terranes scattered along the southern margin of the North China Craton. The timing of formation and thermal overprinting of the Taihua Group have long been contentious, and its relationship with the Qinling orogenic belt has been unclear. In this study, new data from integrated in-situ U–Pb dating and Hf isotope analysis of zircons from an amphibolite (from the Xiong’ershan terrane) and a biotite gneiss (from the Lantian-Xiaoqinling terrane) indicate that the Upper Taihua Group formed during the Paleoproterozoic (2.3–2.5 Ga) and thus was originally part of the southern edge of North China Craton, detached during the Mesozoic Qinling orogeny and displaced about 100 km north from its original location. This suggests that the Taihua Group became part of the tectonic terrane associated with the Qinling orogeny and now forms part of the overthrust basement section of the Qinling belt. Before the Qinling orogeny, the Taihua Group was metamorphosed at 2.1 Ga. The initial Hf-isotope compositions of zircons, together with positive εNd(t) values for the whole-rocks, imply that the original magmas were derived from a juvenile source with some assimilation of an Archean crustal component.     

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.