Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO₃ solution, suspension density = 0.4 g/L [U(VI)]_i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (p_CO2 = 10^−3.45 atm).     

Origin of fine‐grained peridotite xenoliths from Iraya volcano of Batan Island,Philippines: deserpentinization or metasomatism at the wedge mantle beneath an incipient arc?

Abstract Peridotite xenoliths from the subarc mantle, which have been rarely documented, are described from Iraya volcano of the Luzon arc, the Philippines, and are discussed in the context of wedge-mantle processes. They are mainly harzburgite, with subordinate dunite, and show various textures from weakly porphyroclastic (C-type) to extremely fine-grained equigranular (F-type). Textural characteristics indicate a transition from the former to the latter by recrystallization. The F-type peridotite has inclusion-rich fine-grained olivine and radially aggregated orthopyroxene, being quite different in texture from ordinary mantle-derived peridotites previously documented. Despite their strong textural contrast, the two types do not show any systematic difference in modal composition. The harzburgite of C-type has ordinary mantle peridotite mineralogy; olivine is mostly Fo91–92 and chromian spinel mostly has Cr#s (= Cr/[Cr + Al] atomic ratios) from 0.3 to 0.6. Olivine is slightly more Fe-rich (Fo89–91) and spinel is more enriched in Cr (the Cr#, 0.4–0.8) and Fe³⁺ in F-type peridotites than in C-type harzburgite. Orthopyroxene in F-type peridotites is relatively low in CaO (<1 wt%), Al₂O₃ (<2 wt%) and Cr₂O₃ (<0.4 wt%). The F-type peridotite was possibly formed from the C-type one by recrystallization including local dissolution and precipitation of orthopyroxene assisted by fluid (or melt) of subduction origin. Textural characteristics, however, indicate a deserpentinization origin from abyssal serpentinite of which protolith was a C-type peridotite. In this scenario the initial abyssal serpentinite was possibly dehydrated due to an initiation of magmatic activity beneath an incipient oceanic arc like Batan Island. The F-type peridotite is characteristic of the upper mantle of island arc, especially of incipient arc.     

Geochemistry of spinel-hosted amphibole inclusions in abyssal peridotite: insight into secondary melt formation in melt–peridotite reaction

Spinel-hosted hydrous silicate mineral inclusions are often observed in dunite and troctolite as well as chromitite. Their origin has been expected as products associated with melt–peridotite reaction, based on the host rock origin. However, the systematics in mineralogical and geochemical features are not yet investigated totally. In this study, we report geochemical variations of the spinel-hosted pargasite inclusions in reacted harzburgite and olivine-rich troctolite collected from Atlantis Massif, an oceanic core complex, in the Mid-Atlantic Ridge. The studied samples are a good example to examine geochemical variations in the inclusions because the origin and geological background of the host rocks have been well constrained, such as the reaction between MORB melt and depleted residual harzburgite beneath the mid-ocean ridge spreading center. The trace-element compositions of the pargasite inclusions are characterized by not only high abundance of incompatible elements but also the LREE and HFSE enrichments. Distinctive trace-element partitioning between the pargasite inclusion and the host-rock clinopyroxene supports that the secondary melt instantaneously formed by the reaction is trapped in spinel and produces inclusion minerals. While the pargasite geochemical features can be interpreted by modal change reaction of residual harzburgite, such as combination of orthopyroxene decomposition and olivine precipitation, degree of the LREE enrichment as well as variation of HREE abundance is controlled by melt/rock ratio in the reaction. The spinel-hosted hydrous inclusion could be embedded evidence indicating melt–peridotite reaction even if reaction signatures in the host rock were hidden by other consequent reactions.     

Restoration of Exotic Terranes Along the Median Tectonic Line, Japanese Islands: Overview

This paper reviews recent progress on the geotectonic evolution of exotic Paleozoic terranes in Southwest Japan, namely the Paleo-Ryoke and Kurosegawa terranes. The Paleo-Ryoke Terrane is composed mainly of Permian granitic rocks with hornfels, mid-Cretaceous high-grade metamorphic rocks associated with granitic rocks, and Upper Cretaceous sedimentary cover. They form nappe structures on the Sambagawa metamorphic rocks. The Permian granitic rocks are correlative with granitic clasts in Permian conglomerates in the South Kitakami Terrane, whereas the mid-Cretaceous rocks are correlative with those in the Abukuma Terrane. This correlation suggests that the elements of Northeast Japan to the northeast of the Tanakura Tectonic Line were connected in between the paired metamorphic belt along the Median Tectonic Line, Southwest Japan. The Kurosegawa Terrane is composed of various Paleozoic rocks with serpentinite and occurs as disrupted bodies bounded by faults in the middle part of the Jurassic Chichibu Terrane accretionary complex. It is correlated with the South Kitakami Terrane in Northeast Japan. The constituents of both terranes are considered to have been originally distributed more closely and overlay the Jurassic accretionary terrane as nappes. The current sporadic occurrence of these terranes can possibly be attributed to the difference in erosion level and later stage depression or transtension along strike-slip faults. The constituents of both exotic terranes, especially the Ordovician granite in the Kurosegawa-South Kitakami Terrane and the Permian granite in the Paleo-Ryoke Terrane provide a significant key to reconstructing these exotic terranes by correlating them with Paleozoic granitoids in the eastern Asia continent.     

Permian Peri‐glacial Deposits from Central Mongolia in Central Asian Orogenic Belt: A Possible Indicator of the Capitanian Cooling Event

A dropstone‐bearing, Middle Permian to Early Triassic peri‐glacial sedimentary unit was first discovered from the Khangai–Khentei Belt in Mongolia, Central Asian Orogenic Belt. The unit, Urmegtei Formation, is assumed to cover the early Carboniferous Khangai–Khentei accretionary complex, and is an upward‐fining sequence, consisting of conglomerates, sandstones, and varved sandstone and mudstone beds with granite dropstones in ascending order. The formation was cut by a felsic dike, and was deformed and metamorphosed together with the felsic dike. An undeformed porphyritic granite batholith finally cut all the deformed and metamorphosed rocks. LA‐ICP‐MS, U–Pb zircon dating has revealed the following ²⁰⁶Pb/²³⁸U weighted mean igneous ages: (i) a granite dropstone in the Urmegtei Formation is 273 ± 5 Ma (Kungurian of Early Permian); (ii) the deformed felsic dike is 247 ± 4 Ma (Olenekian of Early Triassic); and (iii) the undeformed granite batholith is 218 ± 9 Ma (Carnian of Late Triassic). From these data, the age of sedimentation of the Urmegtei Formation is constrained between the Kungurian and the Olenekian (273–247 Ma), and the age of deformation and metamorphism is constrained between the Olenekian and the Carnian (247–218 Ma). In Permian and Triassic times, the global climate was in a warming trend from the Serpukhovian (early Late Carboniferous) to the Kungurian long and severe cool mode (328–271 Ma) to the Roadian to Bajocian (Middle Jurassic) warm mode (271–168 Ma), with an interruption with the Capitanian Kamura cooling event (266–260 Ma). The dropstone‐bearing strata of the Urmegtei Formation, together with the glacier‐related deposits in the Verkhoyansk, Kolyma, and Omolon areas of northeastern Siberia (said to be of Middle to Late Permian age), must be products of the Capitanian cooling event. Although further study is needed, the dropstone‐bearing strata we found can be explained in two ways: (i) the Urmegtei Formation is an autochthonous formation indicating a short‐term expansion of land glacier to the central part of Siberia in Capitanian age; or (ii) the Urmegtei Formation was deposited in or around a limited ice‐covered continent in northeast Siberia in the Capitanian and was displaced to the present position by the Carnian.     

Silica enrichment of Group II xenoliths by evolved alkali basalt from Jeju Island, South Korea: implication for modification of intraplate deep-seated rocks

Group II xenoliths, corresponding to the lithology of dunite, wehrlite to olivine clinopyroxenite and olivine websterite to websterite, occur in Pleisto-Holocene alkali basalts from Jeju Island, South Korea. The large grain size (up to 5?mm), moderate mg# [=100?×?Mg/(Mg?+?Fe_total) atomic ratio] of olivine (79–82) and pyroxenes (77–83), and absence of metamorphic textural features indicate that they are cumulates of igneous origin. Based on textural features, mineral equilibria and major and trace element variations, it can be inferred that the studied xenoliths were crystallized from basaltic melts enriched in incompatible trace elements and belong to the Jeju Pleisto-Holocene magma system. They appear to have been emplaced near the present Moho, an estimated 5–8?kbars beneath Jeju Island. Consolidation of cumulates was followed by infiltration of silica-enriched metasomatic melt, producing secondary orthopyroxenes at the expense of olivine. The metasomatic agent appears to have been a silica-enriched residual melt evolved from an initially slightly silica-undersaturated alkali basalt to silica-saturated compositions by fractional crystallization under relatively high pressure conditions. The result of this study indicates that relatively young olivine-bearing cumulates could have been metasomatized by a silica-enriched melt within underplates, suggesting that silica enrichment can occur in intraplate Moho-related rocks as well as in the upper mantle of the subarc area.     

Origin of wehrlite cumulates in the Moho transition zone of the Neoproterozoic Ras Salatit ophiolite,Central Eastern Desert,Egypt: crustal wehrlites with typical mantle characteristics

Ultramafic cumulates, mainly crustal true wehrlites, were discovered and described in the mantle–crust transition zone (MTZ) and the extremely lower layered gabbro sequence of the Ras Salatit ophiolite, Central Eastern Desert, Egypt. They form either boudinaged lensoidal tabular bodies or interdigitated layers often concordant with the planolinear fabrics of the Ras Salatit ophiolite rocks. The contact between wehrlites and the host MTZ dunite or layered gabbro is razor sharp, lobate and/or sinuous, without chilled margins or any visible deformations. The Ras Salatit wehrlites are orthopyroxene-free and composed mainly of olivine and clinopyroxene. They are texturally equilibrated and show a characteristic poikilitic texture. Crystallization order of the Ras Salatit wehrlites is olivine/spinel followed by clinopyroxene with the absence of plagioclase. Olivine and clinopyroxene of the Ras Salatit wehrlites are compositionally uniform and conspicuously high in Mg#, mostly around 0.93 and 0.92, respectively. Moreover, the clinopyroxene shows low Ti and Al contents coupled with marked depletion in LILE. The calculated melt in equilibrium with clinopyroxene from the Ras Salatit wehrlites is largely similar to lavas from the Izu-Bonin forearc. Given the above characteristics, the Ras Salatit wehrlites were produced by crystal accumulation from a hydrous depleted basaltic/tholeiitic melt corresponding to temperatures between 1,000 and 1,100°C at the oceanic crustal pressure (~2 kbar). The involved hydrous tholeiitic melt has been probably formed by fluid-assisted partial melting of a refractory mantle source (similar to the underlying harzburgites) in a somewhat shallow sub-arc environment.     

Structural changes of synthetic opal by heat treatment

The structural changes of synthetic opal by heat treatment up to 1,400 °C were investigated using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared and Raman spectroscopies. The results indicate that the dehydration and condensation of silanol in opal are very important factors in the structural evolution of heat-treated synthetic opal. Synthetic opal releases water molecules and silanols by heat treatment up to 400 °C, where the dehydration of silanol may lead to the condensation of a new Si–O–Si network comprising a four-membered ring structure of SiO₄ tetrahedra, even at 400 °C. Above 600 °C, water molecules are lost and the opal surface and internal silanol molecules are completely dehydrated by heat effect, and the medium-temperature range structure of opal may begin to thermally reconstruct to six-membered rings of SiO₄ tetrahedra. Above 1,000 °C, the opal structure almost approaches that of silica glass with an average structure of six-membered rings. Above 1,200 °C, the opal changes to low-cristobalite; however, minor evidence of low-tridymite stacking was evident after heat treatment at 1,400 °C.     

Potential of Oil Palm Trunk Sap as a Novel Inexpensive Renewable Carbon Feedstock for Polyhydroxyalkanoate Biosynthesis and as a Bacterial Growth Medium

Utilization of cheap renewable carbon feedstock for polyhydroxyalkanoate (PHA) production not only brings down its production cost but also ensures sustainability. The scope of this study was to evaluate the potential of sap extracted from felled oil palm trunk (OPT) as a novel inexpensive renewable carbon source for PHA production. OPT sap was found to be nutritionally rich and contained various fermentable sugars (5.5% w/v) as its major constituent. Termite gut isolate, Bacillus megaterium MC1 grew profoundly in mineral medium with OPT sap as carbon source and a cell density of 10.9 g/L was attained after 16 h of cultivation in shake flask cultures. A maximum poly‐3‐hydroxybutyrate [P(3HB)] content (% cell dry weight; CDW) of 30 wt% and a P(3HB) concentration of 3.28 g/L was recorded. Additionally, OPT sap extracted from younger tree trunks with prolonged storage had higher sugar content (10.8% w/v) and, when used as a growth medium without the addition of any nutrients, supported bacterial growth comparable to commercially available media.