Needle Fibre Calcite Research Articles

A discussion on carbon and oxygen isotopes of secondary carbonates in loess-paleosol sequences

Although carbon and oxygen isotopic compositions of carbonates are valuable for Quaternary climate reconstruction due to their sensitivity to paleoclimate changes, a comprehensive understanding regarding the formation, factors influencing isotopic variations, and age uncertainties of secondary carbonates in loess deposits remains elusive. This study investigates the microstructure and stable isotopes of secondary carbonates, specifically calcified root cells (CRC) and needle-fiber calcite (NFC), found within the loess deposits of the last glacial period in the northwestern region of the Chinese Loess Plateau. The average δ13C values of soil total organic matter, CRC, NFC, and total inorganic carbonates in the YuanBao sections are −22.1‰, −14.9‰, −7.0‰, −4.6‰, respectively. Radiocarbon dating results reveal that both CRC and NFC were not of synsedimentary origin. The pronounced negativity of the carbon isotopic composition and the microstructures offer insights that CRC formation is closely tied to C3 plants. The synchronous depletion of δ13CCRC and δ18OCRC values during the transition period from the last glacial to the Holocene, underscores the sensitivity of isotopic composition of CRC to local environmental changes, making it a potential candidate for paleo-climate studies. Additionally, CRC formed during the glacial period provides a close approximation to the true sedimentation age. The radiocarbon dating of NFC highlights a significant fluctuation in carbon source translocation depth, resulting in a pronounced temporal and spatial decoupling between NFC formation and the surrounding deposits. Consequently, values of δ13CNFC and δ18ONFC seem to exhibit no significant trend across the limited depth range in this research. We propose that, when using NFC for paleoclimate reconstruction, careful consideration of variations in translocation depths of carbon sources is imperative to prevent misestimations. NFC could potentially be more fitting for broader temporal-scale paleoclimate reconstructions rather than high-resolution investigations.

A new source of calcium carbonate nanofibres from recarbonated lime in subsoils at European archaeological sites

Calcium carbonate nanofibres have been described from a number of natural environments and have generally been found in similar locations to those of needle-fibre calcite, such as caves, palaeosols and calcretes. Here we report large amounts of calcium carbonate nanofibres in buried archaeological stratigraphy consisting of recarbonated lime from mortar or plaster. The materials were observed in Roman and medieval contexts and could have been associated with either manufacture or use of the lime products. The phenomenon appears to be widespread, occurring in examples from UK and Latvia, with related nanosized material from Spain. Possible mechanisms are discussed, but the reason for nanofibrous crystallisation occurring in these situations is not currently understood.

Micromorphological Study of Site Formation Processes at El Sidrón Cave (Asturias, Northern Spain): Encrustations over Neanderthal Bones

El Sidrón Cave is an archaeological and anthropological reference site of the Neanderthal world. It shows singular activity related to cannibalisation, and all existing processes are relevant to explain the specific behaviour of the concerned individuals. This paper presents geoarchaeological data, primarily based on mineralogical and petrographic techniques, from an investigation of the nature of the encrustations or hard coatings that affect a large part of the Neanderthal bone remains and their relationship with the depositional and post-depositional processes at the archaeological site. Crusts and patina were found to be numerous and diverse, mainly composed of calcite and siliciclastic grains, with different proportions and textures. The analysis indicated different origins and scenarios from their initial post-mortem accumulation to the final deposit recovered during the archaeological work. The presence of micromorphological features, such as clotted-peloidal micrite, needle-fibre calcite (NFC) aggregates, clay coatings, iron–manganese impregnation, and/or adhered aeolian dust may indicate that a significant proportion of the remains were affected by subaerial conditions in a relatively short period of time in a shelter, cave entrance, or shallower level of the karstic system, prior to their accumulation in the Ossuary Gallery.

Gothic-Arch Calcite from Speleothems of the Bohemian Karst (Czech Republic): Its Occurrence, Microscopic Ultrastructure and Possible Mechanism of Growth

Gothic arch calcite, a specific crystallographic variety of calcite known from some hot springs and tufa streams, has been newly recognized in the Koněprusy Caves. The gothic-arch calcite occurs on the exteriors of exotic coralloid speleothems where it coexists with scalenohedral (dogtooth) spar crystals. The crystals exhibit microscopic ultrastructural features including deeply eroded topography, etch pits, and spiky and ribbon calcite crystallites, pointing to its extensive natural etching. Many gothic-arch calcites originated as late-stage, secondary overgrowths on older, etched dogtooth calcite crystals. Its characteristic outward curvature resulted from the recrystallization of etching-liberated fine carbonate grains and newly formed needle-fiber calcite laths, which were accumulated and bound on the faces and at the bases of corroded crystals. These intimately coexisting destructive and constructive processes of carbonate crystal corrosion and growth were probably mediated by bacteria, fungi, or other microorganisms. Fluid inclusions embedded in calcite crystals point to a vadose setting and temperatures below ~50 °C. This, combined with the wider geological context, indicates that the gothic arch calcite crystals originated only during the late Pleistocene to Holocene epochs, when the cave, initially eroded by hypogene fluids in the deeper subsurface, was uplifted to the subaerial setting and exposed to the meteoric waters seeping from the topographic surface. The radiocarbon analysis shows that gothic-arch calcite crystals are generally older than ~55,000 years, but the surface layers of some crystals still reveal a weak 14C activity, suggesting that microbiologically mediated alterations of the speleothems may have been occurring locally until now.

Bio-mineral needle fiber calcite (NFC) in Tunisian Pleistocene calcretes (topology and crystallization)

The microfacies of Pleistocene calcareous crust in Tunisia revealed the presence of diverse aspects of acicular crystallizations in a porous system. These crystallizations are in the shape of branched filaments, mono or polycrystalline rods which are either smooth or serrated (calcite), and serrated edge needle (calcium oxalate). The genesis of these acicular structures seems to be directly or indirectly linked to the organic activity. In fact, the facies are tied to the biological activity or biochemical interactions, which occur between living organisms and the mineral (calcite), triggering a succession of precipitation and dissolution reactions. These reactions, which are characteristic of vadose environments, have actively contributed to the endurance of calcareous crusts due to premature or delayed diagenesis. The acicular calcite, found in the Tunisian Pleistocene calcretes, reflects regional climates that influence the form and mineralogy of needle fiber calcite.

Pedogenic carbonate crusts (calcretes) in karstic landscapes as archives for paleoenvironmental reconstructions – A case study from Yucatan Peninsula, Mexico

In the northeastern margin of the Yucatan Peninsula, which is located in southeastern Mexico, three levels of compact carbonate crusts (calcretes) interlayered with indurated coastal calcareous sediments (calcarenites) are discernible. Since both the calcretes and calcarenites form a continuous carbonate sequence, a combined methodology (macro- and micromorphology, geochemistry and mineralogy) is used to differentiate them. Additionally, the calcrete layers are dated using the Uranium-Thorium method in order to establish a chronological framework. The carbonate differentiation and chronology are then used to establish the paleoenvironmental conditions that prevailed during calcrete formation as well as to reconstruct the coastal landscape evolution and its relation to Pleistocene sea-level changes during Marine Isotope Stages (MIS) 6 and 5. Samples of calcrete layers and calcarenites were taken from two sections in the Cancun-Tulum corridor. The lowest level of calcrete underlies a sequence of calcarenites, and the two younger levels cap the sequence. In calcretes, the micromorphology provides evidence of the presence of a relict soil with subangular blocky microstructure, root traces, and needle-fiber calcite (associated with soil-fungi interactions). In contrast, the micromorphology of the calcarenites shows ooids and bioclasts, typical of a coastal environment. Geochemically, calcretes are depleted in δ13C, compared to calcarenite, with values ranging between −2‰ and −10‰, and they have a lower proportion of rare earth elements. Calcrete mineralogy consists mainly of calcite over aragonite with a low proportion of Mg-calcite. U/Th dating indicates that the oldest calcrete was formed during the Penultimate Glacial Maximum (PGM), in MIS 6, and the two younger calcretes correspond to the Last Interglacial Period, in MIS 5c. The calcarenite formation occurred earlier, also during MIS 5. Soil formation, strong karstification and soil erosion have occurred on younger calcretes. This study suggests that these processes developed between MIS 4 to MIS 1.

The diversity of CM carbonaceous chondrite parent bodies explored using Lewis Cliff 85311

Lewis Cliff (LEW) 85311 is classified as a Mighei-like (CM) carbonaceous chondrite, yet it has some unusual properties that highlight an unrealised diversity within the CMs, and also questions how many parent bodies are sampled by the group. This meteorite is composed of rimmed chondrules, chondrule fragments and refractory inclusions that are set in a fine-grained phyllosilicate-rich matrix. The chondrules are of a similar size to those in the CMs, and have narrow fine-grained rims. LEW 85311 has been mildly aqueously altered, as evidenced by the preservation of melilite and kamacite, and X-ray diffraction results showing a low phyllosilicate fraction and a high ratio of cronstedtite to Fe, Mg serpentine. The chemical composition of LEW 85311 matrix, fine-grained rims, tochilinite and P-rich sulphides is similar to mildly aqueously altered CMs. LEW 85311 is enriched in refractory elements and REEs such that its CI-normalised profile falls between the CMs and CVs, and its oxygen isotopic composition plots in the CV-CK-CO field. Other distinctive properties of this meteorite include the presence of abundant refractory inclusions, and hundreds of micrometer size objects composed of needle-fibre calcite. LEW 85311 could come from part of a single CM parent body that was unusually rich in refractory inclusions, but more likely samples a different parent body to most other members of the group that accreted a subtly different mixture of materials. The mineralogical and geochemical evolution of LEW 85311 during subsequent aqueous alteration was similar to other CMs and was arrested at an early stage, corresponding to a petrologic subtype of CM2.7, probably due to an unusually low proportion of accreted ice. The CM carbonaceous chondrites sample multiple parent bodies whose similar size and inventory of accreted materials, including radiogenic isotopes, led to a comparable post-accretionary evolution.

Origin of strontium and calcium in pedogenic needle fibre calcite (NFC)

Strontium (Sr) and calcium (Ca) isotopic compositions and Sr/Ca ratios have been analysed in different fractions of pedogenic needle fibre calcite (NFC) from the Swiss Jura Mountains (Villiers, Neuchâtel, Switzerland) in order to determine their Ca sources and to investigate the potential role of fungi in the origin of NFC. 87Sr/86Sr ratios have been measured to trace the Ca trapped within different pedogenic carbonate. This ratio was compared for previously identified microscopic morphological groups of NFC, the bulk soil fine earth (<2 mm), the carbonate host rock (CHR), a late calcitic cement (LCC, another pedogenic carbonate precipitated physicochemically at the same depth as NFC in soil pores), the soil solution, and the throughfall. The 87Sr/86Sr indicated a mixing of weathered allochthonous minerals (an atmospheric component) and the dissolved CHR (the local geogenic component). Moreover, the comparison of 87Sr/86Sr ratios of the different types of NFC with LCC suggests that the contribution of Ca from the main Ca sources slightly differs between NFC morphotypes and LCC. In addition, the three NFC morphotypes displayed Sr isotopic compositions different from each other, emphasizing a direct relationship between the microscopic shapes of NFC and the processes involved in their respective formation, including the origin of the Ca. Strontium concentrations and δ44/40Ca values of NFC and LCC crystals were used to determine possible differences in their growth rate and/or micro-environmental conditions during their formation. Crystals described micromorphologically as simple needles (SN) were enriched in 44Ca and depleted in Sr compared to LCC, suggesting that the elongated shape of the SN crystal cannot be related to a rapid precipitation rate, but rather to a slow precipitation. Calculations applied to the soil solution evolution during calcite precipitation demonstrates the utilisation of large portions of the Ca pool for NFC formation within a closed system, e.g. inside an organic mould, such as fungal hyphae. The differences between the three microscopic groups can be explained by a mixing of the SN with a LCC-like compound originating from the soil solution.

Palaeoenvironmental significance and pathways of calcrete development investigated with nuclear and related methods

The genesis and development of calcretes are discussed by using nuclear and related methods of analyses. In the studied calcrete, smectite is the main clay mineral associated with palygorskite. Chemical elements proportions, particularly V, U, Mn, Cu, Ba and REE, indicate a change to more oxidizing conditions and the contribution of bio-mediated processes in the oxalate-carbonate pathway, also confirmed by the presence of needle-fibre calcite. The proposed pathways leading to the studied calcrete development comprise both abiotic and biogenic genesis, emphasizing the polygenetic character due to different agents and processes and the paleoenvironmental trend towards aridification, with a transition between lacustrine and palustrine environments.

Petrography, micromorphology and geochemistry of Mio-Pleistocene palustrine limestones in Kuwait, Arabian Gulf

Elongated lenses of palustrine limestone interbedded with Mio-Pleistocene fluvial sands were exposed within a sand quarry in the north of Kuwait. Detailed field investigations, thorough petrographic and nanoscopic examinations and geochemical analysis revealed that they were originally precipitated as carbonate microbialite in isolated freshwater ponds scattered within a fluvial floodplain. These lacustrine microbialites were subjected to intermittent drying and wetting conditions and eventually altered to pseudobrecciated nodular palustrine limestone through several pedogenic and early diagenetic processes. The pedogenesis is exhibited by cracking, nodulization, mottling, pseudomicrokarst and root traces. The desiccation macrocracks are filled with siliciclastic sands derived from short-lived flash floods. Diagenesis is represented by aggradational neomorphism of micrite, cementation of cracks and voids by sparry calcite and precipitation of biogenic needle-fibre calcite. Concurrently, the cracks filled with siliciclastic sands have been calcretized, forming an embedded interapalustrine calcrete. Mottling postdates the early diagenesis and is manifested by pseudoclotted texture and abundant black spots and dendrites, which may have been developed by the marmorization of iron and manganese ions due to the seasonal fluctuation of groundwater. The δ13C and δ18O values are mostly comparable with those of closed freshwater lakes; however, the high negative values of δ18O may be attributed to diagenetic calcite. The occurrence of this palustrine limestone within a fluvial siliciclastic sequence that lacks clearly developed calcrete profiles may present an exceptional setting for palustrine limestone.

At the water's edge: Micromorphological and quantitative mineral analysis of a submerged Mesolithic shell midden at Hjarnø Sund, Denmark

This study presents the first application of micromorphology and Automated Scanning Electron Microscopy (ASEM) to a submerged shell-bearing midden site in Denmark, one of the few submerged shell-matrix sites in the world to have undergone archaeological excavation. The use of micromorphology in these deposits provides a means to distinguish primary and secondary deposits and degree of preservation. The additional input of quantitative mineral analysis provides an empirical tool for correlation of minerogenic components across the site and assessing change through time. Micromorphological insights into the formation history and post-depositional modification include epizootic infestations within oyster shells at the base of the profile and needle-fibre calcite at the top - the former is indicative of accumulation of at least part of the shell midden below water, whilst the latter is indicative of exposure. Aside from the shell itself, other cultural traces include heated and worked flint fragments, burnt and unburnt hard bone fragments (including fish bone), soft (spongy) bone, charcoal (Ulmus sp., Alnus sp., Corylus sp.), and preservation of what could possibly be antler velvet. Quantitative mineral analyses provide support for the successive stabilisation of the midden site by accumulating minerogenic (silica-rich) sands over the glacial clay and detrital gyttja deposits (defined by smaller grain size, greater heavy mineral content), and subsequently between the shell matrix itself, until the erosion of these protective sediments in more recent times. Further micromorphological profiles are needed to fully assess local versus regional signatures within the site, which otherwise provides an ideal context against which to compare the effects of inundation in similar microtidal contexts.

Calcite moonmilk of microbial origin in the Etruscan Tomba degli Scudi in Tarquinia, Italy

A white deposit covering the walls in the Stanza degli Scudi of the Tomba degli Scudi, Tarquinia, Italy, has been investigated. In this chamber, which is still preserved from any kind of intervention such as cleaning and sanitization, ancient Etruscans painted shields to celebrate the military power of the Velcha family. Scanning electron microscopy analysis has revealed the presence of characteristic nanostructures corresponding to a calcite secondary mineral deposit called moonmilk. Analysis of the microbial community identified Proteobacteria, Acidobacteria and Actinobacteria as the most common phyla in strong association with the moonmilk needle fibre calcite and nanofibers of calcium carbonate. Employing classical microbiological analysis, we isolated from moonmilk a Streptomyces strain able to deposit gypsum and calcium carbonate on plates, supporting the hypothesis of an essential contribution of microorganisms to the formation of moonmilk.

Study of a modern calcrete forming in Guadalajara, Central Spain: An analogue for ancient root calcretes

The Pajares calcrete in Central Spain, a modern calcrete, consists of an accumulation of powder carbonate around the roots of living trees and bushes which penetrates Miocene deposits by more than 3 m. Calcrete development is mostly vertical and oblique, but thinner horizontal calcified root mats also occur. Carbonate accumulation, up to 15 cm thick, is made up of micrite with some etched clasts, alveolar septal structures, calcified rootlets, coated grains and micrite grains. In detail many of these features are composed of needle fibre calcite and micro-rods. Accumulation of carbonate was produced both by roots through direct calcification of their cells and also by microbial activity within the rhizosphere. This case study provides a good example of how carbonate is accumulating around roots at present and may allow better understanding of ancient calcretes, especially those which formed directly around roots in direct contact with the host rock. In addition the calcrete's setting, and its occurrence around roots belonging to various types of plants, suggest that carbonate accumulation in modern landscapes may be a relatively rapid, common process even in erosive regimes, and unrelated to specific vegetation types.

Biogenic (β-fabric) features in the hard laminated crusts of the Mersin and Adana regions, southern Turkey and the role of soil organisms in the formation of the calcrete profiles

This paper describes β-fabric features and their distribution in the calcretes, and emphasizes the role of soil organisms in the formation of the calcrete profiles. Quaternary calcretes are common in the Mersin and Adana provinces occurring as powdery, nodular, tubular, fracture-infill and various forms of crusts. The stable isotope values indicate calcrete development under semi-arid climatic conditions and a pedogenic origin. Biogenic or β-fabric constituents are abundant in the hard laminated crust. These are the rhizoliths, alveolar septal structures, needle-fiber calcites, calcified filaments, spherical calcite bodies, microcodium and vadose (calcrete) pisoliths. Rhizoliths have mainly formed by the petrification of roots, and often contain cellular cortex structures. The alveolar septal structure comprises root-voids separated by a micritic wall or a bundle of tangentially oriented calcite needles. Needle-fiber calcite is common in the hard laminated crust as monocrystalline rods and polycrystalline needles. Monocrystalline rods are smooth and small (<1μm in length), whereas polycrystalline needles consist of a chain of calcite rhombs stacked as parallel c-axes. The elongated crystals generally form interwoven masses. The calcified filaments are straight to slightly curved tubular microstructures with a central hollow. Microcodiums are rosette-like aggregates composed of slightly curved radial-fibrous calcite crystals extending from a central cavity. Vadose pisoliths consist of irregularly coated microbial laminae around a nucleus, and often show a downward elongation indicating an in-situ formation. All these biogenic features indicate a pedogenic origin for calcretes. Their abundance in the hard laminated crust points to calcification in a biologically active zone and maturation in calcrete formation with a thin soil cover.

Growth and development of spring towers at Shiqiang, Yunnan Province, China

Throughout the world, high artesian pressures in hydrothermal areas have led to the growth of tall spring towers that have their vents at their summits. The factors that control their development and formative precipitates are poorly understood because these springs, irrespective of location, are mostly inactive. Spring towers found at Shiqiang (Yunnan Province, China), which are up to 4m high and 3m in diameter, are formed largely of calcite and aragonite crystal bushes, euhedral calcite crystals and coated grains with alternating Fe-poor and Fe-rich zones, calcite rafts, and cements formed of various combinations of calcite, aragonite, strontianite, Mg-Si reticulate, needle fiber calcite, calcified and non-calcified microbes, diatoms, and insects. Collectively, the limestones that form the towers can be divided into (1) Group A that are friable, porous and form the cores of the towers and have δ18OSMOW values of +15.7 to +19.7‰ (average 17.8‰) and δ13CPDB values of +5.1 to +6.9‰ (average 5.9‰), and (2) Group B that are hard and well lithified and found largely around the vents and the tower sides, and have δ18OSMOW values of +13.0 to +22.0‰ (average 17.6‰) and δ13CPDB values of +1.4 to +3.6‰ (average 2.6‰). The precipitates and the isotopic values indicate that these were thermogene springs. Growth of the Shiqiang spring towers involved (1) Phase IA when precipitation of calcite and aragonite bushes formed the core of the tower and Phase IB when calcite, commonly Fe-rich, was precipitated locally, (2) Phase II that involved the precipitation of white cements, formed of calcite, aragonite, strontianite, and Mg-Si reticulate coatings in cavities amid the Phase I precipitates, and (3) Phase III, which formed probably after spring activity ceased, when needle-fiber calcite was precipitated and the mounds were invaded by microbes (some now calcified), diatoms, and insects. At various times during this complex history, pore waters mediated dissolution of the calcite and aragonite and sometimes partial alteration of the aragonite. The diverse array of precipitates, depositional fabrics and diagenetic changes clearly indicate that the composition of the spring water changed frequently. Growth of the spring towers at Shiqiang continued until there was insufficient artesian pressure to lift the water above the top of the tower vent.

Carbon dioxide in scree slope deposits: A pathway from atmosphere to pedogenic carbonate

A continuum of carbon, from atmospheric CO2 to secondary calcium carbonate, has been studied in a soil associated with scree slope deposits in the Jura Mountains of Switzerland. This approach is based on former studies conducted in other environments. This C continuum includes atmospheric CO2, soil organic matter (SOM), soil CO2, dissolved inorganic carbon (DIC) in soil solutions, and secondary pedogenic carbonate. Soil parameters (pCO2, temperature, pH, Cmin and Corg contents), soil solution chemistry, and isotopic compositions of soil CO2, DIC, carbonate and soil organic matter (δ13CCO2, δ13CDIC, δ13Ccar and δ13CSOM values) have been monitored at different depths (from 20 to 140cm) over one year. Results demonstrated that the carbon source in secondary carbonate (mainly needle fiber calcite) is related to the dissolved inorganic carbon, which is strongly dependent on soil respiration. The heterotrophic respiration, rather than the limestone parent material, seems to control the pedogenic carbon cycle. The correlation of δ13Corg values with Rock-Eval HI and OI indices demonstrates that, in a soil associated to scree slope deposits, the main process responsible for 13C-enrichment in SOM is related to bacterial oxidative decarboxylation. Finally, precipitation of secondary calcium carbonate is enhanced by changes in soil pCO2 associated to the convective movement of air masses induced by temperature gradients (heat pump effect) in the highly porous scree slope deposits. The exportation of soil C-leachates from systems such as the one studied in this paper could partially explain the “gap in the European carbon budget” reported by recent studies.

Abiogenic Growth of Needle-Fiber Calcite In Spring Towers At Shiqiang, Yunnan Province, China

Abstract At Shiqiang, China, there are spring towers, up to 4 m high and 3 m in diameter, that are formed of porous, gray to orange to brown, bedded limestones that have a multistage diagenetic history. The walls of many cavities in these limestones are covered with hypocoatings and/or needle-fiber calcite (NFC) that formed during the last stage of diagenesis. Where present, the hypocoatings are ∼ 10 µm thick, appear homogeneous, and typically lie under the NFC mats. The NFC is divided into nanofibers (rods, < 1 µm long, 75–100 nm diameter), composite fibers (bundles of 2 to 16 rods, each rod 300–400 nm in diameter, up to 25 µm wide and 100 µm long), pyramid fibers (pyramid shape with 4 to 6 sides, up to 25 wide at base, tapering to point, up to 100 µm long), and ribbon fibers (blade shape, 2–4 µm wide, ∼ 1 µm thick, up to 100 µm long). Many crystals are highly ornate with epitaxial overgrowths that display elements of skeletal and/or dendritic growth. The wall-covering NFC mats are formed of one crystal type or any combination of different crystal types, with or without epitaxial overgrowths. Precipitation of needle-fiber calcite, known from a diverse array of geological settings throughout the world, is commonly linked to fungi or other biogenic processes. In the Shiqiang spring towers, however, no fungi were found with the NFC and only scattered microbes and minor amounts of exopolysaccharides were associated with some of the NFC in some pores. The NFC crystals appear to have been precipitated from fluids that were highly saturated with respect to calcite as a result of evaporation. The calcium probably came from rainwater, groundwater (via capillary action), and/or dissolution of the calcite framework whereas evaporation was mediated by solar radiation and/or the wind. Available evidence indicates that the NFC found in the spring deposits at Shiqiang were a late diagenetic product that probably formed through abiogenic precipitation.

Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

Abstract. Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3) accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i) purely physicochemical processes, (ii) mineralization of rod-shaped bacteria, and (iii) crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic) or organic in nature. They are very often observed in association with needle fibre calcite (NFC), another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this paper the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of fungi in CaCO3 biomineralization processes, a role still poorly documented. Moreover, on a global scale, the organomineralization of organic nanofibres into calcitic nanofibres might be an overlooked process deserving more attention to specify its impact on the biogeochemical cycles of both Ca and C.

Root Calcretes and Uranium-Bearing Silcretes At Sedimentary Discontinuities In the Miocene of the Madrid Basin (Toledo, Spain)

Abstract This paper reports a detailed study of the calcrete and silcrete profiles in the Miocene detrital deposits in the western area of Madrid, at the boundary of two main sedimentary units. The aims of this work were to better understand the pedogenic and diagenetic environments in which these profiles formed and to determine the cause(s) of their enrichment in uranium. Calcrete and silcrete duricrusts are characteristic features of closed continental basins in semiarid climates; this paper discusses the significance of duricrusts as indicators of important change in such basins. The detailed macromorphological, micromorphological, and geochemical study of three duricrust profiles revealed the sequence of pedogenic, vadose, and groundwater processes responsible for their formation. During the first stage of their development, carbonate laminae formed a white “grill-like” structure within the detrital parent materials. The microstructure and macrostructure of the carbonate, which includes alveolar septal structures and needle-fiber calcite, indicates the important role of roots and their associated microorganisms in calcrete formation. Early silicification occurred in the pedogenic-vadose environment affecting the detrital parent material, roots, and calcretes, forming an early silcrete defined by opaline glaebules and silica rhizoliths. The detailed preservation of the cells in the silicified roots denotes the early replacement of root organic matter. The green or green-yellowish fluorescence of the silicified root structures under short-wavelength UV shows their preferential enrichment in uranium. Calcitization and silicification coexisted in the pedogenic vadose environment, leading to several reversible replacements of calcite and silica. Later, the rise of the water table promoted silicification under phreatic conditions, as indicated by the good preservation of the texture of the detrital host rocks and calcretes. Other silcrete textures, such as ovoidal opaline accumulations, intraclasts produced by autobrecchification, and vadose silica cements, indicate later vadose environments, and consequently variations in the water table. The geochemical features of the calcretes and silcretes (major, minor, and rare earth elements) were inherited from their parent materials. The rare-earth-element patterns of some silcretes show them to have a positive Ce anomaly, suggesting that oxidizing conditions reigned during their formation. The good correlation between silica and uranium suggests that the silica phases acquired uranium through the direct silicification of roots that had fixed uranium from organic matter. This study shows that calcrete–silcrete duricrusts provide detailed information regarding the processes occurring in semiarid continental basins. In the studied basin, roots played a key role in both the development of the duricrust profiles and their enrichment in uranium. These duricrusts provide important information for understanding the overall stratigraphy of the studied basin and its large-scale sequential evolution.

A new form of needle-fiber calcite produced by physical weathering of shells

Needle-fiber calcite is a common crystal form in soils and sediments from diverse environmental settings, and it has been used as evidence of a specific soil development either past or present. However, it can have either a physicochemical or a biological origin and its ubiquity prevents straightforward use as an environmental proxy. In this paper, we present a new form of needle-fiber calcite, derived neither from biologically mediated mineralization in the soil nor from physicochemical precipitation. This needle-fiber calcite is monocrystalline and prismatic, and is associated with the physical weathering of Mytilus edulis (Linnaeus) bivalve shells found in soils from anthropic shell middens located on the northern coast of the Beagle Channel (Argentina). The effects of freeze–thaw cycles can be observed in the local soils and would be responsible for the release of the calcite crystals that make up the outer layer of the shell. In this respect, the new form of needle-fiber calcite would be specific for this process in anthropogenic soils in cold climates, and could provide information on past climatic conditions.