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Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay authigenesis still remains poorly known. In this study, we report on a detailed geochemical investigation of glauconite from the West African continental shelf, near the mouth of the Congo River. Elemental, neodymium, and hafnium isotope analyses were conducted on both acid leachate and separated clay-size fractions of glauconite pellets, in order to investigate the behavior of REE during the formation of authigenic clays. Our data indicate that kaolinite dissolution and subsequent Fe-bearing clay authigenesis act as a net source of REEs to seawater. We show that enhanced glauconitization, as inferred from increasing Fe and K contents, is accompanied by significant decoupling of the REE toward markedly LREE-enriched shale-normalized patterns in neoformed clay separates. Using both Nd and Hf isotopes and SEM observations, we rule out any seawater influence and argue that this shift primarily reflects the progressively overwhelming presence of insoluble nanocrystals of detrital LREE-rich phosphates, which are known to occur in close association with kaolinite in tropical soils. Due to their marked insolubility in surface environments, such nanocrystals can be preserved during kaolinite dissolution and subsequently incorporated into the aggregates of authigenic green clays forming the peloids. Most strikingly, we show that the combined influence of net REE loss (due to kaolinite dissolution) and decoupling (due to subsequent entrapment of inherited LREE-bearing accessory phases into neoformed clay minerals) is accompanied by preferential release of a dissolved REE fraction characterized by seawater-like distribution patterns. These findings reinforce the emerging view that clay mineral dissolution and authigenesis at continental margins possibly play a major role in marine REE cycling.

The characterization of Mg-clays in rock samples (well P1) from the Barra Velha Formation (Early Cretaceous) allowed the establishment of mineral assemblages on the basis of their kerolite and Mg-smectite (stevensite and saponite) content. Kerolite-rich assemblages (A and B) rarely contain saponite. Assemblage B is composed of kerolite-stevensite mixed layers, while assemblage A consists of more than 95% kerolite. Mg-smectite-rich assemblages (C and CB) are made up of both Mg-smectites. The predominance of stevensite in the lower interval of the stratigraphic succession suggests evaporative conditions, higher salinity and pH, which would favor its authigenesis by neoformation. In the upper portion, the occurrence of thick kerolite-rich intervals suggests regular water inputs, contributing with a decreasing in salinity and pH, favoring the neoformation of kerolite and later kerolite-stevensite mixed layering. The saponite would be the result of the transformation from Al-smectite into Mg-smectite in a Mg2+ rich medium. The results indicate that lake hydrochemical processes would have allowed the establishment of a basic depositional sequence, from base to top, as follows: (i) initial lake expansion stage marked by the occurrence of saponite, (ii) later kerolite neoformation, (iii) formation of kerolite-stevensite mixed layer with increasing salinity, and (iv) neoformation of stevensite, marking a final stage of maximum salinity (evaporation) and alkalinity of the lake.

The Curiosity rover has documented lacustrine sediments at Gale Crater, but how liquid water became physically stable on the early Martian surface is a matter of significant debate. To constrain the composition of the early Martian atmosphere during sediment deposition, we experimentally investigated the nucleation and growth kinetics of authigenic Fe-minerals in Gale Crater mudstones. Experiments show that pH variations within anoxic basaltic waters trigger a series of mineral transformations that rapidly generate magnetite and H2(aq). Magnetite continues to form through this mechanism despite high partial pressure of carbon dioxide (pCO2) and supersaturation with respect to Fe-carbonate minerals. Reactive transport simulations that incorporate these experimental data show that groundwater infiltration into a lake equilibrated with a CO2-rich atmosphere can trigger the production of both magnetite and H2(aq) in the mudstones. H2(aq), generated at concentrations that would readily exsolve from solution, is capable of increasing annual mean surface temperatures above freezing in CO2-dominated atmospheres. We therefore suggest that magnetite authigenesis could have provided a short-term feedback for stabilizing liquid water, as well as a principal feedstock for biologically relevant chemical reactions, at the early Martian surface.

Enhanced continental phosphorus input into the ocean has been suggested as a potential trigger for the transient oxygenation events during the mid‐Proterozoic; however, the response of phosphorus cycling to these marine oxygenations remains unclear. Here, we report the changes in phosphorus cycling associated with a ∼1.7 Ga transient oxygenation. Abundant authigenic aluminum phosphate–sulfate mineral svanbergite (SrAl3(PO4) (SO4) (OH)6; 8.02 ± 4.92 wt%) is identified within the ∼1.7 Ga Yunmengshan ironstones from the Xiong'er Basin, North China and other contemporaneous basins. This observation provides new evidence to support the suggestion that early diagenetic aluminum phosphate‐sulfate minerals could have represented a critical sink of marine phosphorus during the Proterozoic. We suggest that atmospheric oxygenation and concomitant changes in porewater redox chemistry may have enhanced the formation of early diagenetic phosphates, leading to a negative feedback on the oceanic phosphorus reservoir and atmospheric oxygen levels. Plain Language Summary It becomes increasingly clear that multiple transient oxygenation events likely punctuated the low background oxygen world during the mid‐Proterozoic. This may imply that a negative feedback could have inhibited a secular rise in atmospheric oxygen, though the deoxygenation mechanisms remain unclear. Phosphorus (P) availability regulated primary production and therefore controlled the atmospheric oxygen levels during this time, and oxygenation would in turn affect phosphorus cycling. Here we investigate the P cycling during a ca. 1.7 Ga transient oxygenation using mineralogical and geochemical methods. The results show an enhanced phosphorus burial during this transient oxygenation. The elevated phosphorus and sulfate inputs from the enhanced continental weathering and oxygenation may have promoted the formation of aluminum phosphate‐sulfate minerals. This, in turn, reduced the bio‐availability of phosphorus in the marine environment, ultimately limiting marine productivity and leading to a negative feedback on the oxygenation event. This study highlights that phosphorus cycling pathway, which was previously overlooked, may have played a role in the deoxygenation during the intermittent oxygenation events in the mid‐Proterozoic. Key Points Abundant phosphorus and sulfur precipitation as authigenic svanbergite is associated with the ∼1.7 Ga transient oxygenation The oxygenation resulted in suboxic and acidic porewater conditions rich in P‐ and sulfate, facilitating the authigenesis of svanbergite The enhanced P and S burial as svanbergite represents a significant but overlooked negative feedback during the transient oxygenation

The terminal Ediacaran Dengying Formation (c. 551.1-538.8 Ma) in South China is one of two successions where Ediacara-type macrofossils are preserved in carbonate facies along with skeletal fossils and bilaterian animal traces. Given the remarkable thickness of carbonate-bearing strata deposited in less than 12.3 million years, the Dengying Formation holds the potential for construction of a relatively continuous chemostratigraphic profile for the terminal Ediacaran Period. In this study, a detailed sedimentological and chemostratigraphic (δ13Ccarb, δ18Ocarb, δ13Corg, δ34Spyrite, and 87Sr/86Sr) investigation was conducted on the Dengying Formation at the Gaojiashan section, Ningqiang County of southern Shaanxi Province, South China. Sedimentological results reveal an overall shallow-marine depositional environment. Carbonate breccia, void-filling botryoidal precipitates and aragonite crystal fans are common in the Algal Dolomite Member of the Dengying Formation, suggesting that peritidal facies were repeatedly karstified. The timing of karstification was likely early, probably soon after the deposition of the dolomite sediments. The presence of authigenic aragonite cements suggests high alkalinity in the terminal Ediacaran ocean. Geochemical analysis of micro-drilled samples shows that distinct compositions are registered in different carbonate phases, which should be considered when constructing chemostratigraphic profiles representative of true temporal variations in seawater chemistry. Integrated chemostratigraphic data suggest enhanced burial of organic carbon and pyrite, and the occurrence of extensive marine anoxia (at least in the Gaojiashan Member). Rapid basinal subsidence and carbonate accumulation during a time of elevated seawater alkalinity and increased rates of pyrite burial may have facilitated the evolutionary innovation of early biomineralizing metazoans.

Marine clay mineral authigenesis, referred to as reverse (silicate) weathering, is one of the first-order controls on seawater pH through the generation of acidity and thus plays a significant role in controlling carbon cycling between marine sediments, oceans and the atmosphere over geological timescales. Reverse weathering is mainly regulated by the rates of silicate and carbonate weathering on the continents, the reactivity of detritus supplied to the oceans and the rates of seafloor weathering. These processes provide essential dissolved components (e.g. K+, Mg2+, Ca2+, Si(OH)4, Al3+, Fe2+/3+) to the marine porewater inventory that cause authigenic clay minerals, such as odinite, glauconite, celadonite and greenalite, to form close to the sediment-seawater interface. Such clay mineral reactions impact the sedimentary cycling versus sequestration of chemical elements, importantly Si, Fe, Mg and K, and consequently contribute to the fluctuations in climate and seawater composition recorded in marine archives over geological time. This review explores the links between reverse silicate weathering and the climate system across geological timescales and provides estimates of the elemental uptake fluxes associated with modern-day clay mineral authigenesis. Novel isotope proxies (e.g. δ41K and δ30Si) and promising new dating techniques (e.g. in situ Rb/Sr geochronology) provide improved constraints on the timing, kinetics and environmental significance of clay mineral reactions on the ocean floor. We also consider recent geoengineering developments linked to reverse weathering reactions, such as ongoing attempts to reduce atmospheric CO2 concentrations via marine alkalinity enhancement and the application of marine clay mineral-based slow-release fertilizers to soils to optimize nutrient availability.

Clay authigenesis mostly concerns: (a) the formation of clays by direct precipitation from solution, called “neoformation” and (b) development of clays by transformation of precursor minerals. Precipitation from solution implies that a new mineral structure crystallizes, so that a prior mineral structure is not inherited. Transformation of precursor detrital minerals, a process also termed “neoformation by addition”, can be conducted whether throughout precipitation on pre-existing natural surfaces or transformation and reaction on pre-existing surfaces. Both processes have been recognized as effective mechanisms in the formation of Mg-clays, which mostly include 2:1 clay minerals, such as talc-kerolite and Mg-smectites, as well as fibrous clays (sepiolite, palygorskite). Authigenic Mg-clay minerals occur in both modern and ancient marine and non-marine depositional environments, although formation of these clays in hydrothermal continental and seafloor settings must be also outlined. Most favourable conditions for the formation of Mg-clays on earth surface are found in evaporitic depositional environments, especially where parent rocks are enriched in ferromagnesian minerals. In these settings, Mg-clays are important constituent of weathering profiles and soils and can form thick deposits of significant economic interest. Based on this review of authigenic clay deposits, we propose three geochemical pathways, mainly related to continental environments, for the origin of authigenic Mg-clays: formation of Al-bearing Mg-clays (pathway 1), formation of Al-free Mg clays (pathway 2) and formation of sepiolite from other Mg-clay minerals (pathway 3).

The rare earth elements (REEs) are an important tool for understanding biogeochemical cycling and sedimentary processes in the global ocean. However, ambiguities in the marine REE budgets, including questions around the dominant source of REEs to the ocean, hinder the application of this tool. A bottom-up model for REE release into the ocean has recently been proposed, driven by early diagenetic processes such as sediment dissolution, with potentially significant implications for the interpretation of marine REE and Nd isotope paleo-records. Here, our goal is to identify the phase or phases that interact with the pore fluids to drive such a benthic flux. We use new pore water REE, microbeam imaging and mineralogical data in combination with published pore water REE data to evaluate potential sedimentary REE host phases. Mineralogical and direct imaging observations suggest that authigenic Fe or Mn oxyhydroxides, which are widely considered a dominant REE host phase, are not sufficiently abundant sediment components to account for the high Nd concentrations recovered in reductive leaches, and are unlikely to be the primary source of pore water REEs. Pore water REE signatures similar to river sourced clays indicate a detrital clay dissolution source, while the spread in heavy to light REE enrichment in pore fluids and bottom waters relative to this clay source is best explained by fractionation during authigenic clay uptake of REEs. We therefore conclude that clay mineral dissolution and authigenesis are likely the primary influences on the REE cycling near the seafloor. We propose that the balance between dissolution and authigenesis controls the concentration, ratio of heavy and light REE abundances, and the isotopic composition of the pore waters. We discuss the implications of this hypothesis on an oceanic REE budget controlled by a benthic flux from a sedimentary REE source, and the use of authigenic neodymium isotopes as a paleoproxy for shifts in ocean circulation.

Clay minerals in structurally complex settings influence fault zone behavior and characteristics such as permeability and frictional properties. This work aims to understand the role of fault zones on clay authigenesis in arkosic, high-porosity sandstones of the Cretaceous Rio do Peixe basin, northeast Brazil. We integrated field, petrographic and scanning electron microscopy (SEM) observations with X-ray diffraction data (bulk and clay-size fractions). Fault zones in the field are characterized by low-porosity deformation bands, typical secondary structures developed in high-porosity sandstones. Laboratory results indicate that in the host rock far from faults, smectite, illite and subordinately kaolinite, are present within the pores of the Rio do Peixe sandstones. Such clay minerals formed after sediment deposition, most likely during shallow diagenetic processes (feldspar dissolution) associated with meteoric water circulation. Surprisingly, within fault zones the same clay minerals are absent or are present in amounts which are significantly lower than those in the undeformed sandstone. This occurs because fault activity obliterates porosity and reduces permeability by cataclasis, thus: (1) destroying the space in which clay minerals can form; and (2) providing a generally impermeable tight fabric in which external meteoric fluid flow is inhibited. We conclude that the development of fault zones in high-porosity arkosic sandstones, contrary to other low-porosity lithologies, inhibits clay mineral authigenesis.

Phosphorus is often invoked as the ultimate limiting nutrient, modulating primary productivity on geological timescales. Consequently, along with nitrogen, phosphorus bioavailability exerts a fundamental control on organic carbon production, linking all the biogeochemical cycles across the Earth system. Unlike nitrogen that can be microbially fixed from an essentially infinite atmospheric reservoir, phosphorus availability is dictated by the interplay between its sources and sinks. While authigenic apatite formation has received considerable attention as the dominant sedimentary phosphorus sink, the quantitative importance of reduced iron-phosphate minerals, such as vivianite, has only recently been acknowledged, and their importance remains underexplored. Combining microscopic and spectroscopic analyses of handpicked mineral aggregates with sediment geochemical profiles, we characterize the distribution and mineralogy of iron-phosphate minerals present in methane-rich sediments recovered from the northern South China Sea. Here, we demonstrate that vivianite authigenesis is pervasive in the iron-oxide-rich sediments below the sulfate–methane transition zone (SMTZ). We hypothesize that the downward migration of the SMTZ concentrated vivianite formation below the current SMTZ. Our observations support recent findings from non-steady-state post-glacial sedimentary successions, suggesting that iron reduction below the SMTZ, probably driven by iron-mediated anaerobic oxidation of methane (Fe-AOM), is coupled to phosphorus cycling on a much greater spatial scale than previously assumed. Calculations reveal that vivianite acts as an important burial phase for both iron and phosphorus below the SMTZ, sequestering approximately half of the total reactive iron pool. By extension, sedimentary vivianite formation could serve as a mineralogical marker of Fe-AOM, signalling low-sulfate availability against methanogenic and ferruginous backdrop. Given that similar conditions were likely present throughout vast swathes of Earth's history, it is possible that Fe-AOM and vivianite authigenesis may have modulated methane and phosphorus availability on the early Earth, as well as during later periods of expanded marine oxygen deficiency. A better understanding of vivianite authigenesis, therefore, is fundamental to test long-standing hypotheses linking climate, atmospheric chemistry and the evolution of the biosphere.