Silica Enrichment Research Articles

Microanalytical approaches on the silicification process of wood fossil from Jasinga, West Java, Indonesia

Worldwide, silicified woods are found in many geological formations. Significantly, the organic materials of wood are no longer dominant; almost all wood fossils have been mineralized into inorganic silica materials. These unique geological processes must be understood to develop better understanding on organic material fossilization, particularly in the micron scale. Therefore, our aim was to characterize the composition of silicified wood using comprehensive microanalysis. The methods utilized were XRF, ICP-MS, XRD, FTIR, and FE-EPMA. Specimens are from Jasinga, West Java, Indonesia. The results showed that wood silicification was controlled by the infiltration of silica from the host rock into the spaces of the wood structure. In Jasinga, they are controlled by Pliocene tuffaceous sedimentary rocks. The ratio of silica phases revealed a trend in the degree of silicification. Besides silica, the distribution of trace elements also demonstrates the geochemical interaction between the wood fossil and host rock. Wood fossils are affected by the gradual replacement of organic carbon-based materials with silica through silicification. Silica enrichment occurs in the internal of wood, facilitates permineralization and recrystallization. Silica replaces organic material and preserves the wood structures. The microanalytical approach provides comprehensive perspectives on wood petrification, leads to better insights for paleontological studies.

In-Depth Endogenous Phosphopeptidomics of Serum with Zirconium(IV)-Grafted Mesoporous Silica Enrichment.

Detection of endogenous peptides, especially those with modifications (such as phosphorylation) in biofluids, can serve as an indicator of intracellular pathophysiology. Although great progress has been made in phosphoproteomics in recent years, endogenous phosphopeptidomics has largely lagged behind. One main hurdle in endogenous phosphopeptidomics analysis is the coexistence of proteins and highly abundant nonmodified peptides in complex matrices. In this study, we developed an approach using zirconium(IV)-grafted mesoporous beads to enrich phosphopeptides, followed by analysis with a high resolution nanoRPLC-MS/MS system. The bifunctional material was first tested with digests of standard phosphoproteins and HeLa cell lysates, with excellent enrichment performance achieved. Given the size exclusion nature, the beads were directly applied for endogenous phosphopeptidomic analysis of serum samples from pancreatic ductal adenocarcinoma (PDAC) patients and controls. In total, 329 endogenous phosphopeptides (containing 113 high confidence sites) were identified across samples, by far the largest endogenous phosphopeptide data set cataloged to date. In addition, the method was readily applied for phosphoproteomics of the same set of samples, with 172 phosphopeptides identified and significant changes in dozens of phosphopeptides observed. Given the simplicity and robustness of the proposed method, we envision that it can be readily used for comprehensive phosphorylation studies of serum and other biofluid samples.

Full-waveform tomography reveals iron spin crossover in Earth’s lower mantle

Three-dimensional models of Earth’s seismic structure can be used to identify temperature-dependent phenomena, including mineralogical phase and spin transformations, that are obscured in 1-D spherical averages. Full-waveform tomography maps seismic wave-speeds inside the Earth in three dimensions, at a higher resolution than classical methods. By providing absolute wave speeds (rather than perturbations) and simultaneously constraining bulk and shear wave speeds over the same frequency range, it becomes feasible to distinguish variations in temperature from changes in composition or spin state. We present a quantitative joint interpretation of bulk and shear wave speeds in the lower mantle, using a recently published full-waveform tomography model. At all depths the diversity of wave speeds cannot be explained by an isochemical mantle. Between 1000 and 2500 km depth, hypothetical mantle models containing an electronic spin crossover in ferropericlase provide a significantly better fit to the wave-speed distributions, as well as more realistic temperatures and silica contents, than models without a spin crossover. Below 2500 km, wave speed distributions are explained by an enrichment in silica towards the core-mantle boundary. This silica enrichment may represent the fractionated remains of an ancient basal magma ocean.

Upwelling-driven biogenic silica accumulation in the Yangtze Sea, South China during Late Ordovician to Early Silurian time: A possible link with the global climatic transitions

Silica accumulation in the Yangtze Sea during the Ordovician–Silurian (O–S) transition appears to have coincided with global climatic fluctuations, widespread upwelling, and volcanism. There is a need to further evaluate their respective contributions to silica deposition and potential relationships among these factors. The current study selected siliceous deposits in the Wufeng and Longmaxi Formations from four sections spanning the inner to outer Yangtze Sea, South China, to gain a deeper understanding of the climatic and oceanographic evolution associated with silica enrichment. Al/(Al + Fe + Mn) values, the presence of radiolarians, and Si isotope values of samples recovered from the investigated shale successions offer compelling evidence that the silica is largely of biogenic origin with some terrigenous contributions. Further, various productivity and redox proxies suggest that biogenic silica (BSi) accumulated under conditions of enhanced marine productivity and anoxic bottom water conditions. Hg/TOC and Zr/Al2O3 profiles suggest intermittent volcanism during the BSi deposition in the Yangtze Sea. However, the lack of correlation between BSi and Hg/TOC values indicates that volcanic iron fertilization was not responsible for BSi accumulation. Instead, most BSi-rich samples are dominated by low MnEF × CoEF values (<0.5), consistent with BSi deposited in modern upwelling settings. Hydrographic reconstruction based on Mo–U covariation indicates a more open water setting in the outer Yangtze Sea, while the coeval inner Yangtze Sea was relatively restricted. Therefore, upwelling events appear to have been more vigorous in the outer Yangtze Sea. Published and new Chemical Index of Alteration (CIA), BSi, and MnEF × CoEF data for the Wufeng and Longmaxi Formations across the inner to outer Yangtze Sea demonstrate that temporal and spatial variations of BSi were controlled by climate-driven upwelling. In particular, cool-water upwelling contemporaneous with Hirnantian glaciation may have been responsible for the establishment of the cool-water fauna of the shallow-water Guanyinqiao Bed and enhanced silica deposition in deeper water. Moreover, a moderate negative relationship between compiled CIA and BSi contents suggests that enhanced upwelling driving BSi accumulation appears to have been favored during cooling events. Integrated analysis of BSi deposits of the Laurentia and Baltica continental margins further suggests that BSi accumulation on continental margins during the O–S transition was primarily influenced by global cooling. Therefore, we suggest that wind patterns or/and thermohaline circulation, influenced by climate fluctuations, induced widespread cold water upwelling events during the O–S transition. Moreover, elevated BSi production diluted accumulating OM resulting in the observed parabolic relationship of BSi and TOC.

Lithospheric underthrusting beneath the northern Eastern Cordillera plateau, Colombian Andes: Insights from analyzing tomographic inversion using local earthquake travel time and gravity data

The northern Eastern Cordillera in the Colombian Andes is a wide (~200 km) high-elevation (>2.5 km) subduction-related asymmetric plateau. This plateau is currently subjected to shortening and magmatic addition, and yet the nature of the lowermost crust and its transition to the underlying mantle remains poorly constrained. To improve our knowledge about the structure of the deep crust beneath the EC plateau, we conducted a joint inversion of travel times of local earthquakes and gravity data. Gravity contributes to up to 0.5% in dVp and dVs with no affectation of the shape or location of the discussed anomalies. Along the latitudinal profile with the highest resolution (~5.7°N), two anomalies are identified at depths of 40–60 km beneath the plateau. A western low-velocity anomaly is interpreted as crustal material underthrust eastward beneath the northwestern EC. This process is triggering the abrupt change in topography between the adjacent low-elevation basin and the orogenic plateau. Additionally, a high-velocity anomaly beneath the eastern flank of the EC is likely related to mantle metasomatism and westward underthrusting of the foreland lithosphere. This metasomatism is either related to the interaction between mafic magmas and the uppermost mantle or silica enrichment that occurred during a past episode of flat subduction. Evidence for foreland underthrusting includes relocated earthquakes at 33–42 km depth within the thrust system between the EC and the foreland, along with increased shortening in the eastern part of the plateau, an increase in exhumation rates, the eastward migration of deformation towards the foreland, and dominated thick-skinned deformation in the upper crust of the foreland with an eastward vergence of thrusts and related folds. Furthermore, within the central part of the plateau, our results show low velocities between 30 and 40 km depth, consistent with previous constraints, suggesting magmatic underplating beneath the Paipa-Iza volcanic complex.

Probing the deep mantle wedge in an active subduction zone: Xenoliths from the Mercaderes Volcanic District, Southern Colombia

In subduction zones, the mantle wedge is the domain where liquid phases released by the oceanic subducting plates cause mantle hydration, metasomatism, and partial melting, producting the arc crust. However, direct petrologic information on mantle wedges overlying active subduction zones remains scarce. Here we constrain key aspects of the petrological evolution of the supra-subduction mantle underneath the active volcanic district of Southern Colombia (Mercaderes) by studying a unique suite of peridotite and pyroxenite xenoliths hosted by andesites and lamprophyres. These garnet-bearing peridotite, websterite, clino- and orthopyroxenite xenoliths equilibrated between 2.5 and 4 GPa and 1100–1200 °C. The studied rocks display considerable heterogeneity in terms of lithotypes, textures, mineral abundance and extent of metasomatic overprint. Most samples display fine-grained mylonitic textures overprinting coarse-grained peridotite and garnet pyroxenite precursors; the EBSD study of undeformed garnet websterite samples suggests crystallization from melts and/or melt-rock reaction processes. Modal enrichment in clinopyroxene as well as in the alkalis and LREE contents in some garnet peridotite implies interaction with alkaline basaltic melts, whereas enrichment in silica, Pb and Sr in the garnet-bearing orthopyroxenites records interaction with metasomatic, slab-derived liquids. Some garnet clinopyroxenite xenoliths display marked positive Sr anomalies and minor Eu anomalies, indicating derivation of these rocks from Mg-rich, plagioclase-bearing (and garnet-absent) low-pressure cumulates. Their equilibration in the garnet field implies that after crystallization these clinopyroxenites were transported to deeper levels in the mantle, as the result of foundering into the mantle of the dense arc roots, as already documented in Mercaderes and elsewhere in the Andes. In conclusion, the Mercaderes xenoliths probe a heterogeneous and chemically active domain of the Colombian mantle wedge, where deep sinking lower crustal rocks, melt metasomatism by distinct venues of chemically different melts, and deformation predate fast exhumation by volatile-rich melts.

Integration of Whole-Rock Geochemistry and Mineral Chemistry Data for the Petrogenesis of A-Type Ring Complex from Gebel El Bakriyah Area, Egypt

El Bakriyah Ring Complex (BRC) is a prominent Neoproterozoic post-collisional granite suite in the southern part of the Central Eastern Desert of Egypt. The BRC bears critical materials (F, B, Nb, and Ta) in appreciable amounts either in the form of rare-metals dissemination or in the form of fluorite and barite vein mineralization. The complex consists of inner syenogranite and outer alkali feldspar granite that have been emplaced in a Pan-African assemblage made up of granitic country rocks (granodiorite and monzogranite), in addition to post-collisional fresh gabbro as a part of the Arabian-Nubian Shield (ANS) in northeast Africa. Granites of the BRC are characterized by enrichment in silica, alkalis, Rb, Y, Ga, Nb, Ta, Th, and U and depletion in Sr, Ba, and Ti. Geochemical characterization of the BRC indicates that the magma is a crustal melt, which originated from the partial melting of metasedimentary sources. Concentrations of rare-earth elements (REEs) differ in magnitude from the ring complex and its granitic country rocks but they have similar patterns, which are sub-parallel and show LREEs enrichment compared to HREEs. The presence of a negative Eu anomaly in these rocks is related to plagioclase fractionation. The abundance of fluorine (F) in the different granite varieties plays an important role in the existence of a tetrad influence on the behavior of REEs (TE1, 3 = up to 1.15). Geochemical parameters suggest the crystallization of the BRC granite varieties by fractional crystallization and limited assimilation. Mn-columbite and Mn-tantalite are the most abundant rare-metals dissemination in the BRC granite varieties. We present combined field, mineralogical and geochemical data that are in favor of magma originating from a metasedimentary source for the BRC with typical characteristics of A-type granites. Our geodynamic model suggests that the Gebel El Bakriyah area witnessed the Neoproterozoic post-collisional stage of the ANS during its late phase of formation. This stage was characterized by the emplacement of fresh gabbros followed by the syenogranite and alkali-feldspar granite of the BRC into an arc-related assemblage (granodiorite and monzogranite). It is believed that the mantle-derived magma was interplated and then moved upward in the extensional environment to a shallower level in the crust owing to events of lithospheric delamination. This presumably accelerated the processes of partial melting and differentiation of the metasedimentary dominated source (Tonian-Cryogenian) to produce the A-type granites building up the BRC (Ediacaran).

Evidence for heterogeneous oxidation on the surface of a plasma SiC nanopowder based on synchrotron-excited XPS

The surface chemistry of a plasma SiC nanopowder was characterized by X-ray photoelectron spectroscopy using a tunable synchrotron X-ray source. The sample surface was representative of SiC nanopowder surfaces in interaction with ambient air, with no significant influence from carbonaceous deposits. By choosing an incident photon energy in the range 200–1200 eV, the escape depth of photoelectrons was altered from 0.5 to 3 nm based on the C 1s, Si 2p and O 1s core-level transitions. The spectral series gave evidence for surface enrichment of silica and sp2-bonded elemental carbon. Several models of surface enrichment were tested against the spectral intensities as a function of escape depth. This analysis led to sp2-carbon islands and two types of oxidation depths. While on the larger part of the surface, the silica is only a near-monolayer in thickness, there are surface regions that are oxidized to a depth of ≥3 nm. These heavily oxidized regions are attributed to defected open channel pores on the outer surface of nanoparticle agglomerates, based on the previous electron tomography results.

Internal Structure of the Lunar Mantle: Matching of Geochemical and Geophysical Models

There are serious contradictions between the geophysical and geochemical classes of models of the chemical composition and internal structure of the Moon, associated with the assessment of the abundance of the main oxides. The search for a potential consensus between the models was carried out on the basis of a set of geophysical and geochemical data using the Monte-Carlo method using the Markov chain scheme in combination with a method of minimization of the Gibbs free energy. The influence of the chemical composition and mineralogy of several conceptual models on the internal structure of the Moon has been studied. Two classes of chemical composition models are considered—the E models with terrestrial values of Al2O3 and CaO and M models with their higher content, as well as two classes of the most popular geochemical models, the Taylor Whole Moon (TWM) and Lunar Primitive Upper Mantle (LPUM) models, with ~45 wt % SiO2, but with different concentrations of refractory oxides and FeO. In both classes of E and M models, the lunar mantle is enriched in silica (~50 wt % SiO2) and FeO (11–13 wt %, Mg# 79–81) relative to the bulk composition of the silicate Earth (BSE, ~45 wt % SiO2, ~8 wt % FeO, Mg# 89). Such high concentrations of SiO2 and FeO become the determining factors for understanding the features of the mineral, velocity, and density structure of the lunar mantle. For the E and M models and geochemical models TWM and LPUM, the speed of sound and the density of stable phase associations are calculated. For E and M models, good agreement was obtained between the velocities of P- and S-waves and seismic sounding data from the Apollo program, which supports the idea of a silica-rich (olivine-pyroxenite) upper mantle. Unlike the Earth’s upper mantle, the dominant mineral in the Moon’s upper mantle is low-calcium orthopyroxene, not olivine. In contrast, the sound velocities of silica-unsaturated compositions, both FeO and Al2O3 enriched (TWM) and depleted (LPUM) models, do not match the seismic signatures. Thermodynamically justified restrictions on the chemical composition, mineralogy, and physical characteristics of the mantle based on the E and M models make it possible to eliminate some contradictions between the geochemical and geophysical classes of models of the internal structure of the Moon. Simultaneous enrichment in ferrous iron and silica is difficult to reconcile with the hypothesis of the formation of the Moon as a result of a giant impact from the substance of the Earth’s primitive mantle or from the substance of a shock body (bodies) of chondrite composition. Limitations on lunar concentrations of FeO and SiO2 probably correspond to the parent bodies of some achondrites.

Boninitic melt percolation makes depleted mantle wedges rich in silica

Abstract Global fore- and sub-arc peridotites show paradoxically highly melt-depleted yet silica-enriched (as excess orthopyroxene) compositions, which have been attributed to either silica-enriched mantle sources or metasomatic overprints by silica-rich fluids/melts. Here, we present robust mineralogical evidence from an ophiolitic peridotite suite and thermodynamic modeling suggesting that boninitic melt percolation is a viable manner to induce silica enrichment and keep the ultra-depleted signature in a nascent lithospheric mantle wedge. The co-occurrence of resorbed olivines and euhedral high-Cr# spinels with a boninitic origin enclosed by porphyroblastic orthopyroxenes in these peridotites documents that the primary olivines were partially melted or dissolved along with precipitation of the euhedral spinels and growth of the orthopyroxene through reactions between the depleted peridotites and boninitic melts. Such metasomatism modulates the geochemistry of mantle wedges and can explain the compositional variations observed in the majority of global fore- and sub-arc peridotites and supra–subduction zone ophiolitic counterparts. Lateral assembly of these mantle domains by accretionary orogenesis may contribute to the growth of continental lithosphere and accounts for the existence of melt-depleted yet silica-enriched mantle domains beneath orogens.

Production and evaluation of alkali-activated binders of low-calcium fly ash with slag replacement

Formulating alkali-activated binders requires a clear understanding of the role of activator concentration and source material composition on product formation and strength gain. Alkali activation of a low-calcium fly ash (FA) binder with slag replacements at 30% and 50% by mass was evaluated. The reactivity and compressive strength gain of the activated binders were evaluated using activating solutions with different sodium hydroxide molarities (SHMs). An increase in SHM produced a higher compressive strength of the activated binder. The primary reaction product formed in the activated binder was calcium silicate hydrate with aluminium substitution (C-(A)-S-H). An increase in SHM led to an increase in C-(A)-S-H content and a reduction in porosity. The slag contributed to early reactivity of the binder and the initial strength development, while the FA contributed to the later age strength by silica enrichment of the C-(A)-S-H. While increasing the SHM produced an increase in early reactivity, the sodium did not directly contribute to the formation of the reaction product. The sodium from the alkaline activator was not chemically bound to the C-(A)-S-H and could be removed by leaching in water. An increase in basicity with SHM enhanced the contribution of the low-calcium FA, leading to higher silica enrichment of the C-(A)-S-H.

Hydrochemical assessment of groundwater in the Kert aquifer using a GIS application: an overview of the control factors for fluoride, arsenic and silica enrichment

Our study was based on using a freshwater aquatic species to assess the short-and long-term toxicity of an organophosphate insecticide commonly adopted by the Moroccan agriculture sector. Recently, groundwater pollution has emerged as one of the most severe environmental challenges, with a particular emphasis on levels of heavy metal pollution. Conservation efforts and efficient management of groundwater resources are required to determine the full scope of this damage. The current research answers the physical-chemical evaluation of the middle Kert basin’s water quality (Mediterranean area, Driouch province, Eastern Morocco) by collecting 42 samples and measuring pH, TDS that vary between 451 and 5841 mg/l, and EC that range from 0.72 to 9.41mS/cm2 according to ISO 5665. The samples were analyzed by ICP-MS and flame atomic absorption spectrometry to detect fluoride and arsenic content. Whose fluoride in the survey area varied from 0.01 mg/l to 2.85 mg/l. The hydro-chemical classification resulting from the Geographic Information System (GIS) statistical data analysis was used to interpret the analytical data on the phenomena responsible for the mineralization. This quantity is considerably higher than the maximum allowable level of 1.5 mg/L, which is the regulation for drinking water in Morocco. It indicates that both natural and artificial factors have contributed to the effects. Most stations have a fluoride concentration in the water, which can be used to identify them. It is a significant amount less than the values that would be ideal; just four wells have concentrations higher than the values that are legally allowed to be. The fluoride levels in the region’s water sources directly result from the natural elements that make up this particular geographic location.The same happened for arsenic, which exceeded 0.1 mg/l in just two samples.

PETROGRAPHY AND GEOCHEMISTRY OF METASEDIMENTS FROM BUGAJI, PART OF MALUMFASHI SHEET 79 NE, KANO STATE, NORTHWESTERN NIGERIA

This research is aimed at determining the protolith of metasediments that underpin the geology of Bugaji region of Kano State. The study area was mapped systematically and the lithologies encountered include phyllite, undifferentiated schist, quartzo-feldspathic schist, and gneiss. Samples taken from several outcrops were subjected to mineralogical and geochemical analyses using X-ray diffraction and X-ray Fluorescence (XRF), respectively. The metasedimentary rocks have evidently undergone significant deformation textures (foliation, lineation, and fractures), and metamorphism, indicating the area is situated in a tectonically active zone. Quartz, feldspar, mica, and a number of accessory minerals make up majority of the metasediments, while the geochemical data show enrichment of aluminum, silica, and iron. The geochemical indicators support the idea that the rocks developed on a continental margin. The mineralogy and geochemistry indicate the rocks likely came from a source region with a predominance of granitic rocks.

On an Extensive Late Hydrologic Event in Gale Crater as Indicated by Water‐Rich Fracture Halos

AbstractWe analyze spatially pervasive, light‐toned “halos” associated with fractures in a sedimentary unit (Stimson) of Gale crater, Mars, and report a similar network of halos discovered in a separate geologic group (Bradbury). Through a dedicated active neutron measurement campaign, we provide independent confirmation of the water‐rich nature of these features. Together with mineralogical and geochemical data, these features are consistent with abundant hydrated amorphous silica (opal‐A). We suggest that the mineral and amorphous assemblages are indicative of formation under low‐temperature and predominantly low‐pH conditions (passive silica enrichment) with minor contribution of silica (active silica enrichment) from adjacent units. We show that there is significant amorphous silica in the array of sedimentary rocks in Gale crater, allowing them to play a role in an active silica enrichment phase of halo formation. We suggest that the involved alteration event was short lived and our finding of vast halo networks in a distant, older unit implies a more vast network of hydrologic subsurface conduits than previously known. This relatively recent subsurface hydrologic system was present long after the transition from a warm and wet to a cold and dry Martian environment, extending the habitability conditions on Mars to an epoch that is generally considered not favorable for life on the surface. Finally, our bulk H quantification of these features, which ranges from ∼3–6 wt% H2O‐equivalent‐H, suggests that the amorphous material in halos hosts ample supplies of readily released water, making them a considerable resource at the otherwise dry Martian equator.

Physicochemical and biological characterization of silica-coated alumina particles.

A tribochemical silica-coating (TSC) method has been developed to improve the adhesion of dental resin composites to various substrates. The method utilizes airborne-particle abrasion using particles having a silica surface and an alumina core. The impact of the TSC method has been extensively studied but less attention has been paid to the characterization of the silica-modified alumina particles. Due to the role of silicate ions in cell biology, e.g. osteoblast function and bone mineralization, silica-modified alumina particles could also be potentially used as a biomaterial in scaffolds of tissue regeneration. Thus, we carried out detailed physicochemical characterization of the silica-modified alumina particles. Silica-modified alumina particles (Rocatec, 3M-ESPE) of an average particle size of 30µm were studied for the phase composition, spectroscopic properties, surface morphology, dissolution, and the capability to modify the pH of an immersion solution. The control material was alumina without silica modification. Pre-osteoblastic MC3T3-E1 cells were used to assess cell viability in the presence of the particles. Cell viability was tested at 1, 3, 7 and 10 days of culture with various particle quantities. Multivariate ANOVA was used for statistical analyses. Minor quantities of silica enrichment was verified on the surface of alumina particles and the silica did not evenly cover the alumina surface. In the dissolution test, no change in the pH of the immersion solution was observed in the presence of the particles. Minor quantities of silicate ions were dissolved from the particles to the cell culture medium but no major differences were observed in the viability of pre-osteoblastic cells, whether the cells were cultured with silica-modified or plain alumina particles. Characterization of silica-modified alumina particles demonstrated differences in the particle surface structure compared to control alumina. Dissolution of silica layer in Tris buffer or SBF solution varied from that of cell culture medium: minor quantities of dissolved Si were observed in cell culture test medium. The cell viability test did not shown significant differences between control alumina and its silica-modified counterpart.

Geology and geochemistry of the high-grade Zankan magnetite ore, Western Kunlun Mountains, NW China

Over the past decade, several magnetite-rich iron deposits have been discovered in the Taxkorgan region of the western Kunlun Mountains of northwestern China. These include the Zankan, Jiertieke, Laobing, Yelike, and Taaxi iron deposits. Prospective iron ore reserves are estimated at over 1 billion tons, with an average magnetite grade of 28% (Feng et al., 2018). The largest of the deposits, the Zankan Iron Deposit (ZID), is estimated to contain 628 million tons of iron ore, with at least 10% of the ores being high-grade (TFe > 50 wt%). However, the geological processes by which the high-grade ores in the ZID were formed remains poorly constrained. In this study, we combine whole rock and ore geochemistry data, oxygen and sulfur stable isotopes, and uranium-lead and hafnium isotopes from zircons to elucidate the plausible mechanisms underpinning the formation of the ZID ores. Based on mineralogy, we define two ore types. Type 1 is essentially comprised of quartz and magnetite, interlayered with schist, and it retains the sedimentary fabrics of the precursor iron-rich sediments which were an iron formation (IF). Type 2 formed by the intrusion of a dacite-porphyry into the IF which led to magnetite remobilization and recrystallization as manifest in magnetite-ferro actinolite veining. Rare earth element (REE) characteristics of the high-grade ores differs from those of the precursor IF, with chondrite normalized REE patterns showing enrichment of LREE and significant negative europium anomalies close to those of the dacite-porphyry. The oxygen and sulfur isotopic composition of magnetite and pyrite in the high-grade ores suggests a further meteoric influence on the ZID with silica enrichment driven by leaching of the precursor IF from elsewhere in the sequence. Circulation of the ore forming fluid is attributable to the development of faults and fracture zones that resulted from the intrusion of the dacite-porphyry. Laser ablation uranium-lead analyses of zircons from the dacite-porphyry yield two groups with ages of 551.25 ± 3.32 Ma and 497.82 ± 3.81 Ma, representing captured detrital zircons and the intrusive age of dacite porphyry, respectively. Given the intimate geological relationship between the dacite-porphyry and T2 ore, we suggest that the high-grade ores are formed after 497.82 Ma. Collectively our field observations and geochemical data reveal the detailed alteration processes that led to the development of the high-grade iron ores in the ZID, identifying distinctive features that may help to guide future exploration for additional high-grade ore deposits in the Taxkorgan region.

Silicified bony fish otoliths from the Vaals Formation (lower Campanian) of Vaals-Eschberg, the Netherlands

The Vaals Formation in its type area, in southern Limburg, the Netherlands and adjoining Aachen area in Germany, comprises predominantly glauconitic sandy deposits that were laid down in a very shallow, nearshore environment. The early Campanian age assignment (c. 81 Ma) of the Vaals Formation is based primarily on ammonites (in particular Scaphites hippocrepis II–III) and belemnitellid coleoids. All aragonite has been dissolved in strata assigned to the Vaals Formation, and silicified macrofossil assemblages are found at certain levels. The silicification is thought to reflect temporary silica enrichment (by riverine input, or dissolution of sponge spicules or silicoflagellate tests). The most important and species-rich silicified assemblages are known from the so-called ‘Müller's Bed’, just below the Vaalsbroek Horizon and within the Gemmenich Member, in the lower part of the formation. Silicified molluscs, serpulids, scleractinian corals, bryozoans and echinoderms have been described in the past. Now, a temporary exposure (1987) of ‘Müller's Bed’ at Vaals-Eschberg has also produced silicified teleost otoliths. A total of 42 specimens have been recovered from this level, 20 of which could be identified and assigned to seven species, including three new ones; Centroberyx vaalsensis sp. nov. (Beryciformes, Berycidae), Protoholocentrus janjanssensi gen. et sp. nov. and Sillaginocentrus crispus sp. nov. (both Holocentriformes incertae sedis). The faunal composition differs distinctly from coeval otolith associations known from elsewhere in Europe and in North America. The putative holocentriform otoliths are the earliest known to date from the fossil record.

Eruption of ultralow-viscosity basanite magma at Cumbre Vieja, La Palma, Canary Islands

The viscosity of magma exerts control on all aspects of its migration through the crust to eruption. This was particularly true for the 2021 eruption of Cumbre Vieja (La Palma), which produced exceptionally fast and fluid lava at high discharge rates. We have performed concentric cylinder experiments to determine the effective viscosities of the Cumbre Vieja magma, while accounting for its chemistry, crystallinity, and temperature. Here we show that this event produced a nepheline-normative basanite with the lowest viscosity of historical basaltic eruptions, exhibiting values of less than 10 to about 160 Pa s within eruption temperatures of ~1200 to ~1150 °C. The magma’s low viscosity was responsible for many eruptive phenomena that lead to particularly impactful events, including high-Reynolds number turbulent flow and supercritical states. Increases in viscosity due to crystallization-induced melt differentiation were subdued in this eruption, due in part to subtle degrees of silica enrichment in alkaline magma.

Mineralogy and geochemical signatures as indicators of differential weathering in natural soil profiles from the West Asturian-Leonese Zone (NW Iberia)

This paper presents detailed mineralogical results together with a geochemical characterization for a sequence of six natural soil profiles. Bedrock samples (R series) and overlying soil samples (S series) were characterized. The soil profiles are distributed in a series of Paleozoic lithological units from lower Ordovician to upper Carboniferous in age (Iberian Massif, NW Iberia). The lithological influence on mineral properties and geochemical composition and, how different weathering may be occurring under very similar temperate and acidic conditions, have been studied. Field observations together with laboratory analyses were indicative of differential weathering. So, a series of selected chemical indices and relations were applied to clarify this assumption. The mineralogy was analysed by Scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD) of rock powder and soil oriented aggregates. X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectroscopy (ICP-MS) were applied to analyse chemical composition. The first results showed how major elements, SiO2, Al2O3 and Fe2O3, slightly enriched in the soil profiles, are consistent with the dominant mineralogy: quartz, chlorite, muscovite and/or illite, together with kaolinite and albite. The bases K2O, Na2O, CaO and MgO are also coherent with mineral composition and experience little variation, but are gradually removed in the profiles. The mobility of major elements leads to a general loss of bases and, in general, a slight enrichment in silica and sesquioxides. SiO2 is enriched, firstly accumulated in soils and partially depleted by dissolution as colloidal form. Al2O3 in some soils is slightly less than in former rocks, so other physical processes are expected to take place, involving clay removal with consequent aluminium depletion too. A special emphasis has been given to albite coexisting with kaolinite, firstly supposed to be directly inherited from parent substrates when present, but finally the chemical index PIA shows it was mainly due to mineral alteration of plagioclases. The best correlations to explain the albite alteration and kaolinitization progress were obtained with chemical indices PIA, CIW, CIA and Al2O3/Na2O ratio. This together with mineralogical signatures, suggest that kaolinite is the result of gradual dissolution due to the acid hydrolysis of albite in such acidic environments, which may also be attributed to the organic matter influence.

Mineralogy and bulk geochemistry of a fumarole at Hverir, Iceland: Analog for acid-sulfate leaching on Mars

AbstractIceland’s Námafjall geothermal area exhibits a range of alteration environments. Geochemical and mineralogical analyses of fumaroles and hot springs interacting with Holocene basaltic lavas at Hverir, and with Pleistocene hyaloclastites atop nearby Námaskar∂, reveal different patterns of alteration depending on the water/rock ratio, degree of oxidation, and substrate composition and age. The focus of this study is a transect of a Hverir fumarole that has formed a bullseye pattern of alteration of a Holocene basaltic lava flow. Surface samples and samples collected from shallow pits were analyzed by X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscopy (SEM) to constrain changes in mineral assemblage and major elemental composition with both distance and depth. Elemental sulfur is concentrated near the vent, with leached deposits with amorphous silica and anatase nearby and kaolinite, hematite, and jarosite/alunite-group sulfate minerals farther out, with smectites and less altered material at the margins, though smaller-scale mineralogical diversity complicates this pattern.Silica phases include amorphous silica (most samples), cristobalite (some samples in the leached part of the apron), and quartz (minor constituent of a few samples). The silica was concentrated through residual enrichment caused by leaching and is accompanied by a significant enrichment in TiO2 (in anatase). The presence of abundant cristobalite in a surface fumarole-altered Holocene basaltic lava flow most likely reflects cristobalite formed during the devitrification of volcanic glass or precipitation from fumarolic vapors, rather than high-temperature processes. Minor, localized quartz likely reflects diagenetic maturation of earlier-formed amorphous silica, under surface hydrothermal conditions. Natroalunite, natrojarosite, and jarosite are all present and even exhibit compositional zonation within individual crystals, showing that under surface hydrothermal conditions, these minerals can form a significant solid solution.The high iron content of the substrate basalt and the prevalence of Fe-sulfates and Fe-oxide spherules among the alteration products makes this geothermal area an especially useful analog for potential martian hydrothermal environments. The residual enrichment of silica in the leached deposits of the Hverir fumarole apron could serve as an acid-sulfate leaching model in which amorphous silica forms without appreciable sulfur-bearing phases in many samples, a possible analog for silica-rich soils in the Columbia Hills on Mars. The coexistence of hematite spherules and jarosite-group minerals serves as an intriguing analog for a volcanic/hydrothermal model for hematite and jarosite occurrences at Meridiani Planum.