Immobile Elements Research Articles

Smectite-rich horizons in Inceptisols trigger shallow landslides in tropical granitic terranes

Puerto Rico was affected by >70,000 landslides in the wake of 2017 Hurricane Maria, and landslide prevalence was especially high in the Utuado region in the Cordillera Central. Landslide density was highest where soil parent material is granodiorite; landslide slip surfaces tended to be shallow (<60 cm), and often were mobilized rapidly and with long runout distances. This study combines field observations with soil mineralogy (bulk and clay fractions), soil geochemistry (bulk fraction), and soil strength as determined by field cone penetrometer testing (CPT) to test the hypothesis that clay-rich subsoil horizons function as slip planes when water-logged. Soil pits were excavated to depths of ~200 cm in Ultisols on an undulating plateau and to ~100 cm in Inceptisols on steep slopes (36-43o) that flank the plateau and cone penetrometer tests (CPT) were done within 2 m of the soil pit. Six pits were located adjacent to scarps from previous landslides, enabling analysis of soil profiles downward through extrapolated slip surfaces. Results from X-ray diffraction (XRD), X-ray fluorescence (XRF) and thermogravimetric analysis (TGA) indicate that soils are heterogeneous, often with subsoil horizons enriched in clay minerals and immobile elements (Al, Fe, Ti). Inceptisols on steep slopes often contain smectite-rich horizons at 30–60 cm depth that appear to function as slip surfaces; in other Inceptisols, such horizons are not present and landslide susceptibility is potentially lower. In Ultisols, soil mineralogy is dominated by kaolinite with minor halloysite, and increased kaolinite content at soil depths ≥80 cm at some sites suggests potential slip surfaces enhancing probability of landslides. The origin of clay-rich horizons appears to be (1) fractures in granodiorite that facilitate water flow and leaching, accelerating mineral dissolution during early weathering stages, and (2) smectite-rich buried soils under permeable colluvium likely deposited by a prior mass wasting event. Where clay-rich layers occur beneath more-permeable horizons, rapid infiltration then absorption of water in clay-rich subsoil horizons causes decreased shear strength and increased landslide susceptibility.

1.38 Ga magmatism and the extension tectonics in East Kunlun, northern Tibetan Plateau

Numerous Paleo- to Mesoproterozoic magmatic rocks were emplaced during the assembly, accretion and break-up of the Columbia supercontinent, and are keys to illustrating the supercontinent circle. The geological, petrological, geochronological and geochemical data of the newly discovered meta-felsic and meta-mafic magmatic rocks from the Wulonggou area are presented in this study to shed light on the Mesoproterozoic geodynamic setting of the Central Kunlun Belt and the Qaidam Block. Zircon U-Pb geochronological results indicate that the crystallization ages of the meta-felsic samples are 1385–1376 Ma, and the meta-mafic is 1379 ± 25 Ma (MSWD=0.17). Samples from the meta-felsic unit have SiO2 contents of 68.37–73.03 wt% and belong to the high-K calc-alkaline series. They exhibit similar REE distribution patterns and display enrichment in light rare earth elements (LREES) and negative Eu anomalies. Enrichments in Rb, Ba, Th, U and K, depletion in Nb, Ta, Sr, P and Ti are seen in the primitive mantle-normalized trace element pattern diagram. Magmatic zircons from different meta-felsic samples yield variable εHf(t) values of −8.14 to + 9.37 corresponding to ca. 1.7–2.0 Ga two-stage Hf model ages. Samples from the meta-mafic unit have low SiO2 concentrations of 49.87–50.43 wt%, high contents of Fe2O3T, MgO, CaO and TiO2, and Mg# values of 52–58. They show low total REE concentrations of 19.8–30.4 µg/g, and depletion in LREES, flat HREES distribution patterns with (La/Yb)N of 0.27–0.53 and insignificant Eu anomalies. Flat distribution pattern of high field strength elements (HFSEs) is observed in the primitive mantle-normalized trace element pattern diagram. They display similar immobile elements’ concentrations and distribution patterns, low Ti/Y, Nb/Y, La/Yb, and high Nb/La ratios, comparable with the present-day normal middle ocean ridge basalt. Zircons from the meta-mafic sample have mostly positive εHf(t) values ranging from −0.10 to + 4.10 with a single stage Hf model ages of ca. 1.7–2.0 Ga. The geochemical result implies that the meta-felsic unit was generated by partial melting of the Paleoproterozoic juvenile mafic lower-crustal material with mantle attributions, and the meta-mafic unit was probably from partial melting of the lithospheric mantle. Synthesizing the above evidences, Wulonggou Mesoproterozoic meta-magmatic rocks are a bimodal suite formed in a continental extensional tectonic setting which is probably related to the break-up of the Columbia supercontinent.

Mineralogical Characterization and Geochemical Signatures of Supergene Kaolinitic Clay Deposits: Insight of Ropp Complex Kaolins, Northcentral Nigeria

This study presents the chemical and mineralogical composition of clay deposits and associated rock types within the Ropp Complex in order to assess the influence of parent lithology on the kaolinization, genesis, and utility of the deposit. Representative kaolin samples from E horizons of the weathering profiles and their bedrocks were collected from six sites in the Ropp Complex. Clay mineralogy was determined via the XRD technique, while a geochemical analysis was conducted using XRF, SEM coupled with EDS, and ICP-MS. The results showed that all kaolins dominantly contain kaolinite with a content of 77%–98% except for the AS1 kaolin with only minor kaolinite (20%) but mainly illite (65%). The notably lower crystallinity of kaolinite (HI value of 0.53–1.1) as well as its markedly small grain size is consistent with the formation of kaolinite from intensive chemical weathering of igneous rocks. The AS1 kaolin was probably formed from hydrothermal alteration in the burial stage due to the heating of groundwater by the late volcanism. Mobile trace elements (Sr, Ba, and Eu) exhibited a depletion trend, while immobile elements (Hf, Ta, Th) showed enrichment. The relatively more zirconium in kaolins implies the formation of low-temperature kaolinization. The notably high kaolinite content, accompanied by reasonable levels of Fe2O3 and TiO2, signifies a medium-grade quality. Furthermore, chondrite-normalized rare earth element (REE) patterns exhibit congruent trends in rocks and kaolin samples, indicating a relative enrichment in light rare earth elements (LREEs) alongside a discernible negative Eu anomaly. The abundant kaolinite and silicon–aluminum composition make the kaolins suitable for refractories, pharmaceutics, cosmetics, and supplementary cementitious material (SCM).

Evidence for isotopically light Fe mobility under oxidising conditions in subduction zone fluids: A record of Monviso meta-serpentinites, Western Alps

The isotopically light Fe signature of arc magmas relative to mid-oceanic ridge basalts (MORB) is expected to be related to the redox state of their source. This implies a link between Fe mobility and redox variations across subduction zones. Here we address slab chemical variations during prograde metamorphism through a comprehensive geochemical study, including major, trace elements and Fe stable isotope (δ56Fe) analyses, of meta-serpentinites composing the eclogitic meta-ophiolite of the Monviso massif (Western Alps, Italy). These rocks partly preserve mantle related geochemical heterogeneities, as supported by negative correlations between fluid immobile elements (High Field Strong Elements) and LREE/HREE (Light – Heavy Rare Earth Elements) ratios. They are however characterized by large Cs enrichments relative to U or alkali elements suggesting that abyssal fluid mobile elements signature was overprinted by subduction related processes. Meta-serpentinites display large δ56Fe variations, from -0.20 ± 0.05 ‰ to +0.09 ± 0.03 ‰. Mineral separate analyses of olivine bearing veins show low Δ56Fe between olivine and magnetite (∼ 0.4 ‰), which according to Fe isotope thermometry correspond to high temperature equilibration, estimated between 530 and 550 °C, compatible with Monviso metamorphic climax (520–570 °C and 2.6–2.7 GPa). These results, in combination with geochemical modelling, confirm a reset of δ56Fe signature of abyssal serpentinites during prograde metamorphism in subduction zones. The bulk rock δ56Fe values of Monviso meta-serpentinites are negatively correlated with their Fe3+/∑Fe and As concentrations (a redox-sensitive and fluid mobile element). These correlations can be attributed to a metasomatism by external fluids derived from slab serpentinites during subduction. It also concords with the oxygen fugacity (fO2) record in meta-serpentinites, with meta-serpentinites equilibrated at high fO2 displaying the lowest δ56Fe values while samples equilibrated at low fO2 display mantle like δ56Fe signatures. These results highlight that oxidising conditions during serpentinite dehydration are likely to boost isotopically light Fe mobility in slab derived fluids.

Geochemistry of BIF in the Quadrilátero ferrífero, Brazil, as a proxy to neoarchean paleoenvironmental and depositional conditions

Precambrian Algoma-type banded iron formations (BIFs) are biochemical metasedimentary rocks formed in the deep water environment relatively close to centers of volcanic expansion and can be characterized on the basis of their paleodepositional environment and the associated rock types. These rocks may contain geochemical signatures indicative of changes in the redox conditions of the Archean ocean. Such variations in the Meso- and Neoarchean are crucial in understanding the processes that led to the gradual increase of oxygen in the early atmosphere, culminating in the Great Oxidation Event (2.4–2.3 Ga). Oxide- and carbonate-facies BIFs were intercepted by drill cores in the Pilar gold deposit in the NE sector of the Quadrilátero Ferrífero (QF), Brazil, located in the Neoarchean Rio das Velhas greenstone belt. These rocks are interbedded with mafic and ultramafic metavolcanic rocks and carbonaceous phyllites. In light of the potential to reconstruct paleodepositional evidence indicative of the Earth's atmospheric redox history based on this stratigraphy, we have considered specific proxies from geological and geochemical observations. Pilar BIFs geochemistry exhibits positive anomalies of La, Eu, and Y, indicating characteristics inherited from seawater and high-temperature hydrothermal fluids. In addition, a superchondritic Y/Ho ratio further supports the influence of seawater. The signatures of the major elements Al2O3 and other immobile elements typical of detrital sediments corroborate the interpretation that these rocks were deposited in a deep marine environment with low clastic influence. Furthermore, negative Ce/Ce*SN anomalies in some sections of the Pilar BIF indicate limited oxygen availability which, together with Mo, U, V, and Zn trace-element enrichment factors, indicate deposition under suboxic/euxinic conditions. This research, together with other similar BIF data from the NW QF provide new insights into the paleoenvironmental conditions prevailing during the formation of the Archean volcano sedimentary basins that compose the southern São Francisco craton (SFC).

Hydrothermal alteration and geochemical proximity indicators to ore at the Metsämonttu Zn–Pb–Cu–Au–Ag deposit, Uusimaa belt, southern Finland

The Paleoproterozoic Metsämonttu Zn–Pb–Cu–Ag–Au deposit (1.5 Mt at 3.5 wt% Zn, 0.8 wt% Pb, 0.3 wt% Cu, 13.2 wt% S, 25 g/t Ag, and 1.4 g/t Au, production 1952–1974) is the largest past-producing mine in the Aijala–Orijärvi area (Orijärvi formation, Aijala member) within the Uusimaa belt, southern Finland. The Aijala member is characterized by 1.9–1.88 Ga felsic-dominated volcanic-sedimentary supracrustal rocks with intercalated sedimentary carbonates and iron formations. The area is underexplored, and little deposit-scale research has been carried out, despite the lateral continuum to the world-class ore district of Bergslagen in south-central Sweden. To better understand the Metsämonttu VMS-related alteration system, we reassessed the previously described metamorphic mineral assemblages and their protolith rock compositions by using mobile and immobile element geochemistry. This resulted in the definition of four metamorphosed alteration mineral assemblages and eight chemostratigraphic rock units. The chemostratigraphic results suggest that the lithological and/or structural setting of the Metsämonttu succession is more complex than previously considered. The stratigraphic footwall is mainly characterized by an extensive cordierite + anthophyllite ± biotite ± phlogopite + pyrite ± pyrrhotite (Mg–Fe–S) assemblage dominated by mafic rocks, designated Mafic B1 and Mafic B2, and Andesite A1. The main sulfide mineralization is hosted by tremolite + diopside ± biotite ± phlogopite ± chlorite skarn (Ca–Mg–K). A sericite-bearing muscovite + quartz ± biotite ± phlogopite + pyrite (K–Si–S) assemblage is composed of felsic to mafic protoliths (Mafic B1–B2, Andesite A1, Dacite A1, Dacite B1, Dacite C1) and extends several tens of meters into the stratigraphic hanging-wall. A quartz + pyrite ± muscovite (Si–S) assemblage represents the immediate ore-proximal alteration and is derived from rocks with a rhyolitic composition (Rhyolite A1).Limited drill core samples near Metsämonttu mineralization, along with restricted surface alteration, pose challenges in studying geochemical variations from distal to ore proximal areas and limits the ability to model the shape and size of the alteration zone. Large mass changes suggest that the alteration was hydrothermal, and due to several protolith compositions, the alteration is interpreted to be predominantly discordant to stratigraphy. A 60-m-wide alteration halo surrounds the Metsämonttu deposit. Major and trace elements, namely MgO, Na2O, K2O, SiO2, Fe2O3, Cu, Zn, Pb, S, Ag, Tl, Hg, Se, Te, Sn, Sb, Rb, and Sr, and the indices modified alteration index (MAI), Ishikawa alteration index (AI), chlorite‑carbonate-pyrite index (CCPI), S/Na2O can be used for chemical vectoring, which can assist regional or near-mine exploration. Elements MnO, Ba, Cd, Bi, As, Ni, Co, W, Ga, Mo, and indices Hashigushi index and advance argillic alteration index (AAAI) were less useful as geochemical exploration indicators.

Petrogenetic evolution of Ramagiri greenstone terrane, Central Dharwar craton, Andhra Pradesh, India: Unravelling ancient oceanic basin of Archean Earth

The Ramagiri greenstone terrane (RGT) of Central Dharwar craton, India, is recognized as remnants of Archean oceanic crust squeezed between ancient proto‐continental terranes. The granites and gneisses formed as a result of partial melting, resisted subduction and collided, sinking the intervening ocean basin. The geochemical characteristics of the bimodal metavolcanics of RGT were carefully assessed using suitable proxy. An insight into them suggests that the mafic rocks bear characteristics of island arc tholeiites belonging to suprasubduction zone setting, as corroborated by their low TiO2/Yb (avg 443) and high Th/Nb (avg 0.8). Their high V/Ti (avg 0.3) ratio points towards a mantle source that has been influenced by subduction, whereas low Ti/Yb echoes high degrees of shallow melting with little residual garnet. The felsic rocks on the other hand are metaluminous–peraluminous, mostly calc‐alkaline and geochemically akin to I‐ and S‐type syncollisional and volcanic arc granite emplaced during intercontinent collision. Their immobile element plot with low Nb + Y (avg 25) concentration also points towards a volcanic arc environment.

Old basalts, young soils ‐ Age constraints for the Golan Heights plateau volcanic soils

AbstractThe Golan Heights plateau in northern Israel is underlaid by volcanic rocks ranging in age from ~5.5 to 0.1 Ma. Throughout the Golan Heights, these rocks are covered by shallow soils that rarely exceed 0.5 m in depth. The soils are generally assumed to form a chronosequence, in which their ages correspond to those of the basalts they cover. Such age correspondence would imply that the soils have been slowly accumulating over hundreds of thousands to a few million years, suggesting a generally stable system. The ages of these soils and their temporal correlation to the basalts, however, have never been determined or tested.Here, we present age constraints for the soils of the Golan Heights. Soils were surveyed and sampled with their corresponding basalt bedrock. Mass balance calculations based on conservative immobile elements, coupled with 36Cl‐based basalt denudation rates, suggest that the soil ages are decoupled from the ages of the underlying basalts, and represent up to a few thousand years of soil production, at most. This time frame is orders of magnitude shorter than the basalt age, challenging the prevalent assumption that the soils form a chronosequence.Our findings strongly suggest that erosion is a significant factor controlling soil formation and accumulation on the plateau, despite the generally flat morphology of the Golan Heights. The erosion is associated with tectonic activity along the Dead Sea transform, with the development of the Kinarot and Hula valleys, and with the consequential development of drainage systems of various sizes on the plateau. Throughout the Golan Heights, the timing of volcanic activity in relation to the development of the valleys and drainage systems also appears to strongly affect soil development and accumulation.

A negligible role for forearc serpentinites and mélange diapirism in contributing halogens to Mariana arc magmas

Trace element enrichment in arc lavas has traditionally been linked to the presence of slab-derived materials introduced by a combination of aqueous slab-fluids derived from altered oceanic crust (AOC) and subducted lithosphere and sediment-melts. However, an alternative is that slab material could be mobilised in mélange diapirs formed from forearc serpentinites admixed with sediments and AOC in a subduction channel. In order to further constrain the relative importance of slab-fluids, sediment-melts and mélange diapirs in the Marianas and track how the contributions of these components evolves across the arc, we selected submarine volcanic glasses from pillow rinds recovered from the Southeast Mariana Forearc Rift, and the Mariana arc and backarc basin. The glasses are all enriched in halogens and other fluid mobile elements relative to immobile elements of similar compatibility, demonstrating a strong subduction signature. Irrespective of their position in the arc, the lavas all have Br/Cl weight ratios of 0.0016–0.0037 and I/Cl of 8.3 × 10−6–127 × 10−6, which encompasses a similar range as reported for arc and backarc glasses from the SW Pacific. The Br/Cl and I/Cl of the subduction component overlaps with altered ocean crust suggesting dehydration of altered ocean crust (± lithospheric serpentinites) as the dominant source of halogens and related slab-fluids. The Br/Cl and I/Cl of the Marianas glasses are much lower than forearc serpentinites from the Marianas, which does not favour a role for either dehydration of forearc serpentinites entrained with the subducting slab or direct melting of mélange diapirs formed from serpentinised forearc material. The halogen data are most easily reconciled with the conventional model for arc magma generation, in which halogen-bearing aqueous fluids are progressively released from a dehydrating subducting slab. The importance of sediment-melts and/or forearc serpentinites in significantly contributing to the subduction zone budgets of other elements is not precluded, but the high halogen content of forearc serpentinites means that direct melting of mélange diapirs is unlikely.

A new insight into metasomatism through mass-density-solid volume variation maps

In order to present a new petrological approach to quantify mass transfer redistribution, especially regarding chemical zonation, published data of a centimeter sized aluminium-rich clinopyroxene from the Bergen Arcs in Norway is used. The sample comes from the island of Holsnøy where the dry granulite-facies protolith underwent hydration reaction under amphibolite-facies conditions. This aluminium-rich clinopyroxene developed kinks during deformation along which fluid has been introduced. It reacted in two different ways: to garnet plus a less aluminous pyroxene along kinks and to chlorite along cleavage planes. Compositional maps from electron probe microanalyzer (EPMA) were coupled to the mass balance equation of Gresens (Gresens, 1967) to quantify for each pixel present in a studied surface area, element gains and losses, density changes and solid volume variations. This new method allows to estimate the solid volume variation associated with the reaction by assuming minimal mass transfer, or by considering an immobile element i.e. aluminium immobile or by preserving the mass during the reaction. Results demonstrate that for all three assumptions made, the actual mass behaviour does not change significantly for major elements as opposed to the solid volume variation and the actual sum of mass transfer. In the high strain domain (kink) the element losses and gains in replacing the aluminium-rich clinopyroxene by garnet, are balanced by the opposite gains and losses associated with the less aluminous clinopyroxene. This implies that the local fluid chemical composition required for the formation of one mineral is equal to that in equilibrium with the second one after the reaction. The same observation can be made regarding solid volume variation that is balanced between garnet and the less aluminous clinopyroxene. Considering now the specific reaction in the kink and outside the kink (chlorite), mass transfer and redox conditions (Fe3+ and Fe2+) tend to behave in the same way supposing a temporal relationship between these two parageneses.

Origin of clays in the interbasaltic red boles of Deccan Volcanics: Pedogenesis versus palagonitization

Red-coloured clay-rich beds (bole beds) occur at flow breaks in parts of the Deccan volcanic province (DVP). These boles in the Deccan province retain paleoenvironmental information that prevailed at the K-T boundary, including the timing of the Deccan eruption synchronous with the K-T mass extinction. This contribution assesses the origin of clays in various red boles, selected based on their field appearances, physical properties, and relation with bounding units. The saprolitic red bole, fragile red bole and grey bole capping red bole have kaolinite and smectite clay with broad 001 peaks (FWHM>0.62°). The selective dissolution of grey bole reveals the highest Alo, Sio and Feo/Fed (>3) characteristics of short-range ordered alumino-silicates and oxyhydroxide. Both red and grey boles show relative enrichment in immobile elements, indicating leaching within the incipient stage of weathering (saprolite equivalent). Clays from these boles show FeFe and AlAl segregated domains in the octahedral sheet, features characteristic of short-range ordered clay, indicative of a pedogenesis. Smectite in these boles shows Fe > 0.3 apfu with trans vacant (tv) nature, suggesting oxidizing conditions at low temperatures. The STEM-EDS of clay FIB section reveal smectite laths with multiple chemistries in each sample, indicating re-equilibrating conditions in a closed system due to fluctuating wet and dry seasons. Contrary to the above two red boles, indurated-structure less and indurated-laminated red boles have glass shards with yellowish rinds and smectite clay (FWHM<0.5°), indicating palagonitization. The cation occurrence probability in the smectite octahedral sheets of later boles has values characteristic of randomly distributed cations, suggesting a relatively higher temperature of interacting solution. We envisage two processes of clay formation in red boles: a) pedogenesis and b) palagonitization of basalt flow top and/or mafic volcanoclastic deposits.

The trace element distribution in peat soils affected by natural burning events: A proxy of the original composition and metals mobility assessment

This work evaluates for the first time the effects on the trace element composition of peat soils affected by natural burning events, a recurrent phenomenon in the reclaimed wetland of the Mezzano Lowland (Padanian plain, NE Italy). The trace element distribution of two neighboring soil profiles, one pristine and one deeply affected by burning events, were compared to identify the original geochemical fingerprint of saltmarsh peat environment. The pre-combustion composition of the fired profile was reconstructed to infer the physico-chemical changes occurred as a consequence of the burning event, with a special attention to the mobility of elements of environmental concern, such as potentially toxic trace metals. The increase in concentration of potentially toxic elements (PTE) was particularly evident in two layers of the fired profile. V, Cr, Cu, Zn, Pb, and As contents progressively increase toward intermediate depths (30–75 cm) together with Th, Sr, Ba, U. On the contrary, Tl, Bi and Cd show a concentration peak in a thin, shallower (14–17 cm depth) horizon. The trace element composition of the unfired profile allowed the identification of specific ratios between immobile elements that can be used as geochemical fingerprint of the soils horizons with different soil organic matter (SOM) content. On the basis of Sr/Rb, Th/U and Ba/Sr it was possible to classify three types of sedimentary deposits characterizing both the unfired and fired profile, as well as to delineate the fire severity trends occurred in the different soil horizons of the fired profile. The distribution of immobile trace element, representative of the organic (U) and mineral (silicate, Th, Ba, REE and non-silicate, Sr) soil fractions with organic matter and bulk density in the non-fired profile, allowed the reconstruction of the original physico-chemical composition of the fired/burned profile and the accurate determination of the relative CO2 lost during the burning event. Moreover, the distribution of PTE with respect to immobile trace elements, used to estimate the element redistribution and mobility after burning in the fired profile, suggested that elements such as Cr, Ni, Zn, V were mainly immobile, whereas Pb, Mo and in particular Tl and Bi suffered a significant redistribution along the burned profile. Nonetheless, results of the gain/loss calculation for the whole soil profile suggested that no significant entry or leak of these elements occurred, limiting their redistribution inside the investigated soil system.

Mechanisms leading to exceptional niobium concentration during lateritic weathering: The key role of secondary oxides

Niobium (Nb) is considered as one of the most immobile elements during supergene weathering due to its low solubility and the expected resistance of the pyrochlore mineral group (A2B2X6Y) in which Nb occupies the B site. Although the resistance of pyrochlore is challenged by direct evidence of alteration in lateritic profiles, the geochemical and mineralogical processes controlling its behavior in the critical zone remains elusive. This study uses a multiscale geochemical, mineralogical and spectroscopic approach to monitor Nb solid speciation in a thick weathering profile. The weathering of the pyrochlore-bearing core carbonatite facies from Morro dos Seis Lagos has resulted in a Fe-enriched laterite with exceptional Nb concentrations (2.91 wt% Nb2O5 on average). The preservation of the successive secondary phases (Ti-, Fe-, Ce-oxides) resulting from weathering processes along the horizons offers the opportunity to track Nb during pyrochlore alteration from the fresh parent rock to the final stages of weathering. Intense lateritization processes have led to an enrichment in Fe and Ti in the pyrochlore B-sites, resulting in the weakening of the structure and its ultimate destabilization due to weaker B-O bonds. After the release of Nb from pyrochlore, the fate of Nb is dependent on the secondary phases formed during weathering. In the lower horizons dominated by Fe oxides, goethite is the main host for Nb (1 wt% Nb2O5) due to its capacity to substitute Fe3+ for Nb5+, in contrast to hematite. In the upper horizons, where Ti oxides have formed during the reworking of the laterite, Nb5+ is preferentially incorporated into brookite and rutile (20 wt% Nb2O5), which may have formed owing to slightly acidic pH and high Nb activity during their growth. The presence of Nb in hollandite and cerianite in a vein from the manganiferous horizon involves the transport of Nb with mobile elements at the scale of the laterite. With this study, we describe a new model accounting for the formation of Nb-enriched laterites. The latter is based on the ability of Nb5+ to substitute for Fe3+, Ti4+, Ce4+ in minerals formed by lateritization processes after its release from pyrochlore. The nature of the secondary Nb-bearing oxides is dependent on the chemistry of the parent rock and the conditions of formation of the laterite. This work, evidencing the mobilization of Nb both at the scale of the mineralogical assemblage and of the entire profile questions the pervasive use of Nb as a geochemical invariant in the critical zone.

Provenance of the Nb-rich bauxite and Li-rich claystone at the base of the Heshan Formation in Pingguo, Guangxi, SW China: Constrained by U–Pb ages and trace element contents of detrital zircon

The base of the Upper Permian Heshan Formation in Pingguo County, Guangxi Province, SW China, can be divided into two layers: a lower Nb-rich bauxite layer and an upper Li-rich claystone layer. The sources of these layers may have played a critical role in their formation. Detrital zircon provenance analysis is an effective method for identifying sediment provenance; however, it has not been applied previously to the Nb-rich bauxite and Li-rich claystone, thus limiting our knowledge of the sources of these two layers. Detrital zircons from the bauxite and the claystone layers yield a single age peak at ∼ 260 Ma, which is consistent with the age of the Emeishan Large Igneous Province (LIP; 263–257 Ma) and the Permian Palaeo-Tethyan magmatic arcs (300–260 Ma). In contrast, detrital zircons from the two layers yield different trace element signatures. Yttrium and Hf contents and U/Yb ratios of detrital zircon grains from the bauxite layer overlap with those of continental and oceanic crust and have similar Hf/Th, Th/Nb, Th/U, and Nb/Hf ratios to those of zircons of within-plate and magmatic arc origins. These results indicate that the bauxite was sourced from volcanic rocks or ash related to the Emeishan LIP and the Permian Palaeo-Tethyan magmatic arcs. However, detrital zircons from the claystone have similar Hf/Th, Th/Nb, Th/U, and Nb/Hf ratios to only those of zircon from magmatic arcs, suggesting a single Permian Palaeo-Tethyan magmatic arc source. Thus, our results reveal an abrupt change in the provenance of zircons at the base of the Heshan Formation. The lower Nb-rich bauxite layer was derived from the weathering of volcanic rocks or ash related to the Emeishan LIP and the Permian Palaeo-Tethyan magmatic arcs, whereas the upper Li-rich claystone layer was derived principally from the weathering of volcanic ash related to the Permian Palaeo-Tethyan magmatic arcs. Since Nb is an immobile element, volcanic rocks/ash related to the Emeishan LIP and the Permian magmatic arc could represent a source for bauxite and Nb. In contrast, Li is chemically highly mobile in the Earth’s surface environment and its origin cannot be constrained easily, further work is needed to identify the sources of Li.

Classification and nomenclature of volcanic rocks using immobile elements: A novel approach based on big data analysis

The proper classification and nomenclature of igneous rocks are cornerstones of geology. In contrast to intrusive rocks, volcanic rocks cannot be named after their mineral assemblages, due to their glassy and dominantly glassy nature. Thus, they are commonly classified based on their major elemental compositions, such as the Total Alkali-Silica (TAS) classification. Unfortunately, these major elements (especially K and Na) are commonly mobile during metamorphism and alteration, making the use of the TAS diagram problematic for altered or metamorphosed volcanic rocks. Though it can be replaced by diagrams employing immobile or less mobile elements, the accuracy is relatively low. By compiling data on volcanic rocks from GEOROC dataset, we confirmed that the classification based on Zr/TiO2-Nb/Y relationship has low accuracy (45.3%), so the results can be misleading. Although we improve this classification to 68.84% accuracy through refinement based on big data, the accuracy is still not satisfying. Such a deficiency can be compensated by the application of Machine Learning methods on a large dataset. Employing the Random Forest algorithm for model training based on 13 immobile elements, we propose a new classification method where the training accuracy increases to 74% for the verification dataset. Our results show that the prediction accuracy of several major rock types, such as basalt and rhyolite, increase to 89.2% and 97.5%, respectively.

Multiscale processes controlling niobium mobility during supergene weathering

Niobium (Nb) is one of the most immobile elements during supergene weathering, widely used for mass-balance calculations, despite elusive information on the mechanisms controlling its dynamics in the critical zone. Here, a multiscale approach, from weathering profile to atomic-scale, is developed to monitor Nb speciation along a thick (about 50 m) lateritic regolith formed over the Pitinga pluton (Amazonas, Brazil). In the A-type parent granite, Nb is mainly hosted in ilmenite (1.5–2 wt% Nb2O5) and, to a lesser extent, in rutile (2–3 wt% Nb2O5). A quantitative assessment of the average Nb speciation from the parent rock to the upper horizons has been carried out by combining spectroscopic and spatially-resolved chemical techniques. The contribution of Nb-bearing Ti oxides (2–6 wt% Nb2O5) and Fe oxides (0.1–0.3 wt% Nb2O5) in the average Nb speciation increases with the degree of weathering and reaches 80% in the most altered horizon. This unusual Nb speciation results from the nature of the primary Nb carriers, less resistant to weathering than common Nb ore minerals such as pyrochlore. X-ray absorption spectroscopy demonstrates that Nb released from the weathering of ilmenite substitutes for Fe and Ti in goethite and Ti oxides, respectively, providing atomic-scale evidence of the high affinity of Nb for these phases. Elemental mobility of Nb, Ta and Sn followed by geochemical mass-transfer calculations evidences lateral transport from Nb-Sn-enriched laterites developed over the surrounding Nb-enriched facies of the Pitinga granite to the studied profile. Elements such as Ti, Zr and Hf, often considered immobile, are leached or redistributed in the studied profile. Our results demonstrate Nb remobilization during intense weathering. Although Nb scavenging by secondary Fe and Ti oxides limits Nb mobility at the mineral scale, this work questions the unrestricted use of Nb as a chemical invariant during surficial alteration processes.

Understanding the provenance and depositional conditions of Triassic sedimentary rocks from the Spiti region, Tethys Himalaya, India

The Spiti region, renowned as the Museum of Indian Geology, is a world-famous sedimentary succession containing well-exposed sequences from Neoproterozoic to Cretaceous age. In this study, Triassic siliciclastic sedimentary rocks of the Lilang Supergroup were chosen to understand weathering history, provenance, paleoclimate, and depositional conditions using a geochemical and isotopic approach. Triassic shales show more or less similar compositions with substantial enrichment in CaO compared to PAAS (Post Archean shales from Australia), which may be attributed to the association with limestones in the region. However, the sandstones display significant depletion in the trace element concentrations signifying the effect of quartz dilution. The relative depletion of mobile elements (Rb, Ba) as against immobile elements (Zr, Nb, Hf) can be noticed in the trace element spider diagram of the shales. The Triassic sedimentary rocks are characterized by enriched LREE and depleted HREE patterns with pronounced negative Eu anomalies. The Chemical Index of Alteration (CIA; 56–86) indicates low to intense chemical weathering in the source area. The unusual decrease in CIA and other weathering indices in the stratigraphically up section is attributed to changes in climate and environmental conditions during the deposition of sediments in the Triassic period. Detangling the signatures is crucial to understanding the mass extinction crisis, particularly the role of anoxia in these events. Triassic black shales represent suboxic to anoxic depositional conditions in the redox-sensitive elemental binary diagrams. The carbon isotope data of the present study is very well supported by the Total Organic Carbon (TOC), which infers that the oceanic biological system tried to recover from the depletion of biological life. The εNd and 87Sr/86Sr systematics record a shift in source terrains from the Early to Late Triassic period. The Early Triassic samples show much older depleted mantle model ages (TDM = 1.94–1.98 Ga) compared to Late Triassic sediments (TDM = 1.76–1.91 Ga). Similar interpretations can be drawn from Th/Sc ratios (from ∼ 6 to ∼ 0.05) and (La/Yb) N ratios (from ∼ 32 to ∼ 5), which record an increase in these ratios from Early Triassic to Late Triassic formations of the Spiti sedimentary rocks. Overall, trace elemental ratios and radiogenic isotopic signatures of the Triassic rocks of the Spiti region point towards Pan African granitic origin with minor impressions from the juvenile mafic-rich sources, such as Panjal Traps, the African craton, and Arabian-Nubian shield.

Mineralogy, Geochemistry, and Genesis of Agates from Chihuahua, Northern Mexico

The present study aimed to investigate the genesis and characteristics of some of the world-famous agate deposits in the state of Chihuahua, Mexico (Rancho Coyamito, Ojo Laguna, Moctezuma, Huevos del Diablo, Agua Nueva). Geochemical and textural studies of host rocks showed that all the studied deposits are related to the same rock type within the geological unit of Rancho el Agate andesite, a quartz-free latite that shows clear indications of magma mixing. As a result of their large-scale distribution and various differentiation processes, as well as transport separation, different textures and local chemical differences between rocks of different localities can be observed. These differences have also influenced the properties of SiO2 mineralization in the rocks. The mixing of near-surface fluids from rock alterations with magmatic hydrothermal solutions led to the accumulation of various elements in the SiO2 matrix of the agates, which were, on the one hand, mobilized during secondary rock alteration (Fe, U, Ca, K, Al, Si) and, on the other hand, transported with magmatic fluids (Zn, Sb, Si, Zr, Cr). Different generations of chalcedony indicate a multi-stage formation as well as multiple cycles of filling the cavities with fluids. The hydrothermal fluids are presumably related to the residual solutions of a rhyolitic volcanism, which followed the latitic extrusions in the area and probably caused the formation of polymetallic ore deposits in the Chihuahua area. The enrichment of highly immobile elements indicates the involvement of volatile fluids in the agate formation. The vivid colors of the agates are almost exclusively due to various mineral inclusions, which consist mainly of iron compounds.

Geochemistry of mudrocks from the Calcare di Base Formation (Catanzaro Basin, Calabria): preliminary data

The Messinian Salinity Crisis (MSC) occurred in the Mediterranean area during the late Miocene, between two glacial stages with a strong tectonic activity characterized by paleoclimate variations (alternated dry and warm/humid period). The geochemical composition of mudrocks of the Calcare di Base Formation (Catanzaro Basin, Calabria) was studied using X-Ray Flurescence. The data reveals that the Si, Ti, Al, Na, K, Mn and P concentrations are generally depleted relative to values of the PAAS (Post- Archaean Australian Shales). In particular, Na, K and Al depletions are probably due to the paucity/absence of feldspars and clay minerals. The relationships between the mobile and immobile elements indicate a weak- moderate source area(s) weathering environments with a paleoclimate characterized by persistent dry and warm/arid conditions alternating with relatively wet conditions. The geochemical proxies of the studied samples based on elemental ratios suggest a provenance from a mainly felsic source such as the rocks composed the Sila Massif.

Relict abyssal mantle in a Caribbean forearc ophiolite (Villa Clara, central Cuba): petrogenetic and geodynamic implications

ABSTRACT The ophiolitic Villa Clara serpentinite-matrix mélange, central Cuba, forms part of the large ophiolitic belt of the Greater Antilles. The composition of ultramafic and mafic rocks allows classifying them into two main groups, revealing a complex multi-stage formation of oceanic lithosphere in varied tectonic settings: i) group 1 matches fertile MORB-like mantle typical of abyssal/transform fault peridotites, while ii) group 2 shows characteristics of refractory mantle-wedge forearc peridotites. These features are consistent with moderate extent of partial melting (4–8%) of depleted mantle at a mid-ocean ridge setting that created residual abyssal peridotite (group 1) and intense remelting (14–18%) of the latter in a forearc setting that created highly refractory peridotite (group 2). The elemental and isotopic characteristics of groups 1 and 2 serpentinites denote the influx of fluids evolved from the subducting slab. Mafic rocks appear as variably sized tectonic blocks within serpentinite that underwent variable alteration at low pressure. Immobile element concentrations allow identifying two main groups: i) group 1 is consistent with forearc basalts formed during the second stage of melting of (abyssal) peridotite, while ii) group 2 has a compositional pattern like island-arc tholeiitic basalts. A geodynamic evolution from abyssal to forearc settings is presented to explain the nature of the oceanic lithosphere of the Villa Clara ophiolitic bodies and ensuing serpentinization and mélange formation. This model may explain other ophiolitic bodies of the Caribbean arc in Cuba, Dominican Republic and Puerto Rico and elsewhere formed in abyssal/transform fault or forearc settings.