Early Diagenesis Research Articles

Early diagenesis, sedimentary dynamics and metal enrichment reveal deep-sea ventilation in Magellan Seamounts during the middle Pleistocene

Seamounts are ubiquitous topographic units in the global oceans, and the Caiwei Guyot in the Magellan Seamounts of the western Pacific is a prime example. In this study, we analyzed a well-dated sediment core using magnetic properties, sediment grain size, and metal enrichment to uncover regional ventilation history during the middle Pleistocene and explore potential linkages to global climate changes. Our principal findings are as follows: (1) The median grain size is 3.3 ± 0.2 μm, and clay and silt particles exhibit minimal variation, with average values of 52.8 ± 1.8% and 38.2 ± 1.6%, respectively, indicating a low-dynamic process; (2) Three grain-size components are identified, characterized by modal patterns of ~3 μm (major one), ~40 μm, and 400–500 μm, respectively; (3) Magnetic coercivity of the deep-sea sediments can be classified into three subgroups, and their coercivity values are 6.1 ± 0.5 mT, 25.7 ± 1.0 mT, and 65.2 ± 2.1 mT. Based on these results, we propose a close linkage between magnetic coercivity and metal enrichment, correlating with changes in deep-sea circulation intensity. Conversely, sediment grain-size changes seem to be more strongly influenced by eolian inputs. Consequently, we suggest that regional ventilation has weakened since ~430 ka, likely linked to a reduction in Antarctic bottom water formation.

Iron redox shuttling and uptake by silicate minerals on the Namibian mud belt

Anoxic marine sediments represent an important source of bioavailable iron (Fe) to the ocean. The highest sedimentary Fe fluxes are observed in open-marine oxygen minimum zones where anoxic bottom waters are in contact with ferruginous surface sediments. Here, sedimentary Fe release, transport and re-deposition (i.e., Fe shuttling) may generate a lateral pattern of sedimentary Fe enrichment and depletion, which can be used to trace redox-related Fe mobility in the paleo-record. However, depending on the balance between terrigenous and authigenic (i.e., shuttle-related) Fe flux, the stability of bottom water redox conditions as well as post-depositional processes of mineral alteration, the sedimentary fingerprint of an Fe redox shuttle may be obscured and difficult to identify.We investigated sedimentary Fe cycling along two transects across the Namibian mud belt with variable terrigenous sedimentation (23°S < 25°S) and during two seasons with opposing bottom water redox conditions (oxic in austral winter versus anoxic to sulfidic in austral summer). On both transects, substantial benthic Fe fluxes up to −50 µmol m−2 d−1 were inferred based on pore water profiles. The magnitude of these fluxes is comparable to those reported for other open-marine oxygen minimum zones. On the transect at 23°S, Fe source areas with ferruginous surface sediments were clearly separated from Fe sink areas with highly sulfidic surface sediments. Therefore, Fe redox shuttling was reflected by a lateral pattern of reactive Fe depletion and enrichment relative to the terrigenous background sedimentation. By contrast, on the transect at 25°S, benthic Fe fluxes were temporally and spatially more variable and surface sediments were ferruginous or only weakly sulfidic. Therefore, sedimentary Fe depletion and enrichment was less pronounced at 25°S. In the Fe sink area at 23°S, hydrogen sulfide was present at the sediment surface during both sampling campaigns and solid phase data suggest that Fe sulfide minerals represented the main burial phase of reactive Fe. By contrast, at 25°S excess Fe was associated with potassium (K) rather than reduced sulfur. While a differing sediment provenance cannot be ruled out entirely, combined evidence from pore water silica profiles, K to Fe stoichiometric relationships and electron microprobe images suggest that laterally derived excess Fe was incorporated into pre-existing and/or authigenic clay minerals during early diagenesis. Iron uptake by clay minerals may be supported by frequent redox oscillations and sediment mixing preventing preservation of Fe sulfide minerals and promoting Fe and K fixation in clay minerals. The burial fluxes of excess Fe associated with sulfide minerals at 23°S and silicate minerals at 25°S were similar. Our findings thus underscore that neoformation or alteration of silicate minerals can be important processes within the low-temperature marine Fe cycle.

Foraminiferal denitrification and deep bioirrigation influence benthic biogeochemical cycling in a seasonally hypoxic fjord

Benthic macro- and micro-biota often play significant roles in controlling the biogeochemical dynamics in sediments. Their activity can be influenced by oxygen availability and impacted by the rise in global hypoxia in coastal regions over the last decades. To understand how these organisms interact with coastal hypoxia and influence sediment biogeochemistry, we undertook a study of early diagenesis in Bedford Basin, a seasonally hypoxic fjord on the West Atlantic coast in Nova Scotia, Canada, using a combination of observations and reaction-transport modeling. We observed that the seafloor was a source of ammonium and sink of nitrate with average fluxes of 2.2 ± 1.8 and −0.9 ± 0.7 mmol m−2 d−1 respectively. The diffusive oxygen uptake was 14 ± 4.6 mmol m−2 d−1 and the total organic carbon content in collected sediment cores was 5–7 % with a C/N ratio of ∼10. The pyrite content increased steadily from 0.5 wt% Fe at surface to ∼2 wt% Fe at 20 cm depth. Hydrogen sulfide was negligible down to 25 cm depth most of the time. The sediment was inhabited by tube-forming polychaete Spiochaetopterus sp. that formed tubes up to ∼30 cm in length. The living foraminiferal assemblage in the top 5 cm sediment was found to be dominated (>85 %) by nitrate-storing and denitrifying benthic foraminifera Stainforthia fusiformis. These observations were used to develop and constrain a biogeochemical reaction-transport model. The model results suggest that the observed decrease in porewater concentrations of ammonium and dissolved inorganic carbon below 5 cm depth, was due to deep bioirrigation by tubeworms, accounting for almost 50 % of the benthic efflux. The model further revealed that the deep bioirrigation along with bioturbation and iron cycling prevented accumulation of free sulfide in the top 25 cm sediment despite oxygen penetration depths of ∼1 mm. Modelled organic carbon and nitrogen deposition was 25.2 and 2.9 mmol m−2 d−1 with burial efficiencies of 23 % and 17 %, respectively. The model indicated a total denitrification rate of 1.3 mmol N m−2 d−1 that was largely (∼70 %) driven by benthic foraminifera. This study reports the first evidence of foraminiferal denitrification in western Atlantic coastal sediments, and suggests that eukaryote mediated denitrification is an important driver of sediment N-loss in seasonally hypoxic environments, a process that has been traditionally assumed to be carried out by prokaryotic microbes.

Transfer of rare earth elements from clay-sized fraction to phosphate in East South Pacific Ocean: Implication for REY-rich sediment related to hydrothermal influence

Pelagic sediment enriched in critical metals (e.g. rare earth elements and yttrium, REY) has attracted much attention in recent years. Extensive research has focused on identifying the specific host mineral of REY in bulk pelagic sediment, however, research on clay-sized fraction of REY-rich sediment has not been fully understood yet. In this study, we aimed to investigate the host phase and migration mechanism of REY in clay-sized fractions from two cores, GC23 and GC17, located on the western and eastern sides of the East Pacific Rise (EPR), respectively. To the best of our knowledge, this is the first comprehensive investigation of the clay-sized fraction of REY-rich sediment associated with hydrothermal activity. Results show that GC23 contains negligible clay minerals but well-crystallized Fe oxyhydroxides, while GC17 is rich in smectite and poor-crystallized Fe oxyhydroxides. REY are predominantly hosted in poorly crystallized Fe-Mn oxyhydroxides, with some phosphorus selectively scavenged by Fe oxyhydroxides from seawater. In addition, fluorapatite nanocrystals were first observed within the matrix of Fe oxyhydroxides using transmission electron microscopy (TEM), indicating the formation of fluorapatite. The post-Archean average shale (PAAS)-normalized REY patterns show similar seawater-like patterns in both the clay-sized and silt-sized fraction. The clay-sized fractions primarily derived from hydrothermal plumes plays an important role in scavenging REY from ambient seawater. This study represents a significant step towards understanding the formation of REY-rich sediment related to hydrothermal activity. A two-stage mineralization process is proposed for the formation of REY-rich sediment near the EPR fields. Firstly, REY are initially scavenged by hydrothermal Fe-Mn oxyhydroxide particles from seawater during their lateral dispersion with hydrothermal plumes under low sedimentation rate until they are buried by newly formed precipitates. With the process of early diagenesis, poor crystallized Fe oxyhydroxides will be experienced recrystallization. Subsequently, REY would be released into porewater with the process of recrystallization due to their tendency to remain in a poorly crystallized phase. Ultimately, they are captured by biogenic apatite and/or fluorapatite. The case study indicates that REY-rich sediments may primarily formed within the dispersion area of hydrothermal plumes. Simultaneously, the necessity of slow sedimentation rates, greater water depth, and deep currents all accountable for the formation of REY-rich layers.

The Ain Dibba and Ain Kissa phosphorites, Tebessa (NE Algeria): REE depletion versus shallow, open depositional environment during the Paleocene-Eocene phosphogenesis in North Africa

The Ain Dibba and Ain Kissa phosphorites, located north of Tebessa town, NE Algeria, belong to the Upper Cretaceous-Paleocene-Eocene Afro-Arabian phosphatic province that extends from Morrocco to the Middle East. These two phosphorite showings, which were partly exploited at the beginning of the 20th century, were deposited during the Late Paleocene (Thanetian) times on the northern basin of the Kasserine Paleo-Island. Although they are not yet economically very important, the present petrological and geochemical study contribute highly to the knowledge of their critical trace and REE contents as well as the understanding of their paleo-depositional environment. Petrographic and XRD data show that these phosphorites are mainly composed of pellets, coprolites, bioclasts and rare glauconite, gypsum, quartz grains and zeolites. These constituents are cemented by calcareous, siliceous or rarely clayey matrix. The pellets and coprolites are composed mainly of cryptocrystalline carbonate fluor-apatite (CFA). The XRF and ICP-MS chemical analyses of these phosphorites, show they are not as rich as those from Kef Essenoun and Bled El Hadba southern basin, neither in P2O5 nor in REE contents. P2O5 concentrations range from 14.16 to 26.57 wt% (average = 20.24 ± 4.33 wt%, n = 15), with only one sample having 31.89 wt% P2O5, whereas ΣREE contents range from 171 to 344 ppm (average = 252 ± 69 ppm, n = 9) and, therefore, considered as moderately REE-enriched phosphorites. Ce anomaly values display a decrease from the lower to the upper phosphorite sub-layers (from −0.57 down to −0.72), suggesting an increase from relatively sub-oxic to more oxic conditions. The Eu anomalies range from 0.89 to 1.35 for Ain Dibba and from 0.93 to 1.35 for Ain Kissa phosphorites. The highest Ce/Ce∗ and lowest Eu/Eu∗ anomalies are recorded in the lower layers, often enriched in both REE and glauconite contents, whereas the lowest Ce/Ce∗ and highest Eu/Eu∗ anomalies, reflecting more oxic conditions, are characteristics of the glauconite-free and REE-poor upper layers. The gradual timewise transition from relatively sub-oxic to oxic conditions (from the lower to the upper layers) is also recorded in the redox-sensitive (Cr, Ni, V, U) trace element data. This implies that during early diagenesis, the sedimentary environment became slightly reduced, which enabled intensive uptake of both REE and some trace element (e.g., Cr, V, Ni, U) mainly from pore-water through substitution and adsorption mechanisms onto apatite and glauconite minerals. This is noticed especially in the lower phosphorite layers of both Ain Dibba and Ain Kissa deposits. In a larger scale, the Ain Dibba and Ain Kissa phosphorites show lower REE contents, lower Ce and Eu anomalies, and lower redox-sensitive trace element contents than those of the southern (Kef Essenoun and Bled El Hadba) and eastern (Tunisian) basins of the Kasserine paleo-Island. These geochemical features indicate that phosphorites from the northern basin were deposited, through upwelling current, in a more open, shallower, oxygenated and agitated environment during the Paleocene-Eocene phosphogenesis in North Africa and Middle East.

Hydrothermal activity near the Permian–Triassic transition in the south‐western Ordos Basin, China: Evidence from carbonate cementation in Upper Permian sandstones

ABSTRACTCarbonate cementation in the Upper Permian sandstones informs the timing and temperature of hydrothermal activity in the south‐western Ordos Basin. This study presents a detailed examination of these hydrothermally influenced carbonate cements, constraining their age, carbonate diagenesis and relationship with regional geodynamic evolution. Sedimentological analyses demonstrate the development of deltaic plain and front sand bodies in the study area, which resulted in interbeds of volcanic matrix‐rich sandstones with matrix‐free sandstones. Petrography and electron microprobe analysis reveal four carbonate mineral growth phases of matrix‐free sandstones in the following sequence; scarce pure siderite, scarce Mg‐rich siderite, abundant blocky calcite and moderately abundant grain‐replacing calcite. The fluid inclusion data show anomalies of homogenization temperature of blocky carbonate cements during early diagenesis, over a wide range of ca 148 to 228°C. In addition, blocky carbonate cements show low δ13C (−5.9 to −13.1‰ Vienna PeeDee Belemnite) and δ18O (clustered tightly from −12.4 to −14.6‰ Vienna PeeDee Belemnite) values, interpreted to result from elevated temperatures during cementation, associated with activation of basement faults and concomitant hydrothermal fluid intrusion triggered by oceanic crust subduction in the south‐west margin of the Ordos Basin. Using in situ calcite U–Pb geochronology, the timing of hydrothermal activity was constrained to ca 247.0 ± 11 to 248.2 ± 4.7 Ma. This work provides a case study for applying intergranular calcite U–Pb dating to determine the absolute timing of fluid flow in sedimentary basins, offering tremendous potential to capture snapshots of various diagenetic evolution stages in sediments. The proposed diagenetic model can also provide new insights and understanding regarding hydrothermally influenced sediments. More importantly, hydrothermal activity may have commenced earlier than previously thought. The North Qinling Orogen uplift and associated Mianlue oceanic crust subduction may have begun at the Permian–Triassic transition with a protracted hydrothermal event in the south‐western Ordos Basin.

Differences in reservoir quality within distributary channel belts at the braided river delta front in the Xinchang area of Western Sichuan’s 2nd member of the Xujiahe Formation: genesis and implications

AbstractThe tight sandstone reservoris are important exploration and production target in the Xujiahe Formation in Xinchang area of Western Sichuan. Due to the various lithofacies and diagenetic alteration in distributary channel belt sandstones, the reservoirs exhibit strong heterogeneity. The strong heterogeneity makes the identification of petrologically superior sandbodies a great challenge. In order to better understand reservoir quality, this study constructs a model between diagenetic alterations and reservoir quality within distributary channel belts. 73 plug samples were taken from 17 wells located in the channel belt. An integration of thin sections, X-ray diffraction, carbon and oxygen isotope ratios, cathodoluminescence, and micro-CT were analysed for the genesis and distribution of reservoir quality. The results show that subaqueous distributary channels are formed under various hydrodynamics, resulting in different lithofacies. The thicknesses of channels can be divided into less than 2 m, 2–6 m, and more than 6 m. The diagenetic alteration in lithofacies were identified. Coarse-grained sandstones with low content of rock fragments are relatively weakly compacted with less calcite and chlorite cementation. Fine-grained sandstones with high content of rock fragments are strongly compacted with calcite cementation during early diagenesis. The dissolution pores are related to the soluble mineral content and the distribution of mudstones. The subaqueous distributary channels formed in high-energy, moderate-energy, and low-energy hydrodynamic settings have experienced different diagenetic intensities. Additionally, fractures can effectively improve the reservoir properties. The distribution of good quality reservoirs is controlled by the combined influence of diagenetic heterogeneity and fractures. This would help to promote better understanding of reservoir quality within the subaqueous distributary channel belts in braided-river delta front.

Silicon isotopes reveal the impact of fjordic processes on the transport of reactive silicon from glaciers to coastal regions

Accelerated mass loss from the Greenland Ice Sheet leads to retreating glaciers and enhanced freshwater runoff to adjacent coastal regions, potentially providing additional essential nutrients, such as silicon, to downstream primary producers. However, the role of fjordic sediments in modulating the supply of silicon from glacial environments to marine ecosystems remains poorly constrained, particularly for the quantification of silicon fluxes from the sediments into overlying waters in high-latitude fjordic systems. In this study, we use the concentration and stable isotopic composition of dissolved silicon in pore waters and core-top waters, and amorphous silica phases (such as glacially-derived amorphous silica) in sediments and suspended particulate matter, collected from two fjords in the southwest Greenland margin to address this knowledge gap. We combine downcore observations with core incubations and isotope mass balance approaches to assess the benthic flux of dissolved silicon and deconvolve potential contributors to this flux during early diagenesis. Our results suggest that molecular diffusion only accounts for a portion of benthic dissolved silicon transport. Relative to surrounding continental shelves and highly-productive open ocean waters, the estimated benthic dissolved silicon flux at our sites is smaller in magnitude, supporting the role of fjords as a ‘trap’ for reactive silicon in high-latitude systems.

The Origin and Nature of Magnetic Particles From Soils and Sediments Constrained by Hydrodynamics and Geochemistry Around a Tropical Lagoon System

AbstractMagnetic iron oxides are commonly enriched in soils and sediments on Earth's surface. Magnetic properties are widely employed in soil taxonomy, sediment tracing and paleoclimate reconstruction as indicators of associated pedogenic and depositional processes. However, in coastal regions, frequent shifts in pedogenesis and diagenesis accompanied by changes in hydrodynamic and geochemical conditions from land to sea can influence the formation and preservation of magnetic particles in sediment sequences. To discern the origin and nature of magnetic particles driven by these processes, we systematically examined soils and sediments around a tropical lagoon that has been closing for two hundred years. We found that the finest superparamagnetic particles are enriched along with hematite from inland soils with high‐Fe and high‐Al backgrounds, which was driven by pedogenesis. Single‐domain ferrimagnetic particles are enriched along with amorphous iron oxides in the lagoon with high‐Mg and high‐Mn backgrounds, which was driven by early diagenesis in quiet and reducing depositional environments. Coarse titanomagnetite particles are strongly enriched in inshore sediments with high‐Si and high‐Ti backgrounds, which was driven by seawater elutriation. However, magnetic particles in barrier bar soils have mixed features depending on the neighboring environment. Identifying magnetic particles derived from different soils and sediments in tropical coastal regions can assist in tropical coastal paleoclimate and paleoenvironment reconstruction on the basis of magnetic properties along coastal sediment sequences.

Depositional control on composition, texture and diagenesis of modern carbonate sediments: A comparative study of tidal channels and marshes, Abu Dhabi, United Arab Emirates

Petrography, geochemistry, radiocarbon dating, and porewater chemistry of modern carbonate sediments in the mangrove marshes and tidal channels along the Abu Dhabi coast, United Arab Emirates, were conducted to compare sediment composition, texture and diagenesis between these two adjacent but distinct depositional environments. Tidal currents and extensive micritization of the allochems in the tidal channels have led to the enrichment of skeletal fragments (average 25 %) and peloids (average 70 %). Ooids, however, are relatively scarce (average 1 %), which is attributed to strong tidal currents flushing them out of channels and depositing them on shoals and deltas. The severe environmental conditions in the tidal channels forced the microorganisms to bore into allochems, promoting micritization via carbonate dissolution and reprecipitation of spheroidal microbial micrite. Spheroidal micrite with the same mineral composition as the host skeletal fragments fills the microbial borings, indicating that micritization does not involve mineralogical alteration. Radiocarbon dating suggests that microbial boring is an important source of micrite, which is transferred into the marshes from channels by tidal currents. The oxidizing environment in marshes, due to the presence of mangrove pneumatophores and crab burrows, reduces the likelihood of anaerobic respiration. In contrast, microbial sulfate reduction and carbonate dissolution induced by microbial boring in tidal channels caused an increase in porewater alkalinity and dissolved inorganic carbon (DIC) concentration, resulting in more abundant aragonite and high-Mg calcite cements. Stable carbon (+2.3 ‰ to +4.6 ‰) and oxygen (+0.8 ‰ to +1.5 ‰) isotopes of the allochems and micrite corroborate derivation of DIC from seawater. The formation of rare scattered rhombic dolomite as cement only in tidal channels is attributed to microbial metabolic processes. This study provides important insights into the characteristics and controlling factors of diagenesis in modern carbonate sediments, which can have wide implications for understanding the early diagenesis of ancient limestones.

Petrological and geochemical evidences for anaerobic and thermochemical oxidations of methane in petroliferous basins

Methane oxidation affects hydrocarbon accumulation and carbon cycling with important geological and paleoclimatic responses. However, the petrological and geochemical evidences that can clearly discern anaerobic (AOM) and thermochemical (TOM) oxidations in petroliferous basins are unclear, causing the disputes if these two processes can take place in specific conditions. Here, the Baikouquan Formation (T1b) in the Mahu Sag, Junggar Basin, China, was used as the first case study for comprehensive petrological and geochemical analyses to explore this scientific issue. Results indicate that the two main types of T1b calcite cement record different methane oxidation mechanisms. Calcite cements filling intergranular pores were formed during early diagenesis in relatively shallow-burial stages, through AOM with high-valence Mn oxides as electron acceptors, and with compositions of −47.5 ‰ < δ13C < −30.9 ‰, 1.1 wt% < MnO < 5.8 wt%, and 0.02 wt% < FeO < 0.13 wt%. Calcite cements filling intragranular dissolution pores were formed through TOM with high-valence Mn oxides as electron acceptors during mesogenesis during relatively deep-burial stages, with compositions of −39.7 ‰ < δ13C < −14.3 ‰, 0.43 wt% < MnO < 11.00 wt%, and 0.03 wt% < FeO < 0.36 wt%. Thus, methane oxidation underwent a transition from AOM to TOM with increasing depth, as recorded by the calcite cements with different occurrences. This transition may be a common feature of clastic strata in petroliferous basins.

New evidence from the Paleoproterozoic Gunflint Iron Formation for microbially-driven, early diagenetic precipitation of siderite

Petrographic, geochemical, C-, O-, and clumped isotope measurements of drill core samples from the Paleoproterozoic (1.88 Ga) Gunflint Iron Formation containing siderite, ankerite, Fe-silicate clays (dominantly greenalite) and silica, reveal variable but light carbonate δ13C values (-21.3 to -7.87‰, VPDB), with heavy and less variable carbonate δ18O values (20.6 to 24.9‰, VSMOW). These measurements are consistent with a model in which siderite is formed during early diagenesis as a by-product of the metabolism of dissimilatory iron reducing (DIR) microbes that consume Fe(III)-oxide and organic carbon delivered from the water column to the sediment-water interface. This model indicates that the oxygen isotope compositions of reactant Fe-oxide, organic matter and dissolved inorganic carbon were set in equilibrium with seawater at T = 5–35 °C and δ18O = -1.0 to -6.5‰, prior to being metabolized to form siderite. Clumped isotope measurements on Fe-bearing carbonates yield temperatures (T(Δ47)) between 40 °C-132 °C, which constrain δ18Ofluid to values between -6.22 to 7.32‰. These measurements record the onset temperature of DIR followed by low water-to-rock ratio diagenetic recrystallization at elevated temperature. Combined petrographic, chemical, and isotopic measurements reveal that the major phases delivered to the shallow seafloor were a disequilibrium assemblage of Fe-oxide, greenalite, silica, and organic matter that underwent microbially mediated modification to form an assemblage of siderite, greenalite, silica, and later diagenetic ankerite. We contend that observed differences between carbonate derived from Gunflint core and outcrop may be reconciled by removal of siderite during exposure and weathering, leaving outcrop enriched in late diagenetic ankerite.

Geochemical fingerprints of early diagenesis in shallow-water marine carbonates: Insights from paired δ44/40Ca and δ26Mg values

We present a suite of major element stable isotope (δ13C, δ18O, δ44/40Ca, δ26Mg), and selected trace element (Sr/Ca and Mg/Ca) data from Pleistocene sediments from the Great Barrier Reef (IODP Expedition 325), as well as Holocene surface sediments from the Bahamas (Triple Goose Creek, Andros Island) to identify geochemical fingerprints associated with early marine and meteoric diagenesis. Sediments from both sites exhibit co-variation in δ13C and δ18O values, depletion in trace elements, and distinct geochemical trends in δ26Mg and δ44/40Ca values that reflect differences between diagenetic alteration in marine and meteoric fluids. While marine diagenesis results in lower Sr/Ca ratios, higher δ44/40Ca values, and little effect on bulk sediment δ26Mg values, meteoric diagenesis leads to lower Sr/Ca ratios, lower δ44/40Ca values, and lower δ26Mg values. Using a numerical model of diagenesis, we show how diagenetic alteration by meteoric fluids must occur after an initial period of diagenetic alteration by marine fluids, a two-stepped diagenetic history that complicates the interpretation of geochemical data in meteorically altered marine carbonate sediments. Finally, we discuss how paired metal isotopes may serve as a robust indicator of meteoric alteration in ancient shallow-water marine carbonate sediments.

Active methane release from the early Cambrian seafloor? Clues from Ba isotopes

The Cambrian Explosion coincided with a global greenhouse climate, but the mechanism behind this warming event remains unclear, impeding our understanding of their essential link. To address this, an integrated study of δ138Ba, δ34S, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy was carried out on the lower Cambrian shales from a range of water depths in the Nanhua Basin of South China. These shales are characterized by variably elevated Ba concentrations (>10,000 ppm), primarily hosted by barite and Ba-feldspar, with the latter found only in a deep-water setting. The Ba-isotopic compositions of the study shales (δ138Ba, −0.15‰ to +0.60‰), along with the large size and euhedral shape of barite crystals and associated soft-sediment deformation, indicate that barite and Ba-feldspar were formed in porewaters close to the sulfate-methane-transition zone during early diagenesis under sulfate-rich and sulfate-poor conditions, respectively. We propose that low sulfate in the early Cambrian ocean, coupled with the high organic matter content of the sediment, may have resulted in large methane emissions from the sediment to the atmosphere, generating an early Cambrian greenhouse climate at the time of the Cambrian Explosion.

Experimental constraints on Mg isotope fractionation during the aragonite–calcite transition and implications for seawater δ26Mg reconstruction

The linkage between the variation of the seawater Mg budget and the long-term carbon cycle can be elucidated by seawater Mg isotope composition (δ26Mg). However, obtaining primary seawater δ26Mg signatures from marine archives is challenging due to the widespread alteration of diagenesis. Aragonite, a common primary marine carbonate, can effectively record seawater δ26Mg but is prone to alteration and transformation into calcite during early diagenesis. Therefore, a comprehensive understanding of Mg isotope behavior during the aragonite–calcite transition is essential to enhance the applicability of aragonite δ26Mg. In this study, we investigate the variation of aragonite δ26Mg during diagenesis with a limited supply of Mg by conducting a series of well-controlled aragonite–calcite transition experiments in a closed system. The experimental conditions encompass temperatures of 60 and 90 °C, the presence of Ca and Na in the solution, varying Na concentrations, as well as the presence of calcite seed. Results demonstrate that the significant decrease of bulk carbonate δ26Mg is accompanied by a substantial amount of Mg released into the solution during the aragonite–calcite transition, and the amount of released Mg is controlled by fluid chemistry via altering Mg partitioning in calcite. Furthermore, Mg isotope fractionation during calcite precipitation is influenced by temperature, ionic strength, and the presence of calcite seed, while kinetics played a negligible role in our experiments. Combined with previous experiments, the temperature-dependent Mg isotope fractionation during calcite precipitation in unseeded experiments is Δ26Mgcal-sol = (−0.13 ± 0.06) × 106/T2 – (0.47 ± 0.68). This fractionation is systematically higher than that of seeded experiments by 0.3–0.6 ‰ from 15 to 90 °C and can mainly be attributed to differences in surface free energy between homogeneous and heterogeneous calcite nucleation. These findings offer fundamental understandings of the Mg isotope behavior during the aragonite–calcite transformation, providing useful insights for interpreting the variation of δ26Mg in experimental and natural carbonates and facilitating ancient seawater δ26Mg reconstruction.

A study of the effects of early diagenesis on the geotechnical properties of carbonate sediments (North West Shelf, Australia)

Carbonate sediments are often regarded as problematic in geotechnical engineering due to the high variability of their properties. Understanding and quantifying this variability will become increasingly critical in the years ahead, notably with respect to upcoming developments in offshore renewable energy, for which limited in-situ data are typically available to characterise large areas. Here, six intervals from the North West Shelf of Australia, each composed of similar carbonate grains but accumulated in different environments, are investigated to better understand how the post-depositional cementation, alteration and dissolution of sediments, known as diagenesis, impact their geotechnical properties. Intervals are primarily affected by mineralogy-driven meteoric diagenesis, comprising in-situ dissolution of metastable grains and subsequent precipitation of cement that occurred when the shelf was exposed during lower sea-levels, and by marine diagenesis. In both cases, increased diagenesis results in a higher cement-to-solid ratio and compressive strength. However, while marine diagenesis is associated with a reduction in void ratio, this is not initially observed with mineralogy-driven meteoric diagenesis. Additionally, for a similar cement-to-solid ratio, microcrystalline cement results in higher compressive strength than sparite cement. The data further reveal that the level of meteoric cementation and the compressive strength increase as a function of the duration of exposure and of the regional climate, along with a reduction of the specific gravity related to the replacement of aragonite by calcite. However, increased meteoric diagenesis also leads to the formation of macro-scale heterogeneities such as calcrete layers and karsts that can affect the holistic geotechnical behaviour of such deposits.

Formation mechanism and implication of analcime in the sandstone reservoirs of the Permian Jingjingzigou formation in the Jinan sag, southern Junggar basin, NW China

Analcime plays a significant role in sandstone reservoirs as an authigenic diagenetic mineral in the Junggar Basin (northwestern China). However, the origin and controls on the reservoirs have received remarkably little attention. This study investigates the formation mechanism of analcime in the Middle Permian strata in the Jinan sag (southern Junggar Basin) through petrography and geochemistry. The results show that analcime is formed through early alkaline hydrolysis of volcanic materials under specific temperature and pressure conditions. The reservoir rocks primarily consist of various lithic sandstones, including volcanic debris such as basalt, andesite, and tuff. Analcime is characterized as rich in aluminium and poor in sodium, classified as low-silica analcime with a low Si-Al ratio (1.98–2.38). Furthermore, various other diagenetic minerals, such as glauconite, chlorite, albite, and calcite have been identified. The primary reservoir space chiefly consists of intragranular dissolved pores of analcime, while secondary pores are formed by intragranular pores of feldspar and lithic, along with some remaining intergranular pores. Cementation of analcime during early diagenesis changes primary pore structures and reduces reservoir properties. The low-silica analcime dissolves due to acidic pore fluids associated with three stages of oil and gas charging, transforming into albite and creating numerous secondary pores, thereby enhancing reservoir quality.

Control of paleoclimate and paleoweathering on chromium contents in a non-ultramafic aquifer hosting high chromium groundwater.

Cr(VI) is a carcinogen with proven mutagenic and genotoxic effects. The effects of the depositional environment (e.g., paleoweathering, paleoclimate, and paleoredox condition) on Crenrichment in non-ultramafic aquifer solids are unclear. In this study, we presented the sedimentary characteristics of a borehole from a typical non-ultramafic aquifer with high Cr groundwater in Jingbian, central Ordos Basin, China. Chromium was enriched in the K1h sandstone aquifer, especially at depths of 400-500m, with the highest value of mass transport coefficient (τAl,Cr) up to 92.13% and τAl,Fe up to 33.5%. The provenance of aquifer Cr was predominantly intermediate and felsic igneous rocks with a mafic rock mixture. This mafic source was inferred from Cr-rich granodiorite and mafic/ultramafic rocks in the Yinshan (Daqingshan-Wulashan) Block, northern Ordos Basin. The Cr-rich aquifer in K1h was developed due to a moderate chemical index of alteration (CIA) (mean, 56.7) under relatively warm and humid paleoclimate, as evidenced by high CIA-temperature (CIA-Temp) (mean, 6.79°C) and paleoclimatic index values (mean, 0.40). Fe-Mn redox cycling in the oxic to suboxic environments contributed to aquifer Cr accumulation. Using path analysis, we identified that paleoclimate created favorable weathering conditions and enrichment of Fe contributed to the formation of high-Cr aquifers. The study reveals the formation of positive Cr anomalies in non-ultramafic aquifers, which is the potential source of groundwater Cr, and highlights the effects of depositional factors on Cr accumulation during aquifer deposition or early diagenesis. It can provide new insights into the natural processes of high-Cr sediments occurring in non-ultramafic aquifers.

The Miocene lacustrine carbonate factory of the Ñirihuau Formation, Ñirihuau Basin, North Patagonian Andes, Argentina

AbstractFacies, microfacies and stable isotope analyses of limestone beds in the northernmost Ñirihuau Basin, North Patagonian Andes, Argentina, document and constrain the past hydrological, sedimentological and climate conditions that prevailed during the deposition of a lacustrine system between ca 15 and 13 Ma. This palaeoenvironment is recorded in the middle section of the Ñirihuau Formation, which holds significance because: (1) It was deposited during a transition from an extensional to a compressional tectonic regime; (2) it spans the Middle Miocene Climatic Optimum and the beginning of the Middle Miocene Climatic Transition; and (3) it contains limestone beds interbedded within a 600 m thick interval of mudstones and siltstones, along with intercalated sandstone and volcaniclastic bodies. Two detailed sedimentary logs were surveyed along the Arroyo Las Bayas, at the western and eastern flank of the David Syncline. Limestones from both stratigraphic sections were sampled as well as isolated limestone beds from two other sites. One facies association was defined and interpreted as a perennial lake associated with a deltaic system and dominated by detrital clastic material. It comprises Facies 1 (Marginal lacustrine) and Facies 2 (Lower delta plain); in both, the presence of grainstones and calcimudstones stands out. Through petrography and cathodoluminescence studies of these continental carbonates, nine microfacies were identified: (a) Intraclastic grainstone, (b) Homogeneous calcimudstone, (c) Silty grainstone, (d) Disrupted micrite, (e) Birds eye micrite, (f) Bioclastic mudstone, (g) Calcimudstone with sparse detrital grains, (h) Fenestral micrite, (i) Stromatolitic boundstone. These indicate mainly bio‐induced subaqueous carbonate precipitation and subordinate deposition by tractive flows with short‐distance transport on a littoral lacustrine environment. Most of these microfacies exhibit very early diagenesis (eogenesis) effects. These features, and the geochemistry results, indicate that they were deposited in a palaeolake system under temperate to warm and humid conditions.

Early diagenetic evolution based on petrography and stable isotope analysis in the Barra Velha Formation of the Brazilian Pre‐salt

AbstractMineralogy and texture of diagenetic phases in the Aptian Pre‐Salt Barra Velha Formation are described, quantified and compared by facies and structural setting to understand their spatial and temporal distribution, and to develop predictive concepts for their genesis. This study examined data from eight wells from one oil‐field in the Santos Basin. Calcite is the most abundant mineral and occurs with fibro‐radial texture as spherulites and shrubs and sparse microcrystalline mudstone. The δ18O values from calcite spherulites and shrubs suggest water of similar composition and temperature, but they have different δ13C values. Mudstones show lower δ18O, suggesting warmer lake water and/or lower evaporation, whereas δ13C values indicate a variable, but commonly strong influence of biogenic CO2. Dolomite with rhombohedral habit was the first to precipitate, followed by lamellar, saddle and anhedral varieties. Rhombohedral dolomites show a positive δ13C‐δ18O correlation and a similar range in values to spherulites and shrubs, suggesting similar lake water. The lamellar dolomite is related to biofilms, whereas anhedral dolomite is attributed to mixing of pore and meteoric waters. Lamellar and anhedral dolomites have similar isotopic values, precipitating after rhombohedral dolomite in slightly warmer and/or less evaporatively concentrated pore water. Saddle dolomite is related to hydrothermal fluids that percolated the formation during early diagenesis. Silica occurs as replacement of primary calcite and Mg‐clay, but also as a cement and more rarely as a depositional chert. Both dolomite and silica display a complex range of petrographic textures, many of which are facies dependent. This study focusses on the most important phases of the paragenetic sequence that took place pre‐burial and are (1) formation of Mg‐clay, calcite spherulites and shrubs, (2) partial dolomitisation of shrubs and spherulites and precipitation of rhombohedral and lamellar dolomites, (3) precipitation of saddle dolomite, matrix and carbonate dissolution and (4) anhedral dolomite and all textures of precipitated or substituted silica.